KR102222742B1 - Black photo sensitive resin composition, a color filter comprising a black metrics and/or a column spacer prepared by using the composition, and a liquid crystal display comprising the color filter - Google Patents

Abstract

The present invention is based on the total weight of the composition (A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of an alkali-soluble resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) 0.01 to 10 of a photopolymerization initiator Weight%, (E) 0.1 to 1.1% by weight of organic cured particles having an average particle size of 20 nm to 300 nm, and (F) a black photosensitive resin composition containing a residual amount of a solvent, a black matrix and/or column spacer prepared using the same It provides a color filter including, and a liquid crystal display including the color filter.

Description

A black photosensitive resin composition, a color filter including a black matrix and/or a column spacer prepared using the same, and a liquid crystal display device including the color filter TECHNICAL FIELD [BLACK PHOTO SENSITIVE RESIN COMPOSITION, A COLOR FILTER COMPRISING A BLACK METRICS AND/OR A COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND A LIQUID CRYSTAL DISPLAY COMPRISING THE COLOR FILTER}

The present invention relates to a black photosensitive resin composition, a color filter including a black matrix and/or a column spacer manufactured using the same, and a liquid crystal display device including the color filter.

The color filter is composed of three primary color pixels of a red pixel, a green pixel, and a blue pixel, and a black matrix that is formed at the boundary of each color pixel and does not substantially transmit visible light as black. The black matrix or black column spacer is a material that secures a space required for liquid crystal to move between the two glass plates constituting the LCD and maintains the elasticity of the LCD, and is formed of a black photosensitive resin composition. The black matrix or black column spacer can be installed wherever you want in a column shape, and it must be able to precisely adjust the spacing and thickness. At this time, it is necessary to adjust the height of the black column spacer in consideration of the height of the device.

Conventionally, in order to form a black column spacer, a method of dispersing bead particles serving as spacers on the entire surface of a substrate has been adopted. However, this method has a disadvantage in that it is difficult to uniformly secure the cell gap, and because the bead is also attached to the pixel display portion, the contrast and image quality of the image are deteriorated. Accordingly, in order to solve these problems, various methods of using a photosensitive resin composition capable of forming a step have been proposed.

Korean Patent Publication 10-2012-033893 proposes a method of forming a black column spacer having a height difference using a photosensitive resin composition, but has a disadvantage in that the elastic recovery rate is not sufficient.

Korean Patent Publication 10-2012-033893

The present invention has been devised to solve the problems of the prior art, and has excellent physical properties generally required such as optical density, electrical insulation, light-shielding, adhesion, heat resistance, etc., and in particular, a black photosensitive resin having an improved elastic recovery rate. It is an object to provide a composition.

Another object of the present invention is to provide a color filter including a black matrix and/or a column spacer manufactured using the black photosensitive resin composition, and a liquid crystal display device having the color filter.

To achieve the above object,

The present invention is based on the total weight of the composition (A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of an alkali-soluble resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) 0.01 to 10 of a photopolymerization initiator It provides a black photosensitive resin composition comprising (E) 0.1 to 1.1% by weight of organic cured particles having an average particle size of 20 nm to 300 nm, and (F) a residual amount of a solvent.

In addition, the present invention provides a color filter including a black matrix or column spacer prepared using the black photosensitive resin composition.

In addition, the present invention provides a liquid crystal display device including the color filter.

The black photosensitive resin composition of the present invention satisfies generally required optical density, electrical insulation, light shielding, adhesion, heat resistance, and the like, and in particular, provides an effect of greatly improving the elastic recovery rate.

In addition, a color filter including a black matrix and/or a column spacer manufactured using the black photosensitive resin composition as described above, and a liquid crystal display device including the color filter provide excellent characteristics in terms of drivability and durability.

The present invention is based on the total weight of the composition (A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of an alkali-soluble resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) 0.01 to 10 of a photopolymerization initiator It relates to a black photosensitive resin composition comprising (E) 0.1 to 1.1% by weight of organic cured particles having an average particle size of 20 nm to 300 nm, and (F) a residual amount of a solvent:

The black photosensitive resin composition of the present invention is characterized by significantly improving the elastic recovery rate of the black matrix and/or column spacer prepared using the (E) organic cured particles having an average particle size of 20 nm to 300 nm. .

Hereinafter, each component constituting the black photosensitive resin composition of the present invention will be described. However, the present invention is not limited by these components.

Colorant (A)

The colorant is used to realize black, and imparts light-shielding property to both the black matrix and the spacer. That is, the black matrix serves to prevent light leakage, and the spacer serves to prevent malfunction of the device due to light generated from the outside.

The colorant is not particularly limited in the present invention as long as it has light-shielding property to visible light, and all known colorants such as organic pigments, dyes and black pigments may be used, and these may be used alone or in combination of two or more.

For example, organic pigments are compounds classified as pigments in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI) The name is given.

C.I. Pigment Yellow No. 1, C.I. Pigment Yellow No. 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 55, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow No. 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment Yellow No. 128, C.I. Pigment Yellow No. 137, C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow No. 153, C.I. Pigment Yellow No. 154, C.I. Pigment Yellow No. 155, C.I. Pigment Yellow No. 166, C.I. Pigment Yellow No. 168, C.I. Pigment Yellow No. 173, C.I. Pigment Yellow No. 180, C.I. Pigment yellow 211;

C.I. Pigment Orange No. 5, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 14, C.I. Pigment Orange No. 24, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 34, C.I. Pigment Orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment Orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment Orange No. 43, C.I. Pigment Orange No. 46, C.I. Pigment Orange No. 49, C.I. Pigment Orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment Orange No. 64, C.I. Pigment Orange No. 65, C.I. Pigment Orange No. 68, C.I. Pigment Orange No. 70, C.I. Pigment Orange No. 71, C.I. Pigment Orange No. 72, C.I. Pigment Orange No. 73, C.I. Pigment orange 74;

C.I. Pigment Red No. 1, C.I. Pigment Red No. 2, C.I. Pigment Red No. 5, C.I. Pigment Red No. 9, C.I. Pigment Red No. 17, C.I. Pigment Red No. 31, C.I. Pigment Red No. 32, C.I. Pigment Red No. 41, C.I. Pigment Red No. 97, C.I. Pigment Red No. 105, C.I. Pigment Red No. 122, C.I. Pigment Red No. 123, C.I. Pigment Red No. 144, C.I. Pigment Red No. 149, C.I. Pigment Red No. 166, C.I. Pigment Red No. 168, C.I. Pigment Red No. 170, C.I. Pigment Red No. 171, C.I. Pigment Red No. 175, C.I. Pigment Red No. 176, C.I. Pigment Red No. 177, C.I. Pigment Red No. 178, C.I. Pigment Red No. 179, C.I. Pigment Red No. 180, C.I. Pigment Red No. 185, C.I. Pigment Red No. 192, C.I. Pigment Red No. 194, C.I. Pigment Red No. 202, C.I. Pigment Red No. 206, C.I. Pigment Red No. 207, C.I. Pigment Red No. 208, C.I. Pigment Red No. 209, C.I. Pigment Red No. 214, C.I. Pigment Red No. 215, C.I. Pigment Red No. 216, C.I. Pigment Red No. 220, C.I. Pigment Red No. 221, C.I. Pigment Red No. 224, C.I. Pigment Red No. 242, C.I. Pigment Red No. 243, C.I. Pigment Red No. 254, C.I. Pigment Red No. 255, C.I. Pigment Red No. 262, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I. Pigment red No. 272;

C.I. Pigment Blue No. 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, C.I. Pigment Blue No. 16, C.I. Pigment Blue No. 60, C.I. Pigment blue 80;

C.I. Pigment Purple No. 1, C.I. Pigment Purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38;

C.I. Pigment Green No. 7, C.I. Pigment Green No. 36, C.I. Pigment green 58;

C.I. Pigment Brown No. 23, C.I. Pigment brown No. 25;

C.I. Pigment Black No. 1, C.I. Pigment Black No. 7.

These organic pigments are rosin treatment, surface treatment using a pigment derivative into which an acidic or basic group is introduced, surface graft treatment using a polymer compound, etc., fine particle treatment using sulfuric acid, or using an organic solvent or water. It may be that cleaning treatment or the like has been performed.

In addition, pigments used in printing inks and inkjets, and water-soluble azo-based, insoluble azo-based, phthalocyanine-based, quinacrytone-based, isoindolinone-based, isoindolin, perylene, perinone, dioxygen, anthraquinone, dianone Traquinonyl, anthrapyrimidine, antantron, indanthrone, pravantrone, pyrantrone pigments, and the like can be used.

The black pigment may be aniline black, perylene black, titanium black, or carbon black, and any one having light-shielding properties may be used without particular limitation.

Examples of usable carbon black include CHBK-17 from Mikuni Saxophone; Donghae Carbon Co., Ltd.'s Systo 5HIISAF-HS, Systo KH, Systo 3HHAF-HS, Systo NH, Systo 3M, Systo 300HAF-LS, Systo 116HMMAF-HS, Systo 116MAF, Systo FMFEF- HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Mitsubishi Chemical Corporation's Diagram Black ?, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, # CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; Daegu Corporation's PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; Columbia Carbon Co., Ltd.'s RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN- 2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170.

The carbon black is not particularly limited as long as it is a light-shielding pigment, and a known carbon black may be used. Specific examples of carbon black as the black pigment include channel black, furnace black, thermal black, and lamp black.

In addition, the carbon black as the black pigment may be a carbon black coated with a resin. Since the carbon black coated with the resin has a lower conductivity than the carbon black not coated with the resin, excellent electrical insulation can be provided when forming a black matrix or a black column spacer.

As a dye, for example, C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent yellow 135; C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent orange 63; C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red 91:1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197; C.I. Solvent Purple No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No. 28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59; C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent blue 70; C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7 and the like.

The colorant may be contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight, based on the total weight of the black photosensitive resin composition. If the content of the colorant is less than the above range, the above-mentioned effect cannot be secured due to insufficient light-shielding property, whereas if the content of the colorant exceeds the above range, the quality of the pattern obtained after patterning may be degraded, so it can be appropriately used within the above range. .

The colorant in the present invention can be used together with a dispersing agent and a dispersing aid, if desired.

As the dispersant, suitable dispersants such as cationic, anionic, and nonionic can be used, but polymer dispersants are preferred. Specifically, acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be mentioned. Such dispersants can be obtained commercially, for example, as acrylic copolymers DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol) ), as polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (above, manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol) ), as polyethyleneimine, Solsperse 24000 (manufactured by Lubrizol), and as polyester, Azisper PB821, Azisper PB822, Azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.), and the like.

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

These dispersants may be used alone or in combination of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 1 to 70 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the colorant. If the content of the dispersant is too large, there is a concern that developability and the like may be impaired.

The colorant may be contained in an amount of 1 to 50% by weight, preferably 5 to 20% by weight, based on the total weight of the black photosensitive resin composition. If the content of the colorant is less than the above range, the above-mentioned effect cannot be secured due to insufficient light blocking, and if the content of the colorant exceeds the above range, the quality of the pattern obtained after patterning may be deteriorated. .

(B) alkali-soluble resin

The alkali-soluble resin has reactivity and alkali solubility due to the action of light or heat, acts as a dispersion medium for solids including colorants, and if it performs the function of a binder resin, a resin known in the art can be selected and used without particular limitation. have.

Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith.

Examples of the unsaturated carboxyl group-containing monomer include an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, and an unsaturated carboxylic acid having one or more carboxyl groups in a molecule such as an unsaturated tricarboxylic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

As said unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. are mentioned, for example.

The unsaturated polyhydric carboxylic acid may be an acid anhydride, specifically maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinate mono (2-acryloyloxyethyl), succinate mono (2-methacryloyloxyethyl) ), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl), and the like. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxy polymer at both ends, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like.

Each of the carboxyl group-containing monomers may be used alone or in combination of two or more.

Other monomers copolymerizable with the carboxyl group-containing monomer include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-methoxy. Toxoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzyl glycidyl ether, m-vinylbenzylglycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Roxybutylacrylate, 2-hydroxybutylmethacrylate, 3-hydroxybutylacrylate, 3-hydroxybutylmethacrylate, 4-hydroxybutylacrylate, 4-hydroxybutylmethacrylate, allylacrylic Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl meth Crylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate Rate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadie Nyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate Unsaturated carboxylic acid esters such as; 2-aminoethylacrylate, 2-aminoethylmethacrylate, 2-dimethylaminoethylacrylate, 2-dimethylaminoethylmethacrylate, 2-aminopropylacrylate, 2-aminopropylmethacrylate, 2-dimethyl Unsaturated carboxyl, such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters 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 cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; And a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. And macromonomers to have. These monomers may be used alone or in combination of two or more.

Preferably, the alkali-soluble resin is selected and used having an acid value of 50 to 500 (KOH mg/g). The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of an acrylic polymer, and is concerned with solubility. When the acid value of the resin falls within the above range, the solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased. As a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio.

In addition, the alkali-soluble resin may consider limiting the molecular weight and molecular weight distribution (MW/MN) in order to improve the surface hardness. Preferably, the weight average molecular weight is 3,000 to 30,000, preferably 5,000 to 20,000, and the molecular weight distribution is directly polymerized or purchased to have a range of 1.5 to 6.0, preferably 1.8 to 4.0. Alkali-soluble resin having a molecular weight and molecular weight distribution in the above range has high hardness, a high residual film rate, as well as excellent solubility of a non-exposed portion in a developer, and can improve resolution.

The alkali-soluble resin may be used in an amount of 5 to 85% by weight, preferably 5 to 70% by weight, based on the total weight of the black photosensitive resin composition. This content is a range selected in consideration of the solubility of the developer and pattern formation, etc., and when used within the above range, the solubility in the developer is sufficient to facilitate pattern formation. The reduction is prevented, and the omission of the non-pixel portion becomes good.

(C) Photopolymerization compound

The photopolymerizable compound is a material that polymerizes and cures under light irradiation such as ultraviolet rays, and is not particularly limited as long as it is a compound that can be polymerized by the action of a photopolymerization initiator. The photopolymerizable compound may be used as a component for enhancing the strength of the pattern, such as a monofunctional monomer, a difunctional monomer, or a trifunctional or higher polyfunctional monomer.

Specific examples of the monofunctional monomer include acrylate, methacrylate, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl Acrylate, N-vinylpyrrolidone, etc., and commercially available products include Aaronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku) or Viscoat 158 (Osaka Yuki Kagaku High School). I can.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanedioldi(meth)acrylate, etc., and commercially available products include Aaronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600 or UA-306H (Kyoeisha Kagaku).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate , Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, thipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylay Tieddipentaerythritol hexa (meth)acrylate, dipentaerythritol hexa (meth)acrylate, etc., and commercially available products include Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku Co., Ltd.) and others.

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

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

The photopolymerizable compound may be used in an amount of 1 to 30% by weight, preferably 2 to 15% by weight, based on the total weight of the black photosensitive resin composition. This content range is a range selected in consideration of the tendency to improve strength or smoothness as a finally obtained black matrix or spacer, and if the content is less than the above range, strength and smoothness are insufficient, and conversely, exceed the above range. In this case, a problem arises in that patterning is not easy due to high strength, so it is appropriately used within the above range.

(D) Light polymerization Initiator

The photopolymerization initiator is a compound for initiating polymerization of the photopolymerizable compound, and is not particularly limited in the present invention, but acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, anthracene-based, anthraquinone-based compound , And biimidazole-based compounds, etc. may be used, and these may be used alone or in combination of two or more.

Acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy) Phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl- Oligomers of 2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. are possible And, among these, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one can be preferably used.

Benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis (Diethyl amino) benzophenone and the like are possible.

Triazine-based compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxy Styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2- (p-methoxy phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-triazine)-4,6-bis(trichloromethyl)-s-triazine, 2- Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(4-methoxy naphtho 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl ( Piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, and the like are possible.

As the thioxanthone compound, 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, and the like can be used.

Examples of oxime compounds include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include Ciba's OXE-01 and OXE-02.

As the benzoin-based compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like can be used.

Examples of anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl-9,10-diethoxyanthracene.

Examples of the anthraquinone-based compound include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benz anthraquinone, and 2,3-diphenyl anthraquinone.

Biimidazole-based compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, the phenyl group at the 4,4',5,5' position by a carboalkoxy group Substituted imidazole compounds, etc. are possible

Such a photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the black photosensitive resin composition. This content range takes into account the photopolymerization rate of the photopolymerizable compound and the physical properties of the final coating film.If it is less than the above range, the polymerization rate is low and the overall process time may be lengthened. In the past, the physical properties of the coating film may be rather deteriorated, and therefore, it is appropriately used within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiation aid. When a photopolymerization initiator is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing them becomes more sensitive, and productivity is improved when a support spacer for maintaining a cell gap is formed by using the photosensitive resin composition.

The photopolymerization initiation aid may be used to increase polymerization efficiency, and an amine-based compound, an alkoxyanthracene-based compound, and a thioxanthone-based compound may be used.

Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid-2-dimethylaminoethyl, 4 -Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzphenone (common name, Michler's ketone), 4,4'-bis(diethylamino)benzo Phenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. are mentioned. Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. I can.

As the thioxanthone-based compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-pro Foxittioxanthone, etc. are mentioned.

The photopolymerization initiation aid may be manufactured directly or purchased commercially, and as an example, a brand name "EAB-F" [manufacturer: Hodogaya Chemical Industry Co., Ltd.] series and the like may be used.

It is preferable to use the photopolymerization initiator auxiliary agent in the range of usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation aid is used within the above range, it is possible to increase the polymerization efficiency and improve productivity.

(E) The average particle size is 20 nm ~ 300 nm Phosphorus Organic Curing Particles

The organic cured particles are used to improve the elastic recovery rate of the black photosensitive resin composition. That is, when the organic cured particles are included, the elastic recovery rate is greatly increased.

The organic cured particles refer to particles prepared by curing an organic material. The organic cured particles are not particularly limited as long as they are compatible with the photosensitive composition, and may be made of materials such as isoprene-based compounds, styrene-based compounds and butadiene-based compounds, and siloxane-based compounds having rubber properties, These materials may be used alone or in combination of two or more. In addition, it may be made of a material containing unsaturated bonds between carbons required for photoreaction.

It is effective that the average particle size of the organic cured particles is 20 nm to 300 nm. When the average size of the organic cured particles is less than 20 nm, the effect of improving the elastic recovery rate is insignificant, and when it exceeds 300 nm, it is not preferable because it adversely affects the smoothness of the formed pattern surface.

The amount of the organic cured particles may be used in an amount of 0.1 to 1.1% by weight based on the total weight of the black photosensitive resin composition. In the case of based on the total weight of the solid content contained in the black photosensitive resin composition, it may be used in an amount of 0.5 to 5.0% by weight. When the content of the rubber particles is less than 0.1% by weight based on the total weight of the black photosensitive resin composition, the effect of improving the elastic recovery rate is insignificant, and when it exceeds 1.1% by weight, it affects the photopolymerization, resulting in pattern formation and resin composition. It is not preferable because it can be difficult to express the characteristic.

(F) solvent

Any solvent can be used as long as it can dissolve or disperse the above-mentioned composition, and it is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200°C may be used in terms of coatability and drying properties.

Representatively, examples of the solvent that can be used include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone.

Among the solvents, preferably alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate or methyl 3-methoxypropionate may be used, and more preferably propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used. These solvents may be used alone or in combination of two or more.

The solvent may be included in a residual amount so that the black photosensitive resin composition satisfies 100% by weight. This content is a range selected in consideration of the dispersion stability of the composition and the ease of processing in the manufacturing process (eg, coatability). In other words, the black photosensitive resin composition according to the present invention can produce a black matrix, a spacer, or a black matrix integrated spacer by wet coating, and at this time, a roll coater, a spin coater, a slit and spin coater, a slit coater ( It may also be referred to as a die coater), and an application device such as an ink jet can be used.

(G) additive

The black photosensitive resin composition of the present invention may further include additives known in the art for various purposes. Examples of such additives include adhesion promoters, dispersants, fillers, other polymer compounds, ultraviolet absorbers, and anti-aggregation agents. One or two or more of these additives may be used, and it is preferable to use 5% by weight or less based on the total weight of the black photosensitive resin composition in consideration of light efficiency and the like.

As the adhesion promoter, for example, a silane coupling agent may be used. As the silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrime And oxysilane.

As the dispersant, a commercially available surfactant may be used, and a fluorine-based surfactant, a urethane-based surfactant, and the like may be used. The fluorine-based surfactants include BM-1000, BM-1100 (BM Chemie), Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M), SH-28PA/-190/SZ-6032 (Toray Silicon Co., Ltd.), etc. may be used. DiperBYK-163 (BYK Co.) may be mentioned as the urethane-based surfactant. In addition, dispersion aids such as Solsperse 5000 (Lubrisol) can be added.

Glass, silica, alumina, etc. can be used as the filler, and other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. , Polyester, a thermoplastic resin such as polyurethane may be used.

As the ultraviolet absorber, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, etc. may be used, and sodium polyacrylate may be used as an anti-aggregation agent. I can.

The preparation of the black photosensitive composition of the present invention is not particularly limited, and a known method for preparing the photosensitive composition is followed.

As an example, after adding a colorant to a solvent, the remaining composition and other additives may be added and obtained through stirring. At this time, the colorant may be added in the form of a mill base in which a pigment or the like is previously dissolved or dispersed in a solvent or alkali-soluble resin. When the additive is in the form of a solution, it may be added in advance to the solvent together with the colorant.

The black photosensitive resin composition thus prepared can be preferably used in the production of a display device, preferably a black matrix of a liquid crystal display device, a spacer for maintaining a cell gap, or a black matrix integrated spacer.

In particular, the black photosensitive resin composition of the present invention can be preferably used in the manufacture of a black matrix-integrated spacer, and the black matrix-integrated spacer does not form a black matrix and a spacer, respectively, but serves as a black matrix and a spacer in one pattern. It is formed in a structure that can perform all of them.

The present invention also relates to a color filter including a black matrix and/or a column spacer prepared using the black photosensitive resin composition.

In addition, it relates to a liquid crystal display device including the color filter.

A typical patterning process for forming a black matrix, a spacer or a black matrix integrated spacer according to the photolithography method includes the following steps:

a) applying a black photosensitive resin composition to a substrate;

b) a prebaking step of drying the solvent;

c) placing a photo mask on the obtained film and irradiating active light to cure the exposed portion;

d) performing a developing process of dissolving the unexposed part using an aqueous alkali solution; And

e) Drying and post-baking steps

As the substrate, a glass substrate or a polymer plate is used. As the glass substrate, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Moreover, polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, polysulfone, etc. are mentioned as a polymer plate.

In this case, the coating may be performed by a wet coating method using a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater), or an inkjet so as to obtain a desired thickness.

Pre-baking is performed by heating with an oven, a hot plate, or the like. At this time, the heating temperature and heating time in the pre-baking are appropriately selected depending on the solvent to be used, and are performed for 1 to 30 minutes at a temperature of, for example, 80 to 150°C.

Further, the exposure performed after the prebaking is performed by an exposure machine and exposed through a photomask, thereby sensitizing only the portion corresponding to the pattern. The irradiated light at this time may be, for example, visible light, ultraviolet light, X-ray, and electron beam.

Alkali development after exposure It is performed for the purpose of removing the photosensitive resin composition in the non-removed part of the non-exposed part, and a desired pattern is formed by this development. As a developer suitable for this alkali development, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate can be used. In particular, using a less alkaline aqueous solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, using a developer or ultrasonic cleaner within a temperature of 10 to 50°C, preferably 20 to 40°C. To do it.

Post-baking is performed to increase the adhesion between the patterned film and the substrate, and is performed through heat treatment at 80 to 220°C for 10 to 120 minutes. Like the post-baking pre-baking, it is carried out using an oven, a hot plate, or the like.

At this time, the thickness of the black matrix is preferably 0.2 µm to 20 µm, more preferably 0.5 µm to 10 µm, and particularly preferably 0.8 µm to 5 µm.

In addition, the film thickness of the column spacer and the black matrix integrated spacer is preferably 0.1 µm to 8 µm, more preferably 0.1 µm to 6 µm, and particularly preferably 0.1 µm to 4 µm.

The black matrix, spacer, or black matrix-integrated spacer made of the black photosensitive resin composition of the present invention not only has excellent physical properties such as optical density, adhesion, electrical insulation, and light-shielding properties, but also has excellent heat resistance and solvent resistance. Can improve the reliability of

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Manufacturing example 1: Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecane-8-yl (meth)acrylate and 3,4-epoxytricyclodecane-9-yl (meth)acrylate in a molar ratio of 50:50 40 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) Stirring was prepared by adding.

Stirring was prepared by adding 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA to the chain transfer agent dropping tank.

Thereafter, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring.

Thereafter, dropping of the monomer and the chain transfer agent was started. The dropwise addition was maintained at 90° for 2 hours, and the temperature was raised to 110° C. after 1 hour and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH/g.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin were measured using the GPC method, and an HLC-8120GPC (manufactured by Tosoh Corporation) apparatus was used.

Measurement conditions were used by connecting the TSK-GELG4000HXL and TSK-GELG2000HXL columns in series, and the temperature of the column was set to 40°C. Tetrahydrofuran was used as a mobile phase solvent, and measured while flowing at a flow rate of 1.0 mL/min. The concentration of the measurement sample was 0.6% by weight, the injection amount was 50 µl, and analyzed using an RI detector. TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) were used as standard materials for calibration, and the weight average molecular weight and number of the alkali-soluble resin obtained under the above conditions The average molecular weight was measured.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Synthesis example 1: Synthesis method of organic hardened particles

The organic hardened particles were prepared using polysiloxane (α,ω-dihydroxy polyorganosiloxane (Triton X-100)), DI-Water, ethanol, and ammonia acid anhydride. First, 10 parts by weight of polysiloxane was mixed with 250 parts by weight of Di-Water, and heat was applied until the polysiloxane was completely dissolved, and the dissolution proceeded within 4 hours at a temperature of 80° C. or less. Then, a mixture was prepared by adding 1 to 15 parts by weight of ammonia acid anhydride to 100 parts by weight of polysiloxane in another beaker, and the mixture was mixed little by little with a solution in which polysiloxane and Di-water were mixed in advance to proceed with stirring. After stirring, the precipitated material was filtered and dried at 70° C. for 2 hours to obtain cured organic particles. Since the particle size changes depending on the amount of ammonia acid anhydride added, particles in the required range in the present invention were obtained. The particle size was measured by adding a small amount of particles to ethanol and dispersing it, and then using DLS-8000 (Otsuka). The measurement result showed a particle size of 20/50/100/200/300/350/400 nm.

Example 1 to 4 and Comparative example 1 to 2: Preparation of black photosensitive resin composition

After the solvent was added to the mixer, a pigment, an organic cured particle, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives were added, and the mixture was uniformly mixed through stirring to prepare a black photosensitive resin composition. At this time, the composition was according to the composition of Table 1 below.

Configuration material Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Pigment R194 3.13 3.13 3.13 3.13 3.13 3.13 B15:6 5.07 5.07 5.07 5.07 5.07 5.07 PBk7 0.60 0.60 0.60 0.60 0.60 0.60 Photosensitive
Suzy Alkali-soluble resin 7.45 7.35 6.90 6.47 7.56 6.35 Photopolymerizable compound 1.89 1.89 1.89 1.89 1.89 1.89 Photopolymerization initiator 0.52 0.52 0.52 0.52 0.52 0.52 Additive 1 3.09 3.09 3.09 3.09 3.09 3.09 Additive 2 0.13 0.13 0.13 0.13 0.13 0.13 Organic hardening particles
(Average particle size) 0.11
(100nm) 0.22
(100nm) 0.66
(100nm) 1.09
(100nm) 0.00 1.21
(100nm) solvent 78 78 78 78 78 78

(Unit: wt%)

week)

Pigment: R194 Red Pigment 194 (Wonil Trading)) / B15:6: Blue Pigment 15:6 (manufactured by DIC) / PBk7 (Carbon Black, MA-8, manufactured by Mitsubishi Corporation)

Alkali Soluble Resin: Preparation Example 1 Synthetic Resin

Photopolymerizable compound: dipentaerythritol hexaacrylate (Kayarad DPHA: Nippon Kayaku Co., Ltd.)

Photoinitiator: Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Irgacure OXE-02: Ciba company)

Additive 1: DiperBYK-163 (manufactured by BYK),

Additive 2: Solsperse 5000 (manufactured by Lubrisol)

Solvent: Propylene glycol monomethyl ether acetate

Test example One: Elastic recovery rate And reliability evaluation

(1) Fabrication of patterned substrates

A 5cm X 5cm glass substrate (Corning) was washed with neutral detergent and water, and then dried. On the glass substrate, each of the black photosensitive resin compositions prepared in Examples and Comparative Examples was spin-coated to a final film thickness of 4.0 μm, pre-baked at 80 to 120°C, and dried for 1 to 2 minutes to remove the solvent. I did. Then, a pattern was formed by exposure with an exposure amount of 40 to 150 mJ/cm ^2, and the non-exposed portion was removed using an alkaline aqueous solution. Subsequently, firing was performed at 200 to 250° C. for 10 to 30 minutes to prepare a colored substrate.

(2) Elastic recovery rate evaluation

The elastic recovery rate of the formed pattern substrate was measured using a Fisher hardness tester (fisherscope HM-2000, Fisher Co., Ltd.), and the results are as follows. The elastic recovery rate was measured by applying a force to 50 mN to the pattern formed in a size of 20 μm, and the results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 result(%) 81 84 86 91 56 72

As can be seen from Table 2, the elastic recovery rate of the pattern made of the black photosensitive resin composition of Examples 1 to 4 of the present invention (including organic cured particles of which the size and content are specified) is the black photosensitive property of Comparative Examples 1 to 3 Compared to the pattern made with the resin composition, it was remarkably excellent.

Test example 2: Evaluation of surface roughness according to the size of organic hardened particles

Examples 5 to 8 and Comparative Examples 3 to 4 were variously changed as shown in Table 3 below to have the same composition as Example 4, where the measured value of the elastic recovery rate of Test Example 1 was the best. A black photosensitive resin composition was prepared, and a patterned substrate was prepared to measure the surface roughness.

The surface roughness of the patterns formed on the patterned substrates of Examples 5 to 8 and Comparative Examples 3 to 4 was measured using Dektak 6M (Veeco). Measured values are Ra and Rq values, and more accurate values are Rq values. The results in the present invention are compared with the value of Rq.

The measurement of the surface roughness was carried out on the prepared colored substrate. After the measurement range was set to 500 μm, a measurement value between 50 μm and 450 μm at two points within the measurement range of 500 μm was used.

As for the measurement method, the measurement scan range of Dektak was set to 500 μm, and the measurement points of the result values were set to 50 μm and 450 μm, respectively, within the entire scan range. The measuring point is the front side of the fabricated substrate.

The range of the allowable surface roughness value is within 950Å, and if it is smaller than this range, there is no significant difference, and if it exceeds 950Å, the surface may become uneven, resulting in insufficient shielding properties. It causes problems such as.

Review Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 3 Comparative Example 4 Particle size (nm) 100 20 50 200 300 350 400 Surface roughness (Rq, Å) 621 350 486 653 752 1220 1591

As can be seen from Table 3, the surface roughness of the pattern prepared with the black photosensitive resin composition of Examples 4 to 8 of the present invention (including organic cured particles having an average particle size of 20 to 300 nm) is black in Comparative Examples 3 to 4 Compared to the pattern made of the photosensitive resin composition, it was remarkably excellent.

Claims (7)

Based on the total weight of the composition, (A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of an alkali-soluble resin, (C) 1 to 30% by weight of a photopolymerizable compound, (D) 0.01 to 10% by weight of a photopolymerization initiator, As a black photosensitive resin composition comprising (E) 0.1 to 1.1% by weight of organic cured particles having an average particle size of 20 nm to 300 nm, and (F) a residual amount of a solvent,
The (A) colorant includes at least one black pigment selected from the group consisting of aniline black, perylene black, titanium black, and carbon black, and further includes red pigment 194 and blue pigment 15:6,
The pattern made of the black photosensitive resin composition has a surface roughness of 950Å or less, and forms a black matrix or column spacer having light blocking properties. The black photosensitive resin composition according to claim 1, wherein the organic cured particles are made of at least one material selected from the group consisting of an isoprene-based compound, a styrene-based compound, a butadiene-based compound, and a siloxane-based compound. The black photosensitive resin composition according to claim 1, wherein the (B) alkali-soluble resin has a molecular weight of 3,000 to 30,000. delete The black photosensitive resin composition according to claim 1, further comprising at least one additive selected from the group consisting of adhesion promoters, dispersants, fillers, other polymer compounds, ultraviolet absorbers, and anti-aggregation agents. A color filter comprising a black matrix or column spacer made of the black photosensitive resin composition of any one of claims 1 to 3 and 5. A liquid crystal display device comprising the color filter of claim 6.