KR102243177B1 - 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 provides at least one component selected from (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, (E) an isoprene-based oligomer and a styrene-butadiene-based rubber, and ( F) Provides a black photosensitive resin composition containing a solvent, a color filter including a black matrix and/or a column spacer prepared using the same, 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 manufactured 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, and heat resistance, and in particular, a black photosensitive resin with improved elastic recovery rate and reliability. 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 provides at least one component selected from (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, (E) an isoprene-based oligomer and a styrene-butadiene-based rubber, and ( F) Provides a black photosensitive resin composition containing 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, heat resistance, and the like, and in particular, provides an effect of greatly improving the elastic recovery rate and reliability.

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 provides at least one component selected from (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photoinitiator, (E) an isoprene-based oligomer and a styrene-butadiene-based rubber, and ( F) It relates to a black photosensitive resin composition containing a solvent.

The black photosensitive resin composition of the present invention includes at least one additive selected from the (E) isoprene-based oligomer and styrene-butadiene-based rubber, thereby improving the elastic recovery rate and reliability of the black matrix and/or column spacer prepared using the same. It is characterized by greatly improving

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.

As the colorant, any colorant known in the art, such as organic pigments, dyes, and black pigments, can be used as long as it has light-shielding properties from visible light, but it is preferable to use a black pigment.

As the black pigment, a known black pigment may be used without particular limitation, but specifically, aniline black, perylene black, titanium black, carbon black, and the like may be used. These may be used alone or in combination of two or more. Examples of the carbon black include channel black, furnace black, thermal black, and lamp black.

If necessary, carbon black coated with a resin on the surface may be used for electrical insulation. Incidentally, since carbon black coated with resin has a lower conductivity than carbon black not coated with resin, excellent electrical insulation can be provided when forming a black matrix, a spacer, or a black matrix integrated spacer.

In addition, the colorant may optionally further include a color correcting agent as needed. As the color correcting agent, organic pigments such as condensed polycyclic pigments such as anthraquinone pigments or perylene pigments, phthalocyanine pigments, or azo pigments may be used.

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 by 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 field 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 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated carboxylic acids having one or more carboxyl groups in a molecule such as unsaturated tricarboxylic acids.

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 20 to 200 (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 5,000 to 100,000, 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 80% by weight, preferably 7 to 50% 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 property of the non-pixel part 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 capable of polymerization 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, anthraquinone-based, and Biimidazole-based compounds and the like may be used, and these may be used alone or in combination of two or more.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-(2-hydroxye). Oxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Oligomers of benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one, etc. Among these, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one may be preferably used.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'- Bis(diethylamino)benzophenone, etc. are mentioned.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dime Toxystyryl)-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, etc. are mentioned.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, and 1-chloro-4-propoxy thioxanthone. have.

Examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercially available products include BASF's OXE01 and OXE02.

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

As the biimidazole-based compound, 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 to the carboalkoxy group And imidazole compounds substituted by.

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) isoprene system Oligomer And at least one component selected from styrene-butadiene-based rubber

The component provides an excellent effect in improving the elastic recovery rate and reliability of the black photosensitive resin composition.

Representative examples of the isprene-based oligomer include oligomers of the following formula 1, LIR-30, LIR-50, the Representative examples of the styrene-butadiene-based rubber include rubber of the following formula (2), L-SBR-820, and the like:

[Formula 1]

In the above formula, m is preferably 70 to 1,200.

[Formula 2]

In the above formula, m is 40 to 600, and n is preferably 50 to 900.

At least one component selected from the isoprene-based oligomer and styrene-butadiene-based rubber may be included in an amount of 0.1 to 5% by weight based on the total weight of the black photosensitive resin composition, preferably 0.1 to 3% by weight, more preferably 0.2 It may be included in to 2% by weight. If the content is less than 0.1% by weight, the effect of improving the elastic recovery rate and reliability may be insignificant, and if it exceeds 5% by weight, the problem of mixing stability occurs, which is not preferable.

(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), Proride 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 dissolved or dispersed in a solvent or an alkali-soluble resin in advance. 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 post-baking and pre-baking, it is carried out using an oven, 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.

Further, 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 more specifically, 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° C. 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?. Tetrahydrofuran was used as a mobile phase solvent, and it was 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 alkali-soluble resins 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.

Example 1-2 and Comparative example 1 to 3: Preparation of black photosensitive resin composition

After adding a solvent to the mixer, at least one component selected from pigments, isoprene-based oligomers and styrene-butadiene-based rubbers, alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators and other additives are added, and uniformly mixed through stirring to black A photosensitive resin composition was prepared. At this time, the composition was according to the composition of Table 1 below.

Configuration Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment R179 3.13 3.13 3.13 3.13 3.13 B15:6 5.07 5.07 5.07 5.07 5.07 CB 0.60 0.60 0.60 0.60 0.60 Alkali-soluble resin 7.76 7.76 8.28 7.76 7.76 Photopolymerizable compound 4.10 4.10 4.22 4.10 4.10 Photopolymerization initiator 0.53 0.53 0.57 0.53 0.53 Isoprene-based oligomer or styrene-butadiene-based rubber A1-1 0.68 A1-2 0.68 additive A1-3 0.68 A1-4 0.68 A2 0.02 0.02 0.02 0.02 0.02 A3 0.11 0.11 0.11 0.11 0.11 solvent 78.0 78.0 78.0 78.0 78.0 Total amount 100 100.0 100.0 100.0 100.0 100.0

(Unit: wt%)

-Pigment

Red 179 (DIC company) / Blue 15:6 (DIC company) / CB (MA-8, Mitsubishi company)

-Alkali-soluble resin: Preparation Example 1 using synthetic resin

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

-Photoinitiator: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone-1-(O-acetyloxime) (Irgacure OXE-02: Ciba)

-Isoprene-based oligomer or styrene-butadiene-based rubber: A1-1: Isoprene oligomer LIR-30 (Kuraray) / A1-2: Styrene-butadiene rubber S-SBR-820 (Kuraray)

- additive

A1-3: Naphthalene epoxy additive (DIC) / A1-4: Phenol novolac epoxy additive (Kukdo Chemical) / A2: DiperBYK-163 (BYK) / A3: Solsperse 5000 (Lubrisol)

-Solvent: Propylene glycol monomethyl ether acetate

Test example One: Elastic recovery rate

(1) Fabrication of colored 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 3.0 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 100 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 colored substrate was measured using a Fisher hardness tester (fisherscope HM-2000, Fisher Company), 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.

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Elastic recovery rate 50.8% 51.2% 40.9% 42.4% 43.0%

As can be seen from Table 2, the elastic recovery rate of the pattern made of the black photosensitive resin composition (including isoprene-based oligomer or styrene-butadiene-based rubber) of Examples 1 to 2 of the present invention is the black photosensitive property of Comparative Examples 1 to 3 It was remarkably excellent compared to the pattern made with the resin composition.

Claims (7)

(A) colorant, (B) alkali-soluble resin, (C) photopolymerizable compound, (D) photoinitiator, (E) at least one component selected from isoprene-based oligomer and styrene-butadiene-based rubber, and (F) solvent Including,
The (A) colorant includes at least one black pigment selected from the group consisting of aniline black, perylene black, titanium black, and carbon black,
The (D) photopolymerization initiator is an O-acetyloxime-based photopolymerization initiator, wherein the black photosensitive resin composition for forming a black matrix or a column spacer. The method according to claim 1,
The molecular weight of the (B) alkali-soluble resin is 5,000 to 100,000, characterized in that, black photosensitive resin composition for forming a black matrix or column spacer. The method according to claim 1,
Based on the total weight of the black photosensitive resin 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,
(E) 0.1 to 5% by weight of at least one component selected from isoprene-based oligomers and styrene-butadiene-based rubbers, and
(F) A black photosensitive resin composition for forming a black matrix or column spacer, comprising a residual amount of a solvent. delete The method according to claim 1,
A black photosensitive resin composition for forming a black matrix or column spacer, further comprising at least one additive selected from the group consisting of an adhesion promoter, a dispersant, a filler, another polymer compound, an ultraviolet absorber, and an anti-aggregation agent. A color filter comprising a black matrix or column spacer made of the black photosensitive resin composition of any one of claims 1, 2, 3 and 5. A liquid crystal display device comprising the color filter of claim 6.