KR20140110372A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition. The colored photosensitive resin composition comprises: (1) a copolymer comprising (1-1) a constituent unit derived from ethylene-based unsaturated carboxylic acid, ethylene-based unsaturated carboxylic acid anhydrite, or a mixture thereof, (1-2) a constituent unit derived from an unsaturated monomer having a Si-O bond in a side chain, and (1-3) a constituent unit derived from an ethylene-based unsaturated compound which is different from the constituent units (1-1) and (1-2); (2) a coloring agent; (3) a polymerizable unsaturated compound; and (4) a photopolymerization initiator. The colored photosensitive resin composition in the present invention has excellent light-shielding properties and also has excellent substrate-adhesive properties, developing properties, chemical resistance and heat resistance. Therefore, the colored photosensitive resin composition can be practically used for the manufacture of a black matrix and a black bezel for a liquid crystal display.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition which can be usefully used as a black matrix and a black bubble material of a liquid crystal display (LCD) and various portable displays.

Description of the Related Art [0002] A liquid crystal display (LCD) is one of widely used flat panel display devices, in which a thin film transistor substrate on which pixel electrodes are formed and a color filter substrate on which common electrodes are formed face each other and a liquid crystal layer is interposed therebetween. In such a liquid crystal display device, a voltage is applied to the pixel electrode and the common electrode to rearrange the liquid crystal molecules in the liquid crystal layer, thereby displaying an image by adjusting the amount of light transmitted through the liquid crystal layer. Liquid crystal display devices have advantages such as light weight, thinness, low cost, low power consumption driving, and bonding with excellent integrated circuits, and the use range of liquid crystal display devices is expanding for display panels of panel computers and color TVs of laptop computers and pocket computers. In recent years, liquid crystal display devices, which have been mainly used for small and medium mobile displays or monitors, have been moving to large-sized monitors or TVs having a larger area, and accordingly, new attempts have been made to thin liquid crystal display devices.

As a result, techniques for directly forming a color filter layer in a TFT structure in a method of separately manufacturing a lower substrate and an upper color substrate of a conventional TFT LCD and attaching the same to each other are emerging. In order to directly form the color filter layer in the TFT structure, it is required to reduce the liquid crystal contamination compared with the conventional black matrix, to have adhesion with the substrate, high light shielding property, excellent developability, and high heat resistance property for maintaining the TFT structure

Accordingly, studies have been made on a positive photosensitive resin composition using an organosiloxane-based polymer compound, which has excellent chemical resistance, heat resistance, and film properties and can realize a precise fine pattern (Korean Patent Laid- 2002-0021005). However, such a photosensitive resin composition has a problem that the dispersibility and dispersion stability of the colored pigment are low, the stability with time is poor, and the compatibility with the alkali-soluble resin is low.

Korean Patent Publication No. 10-2002-0021005

Accordingly, an object of the present invention is to provide a colored photosensitive resin composition having excellent light-shielding characteristics and excellent adhesion to a substrate, developability, chemical resistance, and heat resistance.

(1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (1-2) a structural unit derived from a (1-2) Si-O skeleton And (1-3) a copolymer comprising a constituent unit derived from an ethylenically unsaturated compound different from the constituent units (1-1) and (1-2); (2) a colorant; (3) a polymerizable unsaturated compound; And (4) a photopolymerization initiator.

The colored photosensitive resin composition of the present invention has excellent light-shielding properties, is excellent in adhesiveness to a substrate, developability, chemical resistance, and heat resistance, and can be usefully used for the production of a black matrix and a black bubble for a liquid crystal display device.

The positive photosensitive resin composition according to the present invention comprises (1) a structural unit derived from (1-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (1-2) And (1-3) a copolymer comprising a constituent unit derived from an ethylenically unsaturated compound different from the constituent units (1-1) and (1-2); (2) a colorant; (3) a polymerizable unsaturated compound; And (4) a photopolymerization initiator, and optionally (5) an epoxy resin or a derivative thereof, (6) a silane coupling agent, (7) a surfactant, and / or .

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

(1) Copolymer

(1) a constituent unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (1-2) a constitutional unit derived from an unsaturated monomer containing a Si-O skeleton in a side chain, And (1-3) a structural unit derived from an ethylenically unsaturated compound which is different from (1-1) and (1-2).

(1-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof

In the present invention, the constituent unit (1-1) is derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, wherein the ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, (Meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid and cinnamic acid; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid and cinnamic acid; Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid, and anhydrides thereof; Unsaturated polycarboxylic acids of trivalent or more and their anhydrides; Mono [(meth) acryloyloxyalkyl] acrylate of a dicarboxylic or higher polycarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] And esters. Among them, (meth) acrylic acid can be preferably used from the viewpoint of developability.

The content of the constituent unit derived from the (1-1) ethylenically unsaturated carboxylic acid, the ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof may be 3 to 40% by weight based on the total weight of the copolymer, And preferably 10 to 30% by weight.

In the present invention, the terms (meth) acrylate and (meth) acrylate refer to acrylic and / or methacrylic, and acrylate and / or methacrylate, respectively.

(1-2) Structural unit derived from unsaturated monomer containing Si-O skeleton in side chain

In the present invention, the constituent unit (1-2) may be derived from an unsaturated monomer containing a Si-O skeleton in its side chain, and the unsaturated monomer containing a Si-O skeleton in the side chain may be represented by the following formula (1).

In Formula 1,

In Formula 1,

R ₁ is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms,

R ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms,

R ₃ and R ₄ are each independently hydrogen, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms,

R ₅ is hydrogen, a methyl group, or an ethyl group,

n is an integer of 2 to 20;

The content of the constituent unit derived from the unsaturated monomer containing the Si-O skeleton in the side chain (1-2) may be 5 to 60% by weight based on the total weight of the copolymer. In order to maintain good heat resistance and chemical resistance, Preferably 10 to 50% by weight.

(1-3) a structural unit derived from an ethylenically unsaturated compound which is different from the structural units (1-1) and (1-2)

In the present invention, the constituent unit (1-3) is derived from an ethylenically unsaturated compound different from the constituent units (1-1) and (1-2), and specific examples thereof include methyl (meth) acrylate, ethyl Butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate, methyl (meth) acrylate, ethyl (a) -hydroxymethyl acrylate, propyl (a-hydroxymethyl) acrylate, butyl? -Hydroxymethylacrylate, 2-methoxyethyl ( (Meth) acrylate, methoxytriethyleneglycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (meth) acrylate, Ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, heptadecafluorodecyl Unsaturated carboxylic acid esters including dicyclopentenyloxyethyl (meth) acrylate; N-vinyl tertiary amines including N-vinyl, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; Unsaturated ethers including vinyl methyl ether and vinyl ethyl ether; (Meth) acrylate, 5,6-epoxyhexyl (meth) acrylate, 6,7-epoxy (meth) acrylate, (Meth) acrylate,? -Ethylglycidyl acrylate,? -N-propylglycidyl (meth) acrylate, Acrylate,? -N-butylglycidyl acrylate, N- (4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl) acrylamide, N- One or more epoxy groups such as hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, Unsaturated monomers including; N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide, N-cyclohexylmaleimide , N-benzylmaleimide, N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-naphthylmaleimide, and may be at least one selected from the group consisting of N-

N-phenylmaleimide, N-cyclohexylmaleimide or mixtures thereof, preferably in terms of chemical resistance; (Meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, p-phenoxyethyl (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, tribromophenyl (meth) acrylate; Styrene; Styrene having alkyl substituents such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene; Styrene having a halogen such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; Styrene having an alkoxy substituent such as methoxystyrene, ethoxystyrene, propoxystyrene; 4-hydroxystyrene, p-hydroxy-a-methylstyrene, acetyl styrene; Vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinylbenzyl glycidyl ether, and styrene-based compounds are preferable from the viewpoint of polymerizability.

(1-3) The content of the constituent unit derived from the ethylenically unsaturated compound different from the above (1-1) and (1-2) may be from 15 to 75% by weight based on the total weight of the copolymer, And preferably 20 to 60% by weight for pattern margin properties.

The copolymer according to the present invention is a copolymer comprising a molecular weight modifier, a polymerization initiator, a solvent, (1-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (1-2) Unsaturated monomer, and (1-3) an ethylenically unsaturated compound different from the above-mentioned constituent units (1-1) and (1-2) is added, and nitrogen is added thereto, followed by polymerization while stirring slowly. The weight average molecular weight (Mw) of the prepared copolymer in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) may be 2,000 to 50,000, and the ratio of the upper / Preferably from 5,000 to 20,000.

The molecular weight modifier is not particularly limited, but may be a mercaptan compound such as butylmercaptan, octylmercaptan or the like or? -Methylstyrene dimer.

The polymerization initiator is not particularly limited, Diazo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), and benzoyl peroxide , Lauryl peroxide, t-butyl peroxypivalate or 1,1-bis (t-butylperoxy) cyclohexane.

The solvent may be any solvent used in the production of the copolymer, preferably propylene glycol monomethyl ether acetate (PGMEA).

The copolymer may be contained in the photosensitive resin composition alone or in combination of two or more.

The content of the copolymer used may be 0.5 to 60% by weight, preferably 2 to 50% by weight, based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). Within the above range, the pattern development after development is favorable and the characteristics such as chemical resistance are improved.

(2) Colorant

The colored photosensitive resin composition of the present invention comprises a colorant for imparting light blocking properties to a black matrix and a black bubble.

The coloring agent used in the present invention may be a coloring pigment composed of an inorganic or organic single pigment or two or more mixed pigments. As the coloring pigment, a pigment having high coloring property and high heat resistance is preferable, and a mixture of two or more organic pigments Is particularly preferable.

Specific examples of the inorganic pigments include metal oxides such as carbon black, titanium black, Cu-Fe-Mn-based oxides and synthetic iron black, and the like. Specific examples of the organic pigments include aniline black, lactam black and perylene black, and among them, lactam black can be preferably used in terms of optical density and permittivity. It may also contain compounds classified as pigments as pigments in the color index (The Society of Dyers and Colourists).

Meanwhile, a dispersant may be used to disperse the coloring agent in the colored photosensitive resin composition of the present invention. The dispersant may be any of those known as pigment dispersants. Specific examples thereof include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a silicone surfactant, and a fluorinated surfactant. have. Commercially available dispersing agents include Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-2000, Disperbyk-2150, Disperbyk-2155, Disperbyk-2163 and Disperbyk-2164 of BYK. These may be used alone or in combination of two or more.

The dispersant may be added to the colorant internally in advance by surface treatment with a colorant, or may be used in combination with a colorant in the production of the colored photosensitive resin composition.

The colorant may be mixed with a binder and then used in the production of a colored photosensitive resin composition. The binder used herein may be one or more materials selected from the above-mentioned (1) copolymer or a known copolymer as described in the present invention.

The content of the colorant may be 5 to 75% by weight, preferably 10 to 65% by weight, based on the total weight of the colored photosensitive resin composition excluding the solvent (based on the solid content). When the content of the colorant is within the above range, it is possible to prevent the optical density from becoming too low, achieve high optical density, and improve the processability such as developability.

(3) Polymerizable unsaturated compound

The polymerizable unsaturated compound is a compound which can be polymerized by the action of a polymerization initiator, and is a monomer, oligomer or polymer generally used in a photosensitive resin composition, and may be a copolymer of acrylic acid or methacrylic acid having at least one ethylenic unsaturated double bond Functional or multifunctional ester compound, but from the viewpoint of chemical resistance, it may preferably be a multifunctional compound having two or more functional groups.

Wherein the polymerizable unsaturated compound is at least one selected from the group consisting of ethyleneglycol di (meth) acrylate, propyleneglycol di (meth) acrylate, diethyleneglycol di (meth) acrylate, triethyleneglycol di (meth) (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (Meth) acrylate, monoesters of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified di (Reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol But are not limited to, at least one selected from the group consisting of lithol octa (meth) acrylate, bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate.

When the polymerizable unsaturated compound is used as an oligomer or polymer, it may have a weight average molecular weight of 6,000 to 10,000.

The content of the polymerizable compound may be 5 to 60% by weight, preferably 10 to 55% by weight based on the total weight (solid content) of the photosensitive resin composition excluding the solvent. When the thickness is within the above range, the pattern is easily formed, the surface of the coated film is not roughened after formation of the coating film, the pattern outline is excellent, and the problem of the pattern shape such as scum is not generated at the lower end during development.

(4) Photopolymerization initiator

The colored photosensitive resin composition of the present invention includes a photopolymerization initiator and is not limited as long as it is a photopolymerization initiator used in the art.

Examples of the photopolymerization initiator include an acetophenone based compound, a nonimidazole based compound, a triazine based compound, an onium salt based compound, a benzoin based compound, a benzophenone based compound, a diketone based compound, an? - diketone based compound, a polynuclear quinone based compound, There may be mentioned a photopolymerization initiator composed of an acid-tonide compound, a diazo compound, an imide sulfonate compound, an oxime compound, a carbazole compound, a sulfonium borate compound, and a mixture thereof, preferably an oxime ester-based photopolymerization initiator It can be the best.

Examples of the oxime ester-based photopolymerization initiator include those disclosed in Korean Patent Publication Nos. 2004-7700, 2005-84149, 2008-83650, 2008-80208, 2007-44062, 2007-91110, 2007- 44753, 2009-9991, 2009-93933, 2010-97658 or 2011-59525, WO 2010/102502 or WO 2010/133077 are preferred, , And commercial products such as OXE-01, OXE-02 (manufactured by Ciba) and N-1919 (manufactured by ADEKA) are preferable in view of high sensitivity and resolution.

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.2 to 5% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). In this range, curing is sufficiently achieved by exposure, and it is easy to obtain excellent pattern margin characteristics and can be sufficiently adhered to the substrate.

(5) Epoxy resin or a compound derived therefrom

The colored photosensitive resin composition of the present invention may optionally contain (5) an epoxy resin or a compound derived therefrom, preferably an epoxy resin having a zettenoid skeleton structure or a compound derived therefrom, As the resin, a compound having a weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography of 400 to 10,000 can be used, and an epoxy resin having a 9-xanthene skeleton structure represented by the following formula (2) have.

In Formula 2,

,

,

또는

에 포함된 *로 라벨링된 탄소로 대체되고,Each carbon labeled with * is, independently,

,

,

or

≪ / RTI > is replaced by carbon labeled with < RTI ID = 0.0 &

L ¹ each independently represents a C _1-10 alkylene group, a C _3-20 cycloalkylene group or a C _1-10 alkyleneoxy group,

R ₇ to R ₁₂ are each independently a hydrogen atom, a C _1-10 alkyl group, a C _1-10 alkoxy group, a C _2-10 alkenyl group or a C _6-14 aryl group,

R ₁₃ is a hydrogen atom, a methyl group, an ethyl group, CH ₃ CHCl-, CH ₃ CHOH-, CH ₂ = CHCH ₂ - or a phenyl group,

m is an integer of 0 to 10;

Specific examples of the C _1-10 alkylene group include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, sec-butylene, tert-butylene, A pentylene group, a hexylene group, a heptylene group, an octylene group, an isooctylene group, a tert-octylene group, a 2-ethylhexylene group, a nonylene group, an isononylene group, a decylene group and an isodecylene group. Specific examples of the C _3-20 cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, decalinylene and adamantylene. Specific examples of the C _1-10 alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butylenoxy group, a sec-butyleneoxy group, a tert-butylenoxy group, a pentylenoxy group, An octyloxy group, a 2-ethyl-hexylenoxy group and the like. Specific examples of the C _1-10 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, Hexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl and isodecyl. Specific examples of the C _1-10 alkoxy group include methoxy, ethoxy, propyloxy, butyloxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy, heptoxy, octyloxy and 2 -Ethyl-hexyloxy group and the like. Specific examples of the C _2-10 alkenyl group include a vinyl group, an allyl group, a butenyl group, and a propenyl group. Specific examples of the C _6-14 aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.

The compound derived from the epoxy resin having the xytene skeleton structure of Formula 2 can be obtained by reacting a polybasic acid anhydride with an epoxy adduct obtained by reacting an epoxy resin having the xyhedene skeleton structure of Formula 2 with an unsaturated base acid, Or a compound obtained by further reacting the obtained compound with a monofunctional or polyfunctional epoxy compound.

As the unsaturated basic acid, known ones such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid can be used. As the polybasic acid anhydride, known ones such as succinic acid anhydride, maleic anhydride, trimellitic acid anhydride, or pyromellitic acid anhydride can be used. The monofunctional or polyfunctional epoxy compound may be selected from the group consisting of glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, Epoxycyclohexyl glycidyl ether, epoxycyclohexyl glycidyl ether, and the like can be used.

When the epoxy resin having the xytene skeleton structure of Formula 2 is used, the xytene skeleton structure improves the adhesiveness, alkali resistance, workability, strength, and the like between the cured product and the substrate, It is preferable because it acts as a factor for forming a clear image precisely.

The content of the epoxy resin or the compound derived therefrom may be 0.5 to 50% by weight, preferably 2 to 40% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid basis). In the above range, not only the resolution and the chemical resistance are improved, but a certain step between the patterns can be realized with a desired margin width (allowable width) while maintaining the pattern shape.

(6) Silane coupling agent

The colored photosensitive resin composition according to the present invention may further include a silane coupling agent in order to improve the adhesiveness with the substrate. Such a silane coupling agent may have a reactive substituent selected from the group consisting of, for example, a carboxyl group, (meth) acryloyl group, isocyanate group, amino group, mercapto group, vinyl group, epoxy group and combinations thereof.

The kind of the silane coupling agent is not particularly limited, and examples thereof include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltri Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and mixtures thereof can be exemplified Isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu) having an isocyanate group with good adhesion to the substrate while maintaining chemical resistance.

The content of the silane coupling agent may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). Within the above range, the adhesiveness of the colored photosensitive resin composition can be improved.

(7) Surfactants

The colored photosensitive resin composition of the present invention may further contain a surfactant for improving coatability and preventing defect formation, if necessary. The kind of the surfactant is not particularly limited, but it may preferably be a fluorine-based surfactant or a silicon-based surfactant. Examples of commercial products of the above fluorine-based surfactants include Megafiz F-470, F-471, F-475, F-482 and F-489 manufactured by Dainippon Ink and Chemicals, Incorporated. Of these, BYK 333 manufactured by BYK Corporation may be preferably used in terms of dispersibility. Examples of commercially available silicone surfactants include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicone Co., , BYK 333 manufactured by BYK, and the like. These may be used alone or in combination of two or more.

The surfactant may be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight based on the total weight of the photosensitive resin composition excluding the solvent (based on the solid content). Within the above range, coating of the photosensitive resin composition is smooth.

(8) Solvent

The colored photosensitive resin composition of the present invention can be prepared by a conventional method, and preferably, a liquid composition in which the above-mentioned components are mixed with a solvent. The solvent is compatible with the above-described photosensitive resin composition components and does not react with the above photosensitive resin composition components, and any known solvent used in the photosensitive resin composition can be used.

Examples of such solvents include glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Diethylene glycol such as diethylene glycol monomethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate. These solvents may be used alone or in combination of two or more.

The content of the solvent is not particularly limited, but may be an amount such that the total concentration of each component other than the solvent of the composition is usually from 5 to 70% by weight from the viewpoint of coatability, stability, etc. of the obtained colored photosensitive resin composition, Preferably 10 to 55% by weight.

In addition, the colored photosensitive resin composition of the present invention may contain other additives such as an antioxidant, a stabilizer and the like within a range not lowering the physical properties.

As an example of the method for producing the colored photosensitive resin composition of the present invention, the following method can be exemplified.

The colorant is mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes a desired level. At this time, a surfactant may be used if necessary, and some or all of the copolymer may be blended. A compound derived from a copolymer, a polymerizable unsaturated compound, a photopolymerization initiator, a silane coupling agent and an epoxy resin having a xanthene skeleton structure is added to the resulting dispersion, and if necessary, other additives or additional solvents are added at a predetermined concentration , And then sufficiently stirred to obtain a desired colored photosensitive resin composition.

The present invention also provides a black matrix produced using the colored photosensitive resin composition.

The black matrix is produced through a film forming step, an exposure step, a development step, and a heat treatment step.

In the coating film forming step, the colored photosensitive resin composition according to the present invention is coated on a predetermined pretreated substrate by a method such as a spin or slit coating method, a roll coating method, a screen printing method, an applicator method, And the solvent is removed by heating at a temperature of 70 to 90 DEG C for 1 to 10 minutes to form a coating film.

In order to form a pattern necessary for the obtained coating film, an active line of 200 to 500 nm is irradiated after a predetermined type of mask is interposed. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used. The exposure dose varies depending on the kind of each component of the composition, the blending amount and the dried film thickness, but may be 500 mJ / cm ² (at a wavelength of 365 nm) or less when a high-pressure mercury lamp is used.

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, or the like as a developing solution, so that only the exposed portion can be left to form a pattern. After the image pattern obtained by the development is cooled to room temperature, it is post-baked at 230 캜 for 20 minutes in a hot-air circulating drying oven to finally obtain a light-shielding black matrix.

As described above, the colored photosensitive resin composition of the present invention has excellent light-shielding properties and is excellent in adhesiveness to substrates, developability, chemical resistance, and heat resistance, and is suitable for use in a variety of electronic components including a liquid crystal display device, . ≪ / RTI >

Accordingly, the present invention provides an electronic component including the black matrix and the black bubble.

The liquid crystal display device of the present invention may include a configuration known to those skilled in the art, except that the black matrix and the black bubble of the present invention are provided. That is, the liquid crystal display device to which the black matrix and the black bubble of the present invention can be applied can be included in the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.

The weight average molecular weight described in the following Production Examples is a polystyrene reduced value measured by gel permeation chromatography (GPC).

Preparation Example 1: Preparation of copolymer A

400 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was introduced into a four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer and heated to 80 DEG C, A mixture of 2 parts by weight of 2,2'-azobisisobutyronitrile, 57 parts by weight of benzyl methacrylate, 13 parts by weight of methacrylic acid and 30 parts by weight of methacryloxypolysiloxane (product name: silaplane TM0701, manufactured by Chisso Corporation) Was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic copolymer resin solution having a siloxane skeleton in the side chain having a weight average molecular weight (Mw) of 13,500. After cooling to room temperature, about 2 parts by weight of the resin solution was sampled, heated and dried at 180 캜 for 20 minutes, and nonvolatile content was measured. To the resin solution thus synthesized, propylene glycol monomethyl ether acetate (PGMEA ) Was added to obtain copolymer A.

Production Example 2: Preparation of colorant dispersion (1)

15 g of a polymer dispersant (DISPERBYK ^占 -2000), 100 g of carbon black (CB 597) and 375 g of PGMEA were dispersed in a paint shaker at 25 to 60 占 폚 for 6 hours. Dispersion was carried out using 0.3 mm zirconia beads, and beads were added to the same weight as the dispersion. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a black colorant dispersion (1).

Production Example 3: Preparation of colorant dispersion (2)

15 g of the copolymer (solid content), 15 g of the polymer dispersant (DISPERBYK ^® -2000), 90 g of organic black (Black 582) and 380 g of PGMEA were dispersed in a paint shaker at 25 to 60 캜 for 6 hours. Dispersion was carried out using 0.3 mm zirconia beads, and beads were added to the same weight as the dispersion. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a black colorant dispersion (2).

Production Example 4: Preparation of a compound derived from an epoxy resin

A 3,000 ml three-necked round-bottomed flask was charged with 125.4 g of spiro [fluorene-9,9'-xanthene] -3 ', 6'-diol (spiro [fluorene-9,9'-xanthene] And 0.1386 g of t-butylammonium bromide were mixed and 78.6 g of epichlorohydrin was added, followed by heating at 90 占 폚 for reaction. When the spiro [fluorene-9,9'-xanthene] -3 ', 6'-diol was completely consumed by the analysis by liquid chromatography, the solution was cooled to 30 ° C and 50% NaOH aqueous solution (3 equivalents) was slowly added. Then, when the epichlorohydrin was completely exhausted, the reaction mixture was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and the dichloromethane was removed by distillation under reduced pressure. Then, dichloromethane and methanol (Mixing ratio 50:50 (v: v)).

One equivalent of the synthesized epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid were mixed and then 8.29 g of PGMEA as a solvent was added and mixed. The reaction solution was heated to 90 to 100 占 폚 while blowing air into the reaction solution at 25 ml / min to dissolve the reaction product. The reaction solution was completely dissolved in the cloudy state by heating to 120 ° C. When the solution became transparent and the viscosity increased, the acid value was measured and stirred until the acid value became less than 1.0 mg KOH / g. It took 11 hours until the acid value reached the target value (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent solid.

43 g of the obtained product, 33.6 g of acrylic acid, 0.04 g of 2,6-di-tert-butyl-p-cresol, 0.21 g of tetrabutylammonium acetate and 18 g of PGMEA were placed in a reaction flask and stirred at 120 DEG C for 13 hours. After cooling to room temperature, 24 g of PGMEA and 10 g of acetic anhydride were added, and the mixture was stirred at 100 占 폚 for 3 hours. After addition of 8 g of bisphenol Z glycidyl ether, the mixture was stirred at 120 ° C for 4 hours, at 90 ° C for 3 hours, at 60 ° C for 2 hours, and at 40 ° C for 5 hours, and then reprecipitated in water and alcohol, To obtain a target resin. Thereafter, PGMEA was added so that the solid content became 48%. The obtained resin had an acid value of 105 mgKOH / g and a weight average molecular weight (Mw) of 5500. [

Production Example 5: Preparation of Copolymer B

2 parts by weight of octylmercaptan, 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added to a three-necked flask equipped with a cooling tube and a stirrer , 40 parts by weight of N-phenylmaleimide, 25 parts by weight of styrene, 10 parts by weight of methylmethacrylate, and 25 parts by weight of methacrylic acid were charged and nitrogen was added thereto. Then, the temperature of the solution was raised to 60 DEG C And polymerization was carried out while maintaining the temperature for 5 hours to obtain an acrylic copolymer resin solution having a weight average molecular weight (Mw) of 10,100. Then, PGMEA was added so that the solid content was 30%.

Example 1

6.567 g of Copolymer A prepared in Preparation Example 1, 3.22 g of the colored dispersion (1) prepared in Preparation Example 2, 7.82 g of the colored dispersion (2) prepared in Preparation Example 3, 7.8 g of dipentaerythritol hexa Acrylate (trade name: DPHA, manufactured by Nippon Kayaku), 0.44 g of a first photopolymerization initiator (product name Irgacure OXE-01, manufactured by Ciba Specialty Chemicals), 0.44 g of a second photopolymerization initiator (product name Irgacure- Ciba Specialty Chemical's Co., Ltd.) 0.53 g, and a surfactant (product name by DISPERBYK ^® -333) 0.046 g and the mixture stirred and put in a propylene glycol monomethyl ether acetate (PGMEA) solvent so that the solid content is 23%, the black Thereby preparing a colored photosensitive resin composition.

Example 2

Except that 5.911 g of Copolymer A prepared in Preparation Example 1 was used and 0.656 g of the compound derived from the epoxy resin prepared in Preparation Example 4 was further mixed to prepare a colored photosensitive resin composition .

Example 3

Except that 4.597 g of Copolymer A prepared in Preparation Example 1 was used and 1,967 g of the compound derived from the epoxy resin prepared in Preparation Example 4 was further mixed to prepare a colored photosensitive resin composition .

Example 4

Except that 3.284 g of Copolymer A prepared in Preparation Example 1 was used and 3.278 g of the compound derived from the epoxy resin prepared in Preparation Example 4 was further mixed to obtain a colored photosensitive resin composition .

Example 5

Except that 1.971 g of the copolymer A prepared in Preparation Example 1 and 4.588 g of the compound derived from the epoxy resin prepared in Preparation Example 4 were further mixed to prepare a colored photosensitive resin composition .

Comparative Example 1

A colored photosensitive resin composition was prepared in the same manner as in Example 2, except that the copolymer B prepared in Preparation Example 5 was used in place of the copolymer A prepared in Preparation Example 1.

Comparative Example 2

A colored photosensitive resin composition was prepared in the same manner as in Example 1, except that 6.590 g of Copolymer B prepared in Preparation Example 5 was used in place of Copolymer A prepared in Preparation Example 1. [

Test Example 1: Developability Measurement

≪ Preparation of specimen &

Each of the colored photosensitive resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 was coated on a glass substrate using a spin coater and then dried at 90 DEG C for 100 seconds to form a coating film having a thickness of 2.5 mu m . The obtained coating film was irradiated with light having a wavelength of 365 nm at a dose of 40 mJ / cm < 2 > using a pattern mask having a different transmittance. Subsequently, the substrate was developed with an aqueous solution diluted with 1% by weight of potassium hydroxide at 23 DEG C for a break point (BP) + 20 seconds, and then washed with pure water for 1 minute. At this time, the break point means the time from the moment when the developer reaches the surface of the coating film to the time when the bottom of the glass substrate is exposed. By this operation, unnecessary portions were removed and only the black pattern was left. The black pattern formed was heated in an oven at 230 DEG C for 30 minutes to cure the black matrix pattern.

<Developability Measurement>

The developability of the specimen was measured during the development process. The breakpoint was measured to check developability values.

Test Example 2: Resolution Measurement

For each of the specimens obtained in the production of the specimen, the resolution was measured by observing the minimum size at which the light-shielding spacer pattern was generated using a micro-optical microscope. The results are shown in Table 1.

Test Example 3: Measurement of chemical resistance

Using the colored photosensitive resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2, a black matrix pattern having a thickness (T) of 2.2 (+/- 0.1) 占 퐉 was prepared in the same manner as in the preparation of the above- The initial thickness of the pattern was measured. Thereafter, the specimen was immersed in a 100% solution of NMP (N-methylpyrrolidone), and then heated in a constant temperature bath at 100 ° C for 10 minutes, baked in an oven at 100 ° C for 2 minutes, and then measured for secondary thickness. Then, it was finally baked in an oven at 230 ° C for 20 minutes, and the final thickness was measured. Based on the obtained measurement value, the chemical resistance was calculated using the following equation (1). The lower the value of chemical resistance (%), the better.

[Equation 1]

Chemical resistance (%) = ((final thickness / initial thickness) X 100) -100

Test Example 4: Measurement of heat resistance characteristics

The black matrix pattern was scratched with each of the specimens obtained in the preparation of the above specimen, and 1 to 2 g of the scratched black matrix pattern was placed in a TGA cell and subjected to TGA (thermal analysis equipment, manufactured by TA Instruments) , The temperature was maintained at 300 ° C for 60 minutes, and then the weight loss (weight%) was measured. The lower the weight loss ratio at each temperature, the better the heat resistance.

Test Example 5: Shading ability measurement

OD was measured using an OD measuring instrument (T264, X-Rite) to determine the difference in light shielding ability between the respective specimens obtained in the preparation of the specimens. The OD of the specimen was 2.29 ㎛ (± 0.1 ㎛) It can be said that the light shielding ability is excellent.

Test Example  6: Pattern straightness measurement

Straightness was confirmed using an SEM (SIS-3000, Hittachi) for a 20 탆 line pattern in each specimen obtained in the preparation of the above specimen. At this time, it can be said that the straight line pattern has the straight line shape.

From the experimental results shown in Table 1, it was found that when the black matrix was prepared by using the photosensitive resin compositions of Examples 1 to 5 according to the present invention, it had excellent resolution and pattern straightness, and particularly excellent chemical resistance and heat resistance .

On the other hand, the photosensitive resin compositions of Comparative Examples 1 and 2 do not contain a copolymer included in the photosensitive resin composition according to the present invention, and in particular, do not contain a constituent unit derived from an unsaturated monomer having a Si-O skeleton on the side chain , And it was found that the black matrix produced using the same had poor chemical resistance and heat resistance.

In particular, when the black matrix was prepared using the photosensitive resin compositions of Examples 2 to 5, the photosensitive resin composition contained an epoxy resin compound or a compound derived therefrom, indicating that the pattern straightness was more excellent. On the other hand, when the black matrix was produced using the photosensitive resin composition of Comparative Example 2 which did not contain an epoxy resin, it was found that the pattern straightness was not good.

Claims (6)

(1) a structural unit derived from (1-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a mixture thereof, (1-2) a structural unit derived from an unsaturated monomer having a Si- , And (1-3) a copolymer comprising a constituent unit derived from an ethylenically unsaturated compound different from the constituent units (1-1) and (1-2);
(2) a colorant;
(3) a polymerizable unsaturated compound; And
(4) Photopolymerization initiator
And the coloring photosensitive resin composition.
The method according to claim 1,
Wherein the unsaturated monomer having a Si-O skeleton in the side chain is represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

In Formula 1,
R ₁ is hydrogen or a straight, branched or cyclic alkyl group of 1 to 8 carbon atoms,
R ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms,
R ₃ and R ₄ are each independently hydrogen, a straight, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms,
R ₅ is hydrogen, a methyl group, or an ethyl group,
n is an integer of 2 to 20;
The method according to claim 1,
The copolymer (1) comprises 3 to 40% by weight, 5 to 60% by weight, and 15 to 60% by weight of the constituent units (1-1), (1-2) By weight based on the total weight of the colored photosensitive resin composition.
The method according to claim 1,
(2) a colorant, (3) a polymerizable unsaturated compound, and (4) a photopolymerization initiator, based on the total weight of the colored photosensitive resin composition (based on the solid content) %, 10 to 65 wt.%, 10 to 55 wt.%, And 0.2 to 5 wt.%, Further comprising (5) an epoxy resin or a compound derived therefrom in an amount of 2 to 40 wt.% Wherein the coloring photosensitive resin composition is a colored photosensitive resin composition.
5. The method of claim 4,
Wherein the epoxy resin is an epoxy resin having a xanthene skeleton structure.
The method according to claim 1,
Wherein the colorant comprises a lactam black.