KR20160115151A - 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 a black photosensitive resin composition, a color filter comprising a black matrix and/or a column spacer produced by using the same, and a liquid crystal display device comprising the color filter. The black photosensitive resin composition comprises: (A) a colorant; (B) an alkali-soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; (E) a curing accelerator represented by chemical formula 1; and (F) a solvent.

Description

TECHNICAL FIELD [0001] 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. 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 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 formed at the boundary of each color pixel and not transmitting substantially visible light as black. The black matrix or black column spacer is a material for securing the space required for moving the liquid crystal between the two glass plates constituting the LCD and maintaining the elasticity of the LCD, and is formed of a black photosensitive resin composition. The black matrix or black column spacers can be installed in any desired position in a column shape, allowing for precise spacing and thickness control. In this case, 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 which become spacers on the entire surface of a substrate has been adopted. However, this method has a disadvantage in that it is difficult to uniformly maintain the cell gap, and the bead is attached to the pixel display portion, resulting in lower contrast and image quality of the image. In order to solve these problems, various methods using a photosensitive resin composition capable of forming a step difference have been proposed.

Korean Patent Laid-Open Publication No. 10-2012-033893 discloses a method of forming a black column spacer having a height difference by using a photosensitive resin composition, but it has disadvantages such as insufficient adhesion and chemical resistance.

Korean Patent Publication No. 10-2012-033893

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a resin composition which not only has excellent physical properties such as optical density, electrical insulation, light- ) Of the black photosensitive resin composition.

It is another object of the present invention 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.

In order to achieve the above object,

The present invention relates to a black photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a curing accelerator represented by the following formula (1) A resin composition is provided:

[Chemical Formula 1]

Wherein R ¹ is a divalent aromatic hydrocarbon of at least carbon number of 1 to 10 aliphatic hydrocarbon, or a divalent or more carbon atoms of 5 to 20, wherein R ² is an alkyl group having 1 to 10 carbon atoms, and wherein n is an integer from 2 to 4,

The aliphatic hydrocarbon or aromatic hydrocarbon may contain one or more heteroatoms selected from O, S, and N.

The present invention also provides a color filter comprising a black matrix or a column spacer manufactured using the black photosensitive resin composition.

The present invention also provides a liquid crystal display device having the color filter.

The black photosensitive resin composition of the present invention satisfies generally required optical density, electrical insulation, light shielding property, heat resistance and the like, and particularly provides an effect of greatly improving coating property, adhesion property, and reliability (chemical resistance).

Further, 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 properties in terms of driving performance and durability.

The present invention relates to a black photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a curing accelerator represented by the following formula (1) A resin composition comprising:

[Chemical Formula 1]

Wherein R ¹ is a divalent aromatic hydrocarbon of at least carbon number of 1 to 10 aliphatic hydrocarbon, or a divalent or more carbon atoms of 5 to 20, wherein R ² is an alkyl group having 1 to 10 carbon atoms, and wherein n is an integer from 2 to 4,

The aliphatic hydrocarbon or aromatic hydrocarbon may contain one or more heteroatoms selected from O, S, and N.

The black photosensitive resin composition of the present invention contains (E) the curing accelerator represented by the following formula (1), thereby improving the coatability, adhesion, and reliability (chemical resistance) of the black matrix and / or the column spacer .

Each component constituting the black photosensitive resin composition of the present invention will be described below. However, the present invention is not limited to these components.

The colorant (A)

The colorant is used for black implementation and imparts light shielding to both the black matrix and the spacer. That is, the black matrix serves to prevent the light leakage, and the spacer can prevent the malfunction of the device caused by the light generated from the outside.

As the colorant, any colorants known in the art such as organic pigments, dyes and black pigments can be used as long as they have light shielding properties in visible light, but it is preferable to use black pigments.

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

Carbon black coated with a resin on its surface may be used for electrical insulation if necessary. In addition, since the resin-coated carbon black has a lower conductivity than carbon black not coated with the resin, excellent electrical insulation can be imparted to the black matrix, the spacer, or the black matrix integrated spacer.

In addition, the colorant may further optionally include a color correcting agent. As the color correcting agent, condensation polycyclic pigments such as anthraquinone pigments or perylene pigments, phthalocyanine pigments or organic pigments such as azo pigments can 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 light shielding property is not sufficient and the above-mentioned effect can not be ensured. On the other hand, if the content exceeds the above range, the quality of the pattern obtained after patterning may deteriorate. .

(B) an 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 a colorant, and may be selected from resins known in the art without any particular limitations as long as it functions as a binder resin have.

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

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

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be mono (2-methacryloyloxyalkyl) ester thereof, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the dicarboxylic polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate.

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

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentane Dienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl 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,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide 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 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 the like. These monomers may be used alone or in combination of two or more.

Preferably, the alkali-soluble resin having an acid value of 20 to 200 (KOH mg / g) is selected and used. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and is related to the solubility. When the acid value of the resin falls within the above range, the solubility in the developer is improved, and the non-exposed portion easily dissolves and the sensitivity increases. As a result, the pattern of the exposed portion remains at the time of development and the film remaining ratio is improved.

In order to improve the surface hardness of the alkali-soluble resin, the molecular weight and molecular weight distribution (MW / MN) may be limited. Preferably a weight average molecular weight of 5,000 to 100,000 and a molecular weight distribution of 1.5 to 6.0, preferably 1.8 to 4.0. The alkali-soluble resin having the molecular weight and molecular weight distribution in the above range is high in hardness, has a high residual film ratio as well as excellent solubility in the non-exposed portion in the developer and can improve the 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. Such a content is a range selected considering various factors such as solubility in a developing solution, pattern formation, etc. When used within the above range, solubility in a developing solution is sufficient and pattern formation is easy, So that the dropout of the non-pixel portion is improved.

(C) Photopolymerization  compound

The photopolymerizable compound (C) is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

The photopolymerizable compound (C) used in the present invention is a compound having two or more different structures or functional groups of the functional group in order to improve developability, sensitivity, adhesion, surface problems, etc. of the photosensitive resin composition for forming the front light- And a photopolymerizable compound may be mixed and used. As long as it is generally used in this field, the kind thereof is not particularly limited.

Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

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) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (metha) acrylate, propoxylated dipenta (Meth) acrylate, erythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound may be used in an amount of 1 to 50% by weight, preferably 5 to 40% by weight based on the total weight of the black photosensitive resin composition. Such a content range is a range determined in consideration of various factors such as strength or smoothness as a black matrix or a spacer to be finally obtained. If the content is less than the above range, strength and smoothness are insufficient and conversely, , There arises a problem that patterning is not easy due to high strength, and therefore, it is appropriately used within the above range.

(D) Light curing Initiator

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

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- Oligomers of benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2- methyl [4- (1-methylvinyl) phenyl] propan- Among them, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one can be preferably used.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, Bis (diethylamino) benzophenone, and the like.

Examples of the triazine compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2 - (p-methoxyphenyl) -4,6-bis -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho 1-yl) -4,6-bis (trichloromethyl) (Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro-4-propanecioxanthone. have.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, and OXE01 and OXE02 commercially available from BASF.

Examples of the benzoin compound include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the anthraquinone-based compounds include 2-ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, and 2,3-diphenylanthraquinone.

Examples of the nonimidazole-based compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, a phenyl group in the 4,4', 5,5 'position is bonded to a carboalkoxy group And an imidazole compound substituted by a halogen atom.

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. Such a content range takes into consideration the photopolymerization rate of the photopolymerizable compound and the physical properties of the resultant coating film. If the amount is less than the above range, the polymerization rate is low and the overall process time may be prolonged. On the other hand, Since the physical properties of the coating film may be lowered, it is suitably used within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiator. When the photopolymerization initiator is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing the photopolymerization initiator is more preferable because productivity is improved when the support spacer for holding the cell gap is formed by using the black photosensitive resin composition.

The photopolymerization initiation auxiliary may be used for increasing the polymerization efficiency, and amine compounds, alkoxyanthracene compounds, and thioxanthone compounds may be used.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid- (Dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, Phenanone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 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, .

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- And the like.

The photopolymerization initiator may be directly produced or commercially available. For example, a trade name of "EAB-F" [manufactured by Hodogaya Chemical Industry Co., Ltd.] may be used.

The photopolymerization initiator is preferably used in an amount of usually not more than 10 mol, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When the photopolymerization initiator is used within the above range, the polymerization efficiency can be increased and the productivity improvement effect can be expected.

(E) a curing accelerator represented by the general formula (1)

The curing accelerator represented by the following formula (1) is used for improving the coatability and adhesion of the black photosensitive resin composition. That is, since it has a structure containing a carboxyl group protected in an ester form, it functions as a curing agent for promoting the curing of the photocurable monomer, especially the epoxy compound, and enhances the coatability, adhesion and reliability of the black photosensitive resin composition .

[Chemical Formula 1]

Wherein R ¹ is a divalent aromatic hydrocarbon of at least carbon number of 1 to 10 aliphatic hydrocarbon, or a divalent or more carbon atoms of 5 to 20, wherein R ² is an alkyl group having 1 to 10 carbon atoms, and wherein n is an integer from 2 to 4,

The aliphatic hydrocarbon or aromatic hydrocarbon may contain one or more heteroatoms.

Examples of the compound represented by the above formula (1) include compounds represented by the following formulas (2) and (3):

(2)

(3)

The curing accelerator represented by the formula (1) may be contained in an amount of 0.1 to 10% by weight, preferably 0.3 to 5% by weight, more preferably 0.5 to 3% by weight based on the total weight of the black photosensitive resin composition. If the content is less than 0.1% by weight, the effect of improving coatability, adhesion, and reliability may be insignificant. If the content is more than 10% by weight, gelation of the black photosensitive resin composition is not preferred.

(F) Solvent

The solvent may be any solvent capable of dissolving or dispersing the above-mentioned composition, and is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness can be used.

Representative examples of usable solvents 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? -butyrolactone.

Among the above solvents, alkylene glycol alkyl ether acetates, ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate may be preferably used, and 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 singly or in combination of two or more.

The solvent may be contained in a balance such that the black photosensitive resin composition satisfies 100 wt%. Such a content is selected in consideration of dispersion stability of the composition and easiness of process in the production process (for example, applicability). 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, wherein the wet coating method is a roll coater, a spin coater, a slit and spin coater, Or a die coater), a coating device such as an inkjet can be used.

(G) Additive

The black photosensitive resin composition of the present invention may further contain additives known in the art for various purposes. Such additives include adhesion promoters, dispersants, fillers, other polymer compounds, ultraviolet absorbers, and anti-aggregation agents. These additives may be used singly or in combination of two or more, and it is preferable to use not more than 5% by weight 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. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane, 2- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Ethoxy silane, and the like.

As the dispersing agent, a commercially available surfactant may be used, and a fluorine-based surfactant, a urethane-based surfactant, or the like may be used. Examples of the fluorine-based surfactant include BM-1000, BM-1100 (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 / SZ- Ltd.) and the like can be used. The urethane surfactant includes DiperBYK-163 (BYK). Dispersion aids such as Solsperse 5000 (Lubrisol) may also be added.

Examples of the filler include glass, silica and alumina. Other polymer compounds include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate , Polyester, polyurethane and the like can be used.

Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Examples of the antiflocculating agent include sodium polyacrylate .

The other polymeric compound is not limited as far as it does not affect compatibility, but is preferably a bisphenol A type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a cyclic aliphatic epoxy resin, a glycidyl ester type epoxy A resin obtained by (co) polymerization of a glycidylamine type epoxy resin, a heterocyclic epoxy resin, and glycidyl methacrylate. Among them, bisphenol A type epoxy resin, cresol novolak type epoxy resin, glycidyl ester type epoxy resin and the like are preferable.

The production of the black photosensitive composition of the present invention is not particularly limited and follows the known production method of the photosensitive composition.

For example, a coloring agent may be added to a solvent, followed by addition of the rest of the composition and other additives, followed by 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 advance in a solvent or an alkali-soluble resin. The additive, if in solution form, may be added in advance to the solvent along with the colorant.

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

In particular, the black photosensitive resin composition of the present invention can be preferably used for producing a black matrix-integrated spacer, and the black matrix-integrated spacer does not form a black matrix and a spacer but forms a black matrix and a spacer All of which can be performed.

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

Further, the present invention relates to a liquid crystal display device including the color filter

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

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

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

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

e) drying and post-baking steps

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, in particular, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

The coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

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

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure is carried out for the purpose of removing the photosensitive resin composition in the portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 ° C, preferably 20 to 40 ° C, using a developing machine or an ultrasonic cleaner .

The post bake is performed to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 230 ° C for 10 to 120 minutes. Post-baking Pre-baking is carried out using an oven, hot plate or the like.

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

The film thickness of the column spacer and the black matrix integrated spacer is preferably 0.1 mu m to 8 mu m, more preferably 0.1 mu m to 6 mu m, and particularly preferably 0.1 mu m to 4 mu m.

The black matrix, the spacer or the black matrix integrated spacer manufactured from the black photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesion, electrical insulation and light shielding property, and is excellent in heat resistance and solvent resistance, It is possible to improve the reliability.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, 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 funnel and a nitrogen inlet tube was prepared. As a monomer dropping lot, a mixture 40 of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate in a molar ratio of 50:50 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) And stirring was prepared.

To this mixture, 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added by a chain transfer agent dropping funnel to prepare a stirrer.

Then, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring.

The dropping of monomer and chain transfer agent was then initiated. The mixture was allowed to stand at 90 DEG C for 2 hours, elevated to 110 DEG 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 by GPC method and HLC-8120GPC (manufactured by Tosoh Corporation) was used.

For the measurement conditions, TSK-GELG4000HXL and TSK-GELG2000HXL columns were connected in series and the temperature of the column was set at 40 ° C. Tetrahydrofuran was used as mobile phase solvent and flow rate was measured at 1.0 mL / min flow rate. The concentration of the measurement sample was 0.6% by weight, and the injection amount was 50 이며, and analyzed using an RI detector. As the standard materials for calibration, TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) The average molecular weight was measured.

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

Synthetic example  1: Synthesis of curing accelerator of formula (1) (A1)

75.0 g of phthalic acid and 15.0 g of isobutyl vinyl ether as a monofunctional vinyl ether compound were mixed in 30 g of propylene glycol methyl ether acetate solvent, stirred at 80 DEG C for 18 hours, and then allowed to stand still And the solvent was removed to obtain a compound of the following formula (5).

(2)

Synthetic example  2: Synthesis of curing accelerator of formula (1) (A2)

The atmosphere in the flask was changed from nitrogen to air, and 70.0 g of 4,4-oxydiphthalic anhydride and 20.0 g of isobutyl vinyl ether as a monofunctional vinyl ether compound were mixed with 30 g of propylene glycol methyl ether acetate solvent, After stirring for 20 hours, the remaining monomers and solvent were removed to obtain the following structural formula (6).

(3)

Example  1 to 4 and Comparative Example  1 to 3: Preparation of black photosensitive resin composition

After adding a solvent to the mixer, a pigment, a curing accelerator of formula (1), an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives were added and uniformly mixed by stirring to prepare a black photosensitive resin composition. The composition was as shown in Table 1 below.

Configuration Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pigment Pigment 1 4.58 4.58 4.58 4.58 4.58 4.58 4.58 Pigment 2 3.61 3.61 3.61 3.61 3.61 3.61 3.61 Pigment 3 0.62 0.62 0.62 0.62 0.62 0.62 0.62 Alkali-soluble resin 5.64 5.64 5.64 5.64 5.64 5.64 6.64 Photopolymerizable compound 4.84 4.84 4.84 4.84 4.84 4.84 6.06 Photopolymerization initiator 0.50 0.50 0.50 0.48 0.50 0.50 0.50 The curing accelerator of formula (1) A1 0.83 0.415 - - A2 0.83 0.415 1.00 - additive A3 - - 0.83 - A4 1.24 1.24 1.24 1.24 2.07 1.24 - A5 0.15 0.15 0.15 - 0.15 0.15 - solvent 78.0 78.0 78.0 78.0 78.0 78.0 78.0 Total amount 100 100.0 100.0 100.0 100.0 100.0 100.0 100.0

(Unit: wt%)

Blue 1: Red 179 (DIC) / Pigment 2: Blue 15: 6 (DIC) / Pigment 3: CB (MA-8, Mitsubishi)

- Alkali-soluble resin: Synthesis in Preparation Example 1

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

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

Curing accelerator of formula (1)

A1: Synthesis Example 1 Preparation 2 Compound / A2: Synthesis Example 2 Preparation 3 Synthesis of Compound

- additive

A3: phthalic acid (1,2-benzene dicarboxylic acid) (Sigma-aldrich, ACS reagent ≥99.5%) / A4: HP-4710 (DIC) / A5: Solsperse 5000 (Lubrisol)

Solvent: propylene glycol monomethyl ether acetate

Test Example  One: Elastic recovery rate  And reliability evaluation

(1) Preparation of colored substrate

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the black photosensitive resin compositions prepared in the above Examples and Comparative Examples was spin-coated on the glass substrate to a final film thickness of 3.0 탆, prebaked at 80 to 120 캜 and dried for 1 to 2 minutes to remove the solvent Respectively. Then, exposure was performed at an exposure amount of 40 to 100 mJ / cm ² to form a pattern, and an unexposed area was removed using an aqueous alkaline solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

(2) Reliability evaluation

To evaluate the solvent resistance of the NMP solvent, the colored substrate was cut to a size of 3 cm x 3 cm, placed in 15 g of NMP, allowed to stand in an oven at 100 ° C for 30 minutes, and then the NMP solvent was recovered and measured with a UV- vis spectrometer (UV- ) And the absorbance was measured to evaluate the reliability. The results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Abs. * 0.149 0.116 0.123 0.072 0.420 0.255 1.550

* Abs: Absorbance. It is considered that the lower the numerical value showing the maximum absorption in the wavelength range of 400 ~ 800nm, the better the reliability.

From the results shown in Table 2, it was found that the films prepared from the black photosensitive resin compositions (including the curing accelerator of Examples 1 to 4) of the present invention had a small dissolution rate with respect to NMP, and thus the black photosensitive resin compositions of Comparative Examples 1 to 3 It was confirmed that the reliability (chemical resistance) was remarkably superior to that of the prepared film.

Claims (7)

A black photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a curing accelerator represented by the following formula (1)
[Chemical Formula 1]

Wherein R ¹ is a divalent aromatic hydrocarbon of at least carbon number of 1 to 10 aliphatic hydrocarbon, or a divalent or more carbon atoms of 5 to 20, wherein R ² is an alkyl group having 1 to 10 carbon atoms, and wherein n is an integer from 2 to 4,
The aliphatic hydrocarbon or aromatic hydrocarbon may contain one or more heteroatoms selected from O, S, and N. The black photosensitive resin composition according to claim 1, wherein the (B) alkali-soluble resin has a molecular weight of 5,000 to 100,000. (A) 1 to 50% by weight of a colorant, (B) 5 to 80% by weight of an alkali-soluble resin, (C) 1 to 50% by weight of a photopolymerizable compound, (D) And (C) 0.01 to 10% by weight of a photopolymerization initiator, (E) 0.1 to 10% by weight of a curing accelerator represented by the following formula (1), and (F) remaining amount of a solvent. 4. The black photosensitive resin composition according to claim 3, wherein the colorant (A) is at least one selected from the group consisting of aniline black, perylene black, titanium black, and carbon black. 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 a column spacer made of the black photosensitive resin composition according to any one of claims 1 to 5. A liquid crystal display device comprising the color filter of claim 6.