KR20180086149A - A photo sensitive resin composition, a colored photo sensitive resin composition comprising the same, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter - Google Patents

Abstract

An objective of the present invention is to provide a photosensitive resin composition which is capable of improving solvent resistance, development properties and pattern step margin by enhancing epoxy thermosetting reaction and improving adhesion. The present invention provides: a photosensitive resin composition comprising an alkali soluble resin (A) including a monomer represented by chemical formula 1, a photopolymerizable compound (B), a photopolymerization initiator (C), a silane coupling agent (D) represented by chemical formula 2, and a solvent (E); a color filter comprising a black matrix, a column spacer, or a black column spacer; and a display device comprising the color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a color filter including a black matrix, a column spacer, or a black column spacer manufactured using the same, and a display device including the color filter. [0002] A PHOTO SENSITIVE RESIN COMPOSITION, A COLORED PHOTO SENSITIVE RESIN COMPOSITION COMPETITION THE SAME, A COLOR FILTER COMPRISING A BLACK METRICS, A COLUMN SPACER OR BLACK COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND A DISPLAY DEVIDE COMPRISING THE COLOR FILTER}

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

The photosensitive resin is a representative functional polymer material practically used in production of various precision electronic and information industrial products and is currently being used for the production of high-tech industries, especially semiconductors and displays. Generally, a photosensitive resin means a polymer compound in which a chemical change of a molecular structure occurs within a short period of time by light irradiation, and a change in physical properties such as solubility, coloring, and curing for a specific solvent occurs. By using a photosensitive resin, fine precision processing is possible, energy and raw materials can be largely reduced as compared with a thermal reaction process, and work can be performed quickly and accurately in a small installation space, , Photocurable surface coating materials, and so on.

Among them, in the display field, the photosensitive resin composition is used for forming various photo-curing patterns such as a photoresist, an insulating film, a protective film, a color filter, a black matrix, and a column spacer. Specifically, the photosensitive resin composition is selectively exposed and developed by a photolithography process to form a desired photo-curable pattern. In order to improve the process yield in this process and improve the physical properties of the object to be applied, And adhesion and the like have been demanded.

As such a photosensitive resin composition, a composition containing a photopolymerizable compound and a photopolymerization initiator together with a binder resin is widely used. In addition, a photosensitive resin composition containing a black pigment is also used for forming a black matrix. As such a photosensitive composition, an acrylic resin having a carboxyl group on its side chain is used as a resin excellent in light resistance and little change in color.

If the pattern formed of such a photosensitive resin composition has poor adhesion to a substrate, there arises a problem such as peeling of a pattern in a subsequent step, resulting in lower yield of the product in the mass production process. Therefore, a photosensitive resin composition to which various silane coupling agents have been added has been proposed in order to improve the adhesion.

However, conventional techniques such as Korean Patent Laid-Open No. 10-2008-0046560 have disadvantages in that the silane coupling agent is lost during the curing process and thus the adhesion required even when a large amount is added can not be satisfied.

Korean Patent Publication No. 10-2008-0046560

SUMMARY OF THE INVENTION The present invention has been conceived to solve the above problems of the prior art and provides a photosensitive resin composition capable of improving the epoxy thermosetting reaction and improving the adhesiveness to improve the solvent resistance, developability and pattern step margins .

It is another object of the present invention to provide a photosensitive resin composition which is easy to form steps and patterns and is excellent in processability.

It is another object of the present invention to provide a color filter comprising a black matrix, a column spacer or a black column spacer made of a photosensitive resin composition.

In order to achieve the above object,

The present invention relates to (A) an alkali-soluble resin comprising a monomer represented by the following formula (1), (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a silane coupling agent represented by the following formula A photosensitive resin composition comprising a solvent is provided:

[Chemical Formula 1]

In this formula,

R ₁ is hydrogen or an alkyl or cycloalkyl group having 1-20 carbon atoms with or without a heteroatom;

R ₂ is a single bond, or an alkylene or cycloalkylene group having 1-20 carbon atoms with or without a hetero atom;

The R ₁ and R ₂ may be independently substituted with a hydroxy group.

(2)

In this formula,

Wherein n is an integer of 1 to 8, X is an acid anhydride, Y is -CH ₂ - or an oxygen atom, and R is a methyl group or an ethyl group.

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

Further, the present invention provides a display device including the color filter.

The photosensitive resin composition of the present invention improves the epoxy thermosetting reaction by introducing an alkoxysilane containing a carboxylic acid and improves the adhesiveness, thereby providing an effect of improving the solvent resistance, developability and pattern step margins.

Further, the photosensitive resin composition of the present invention is easy to form a step and a pattern, and thus provides excellent processability.

Further, the color filter and display device made of the photosensitive resin composition of the present invention provide excellent color reproduction characteristics.

1 is a view showing a black column spacer pattern.

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

The present invention relates to (A) an alkali-soluble resin comprising a monomer represented by the following formula (1), (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a silane coupling agent represented by the following formula The present invention relates to a photosensitive resin composition comprising a solvent,

[Chemical Formula 1]

In this formula,

R1 is hydrogen or an alkyl or cycloalkyl group having 1-20 carbon atoms, with or without a heteroatom;

R2 is a single bond or an alkylene or cycloalkylene group having 1-20 carbon atoms with or without a heteroatom;

The R 1 and R 2 may be independently substituted with a hydroxy group.

 (2)

In this formula,

Wherein n is an integer of 1 to 8, X is an acid anhydride, Y is -CH ₂ - or an oxygen atom, and R is a methyl group or an ethyl group.

Hereinafter, constituent components constituting the photosensitive resin composition of the present invention will be described in detail.

(A) an alkali-soluble resin

The alkali-soluble resin (B) used in the present invention is a component that imparts solubility to an alkali developing solution used in a development processing step for forming a pattern.

The alkali-soluble resin (B) according to the present invention preferably contains a monomer represented by the following formula (1) in view of solvent resistance, adhesion, and pattern step margins.

[Chemical Formula 1]

In this formula,

R1 is hydrogen or an alkyl or cycloalkyl group having 1-20 carbon atoms, with or without a heteroatom;

R2 is a single bond or an alkylene or cycloalkylene group having 1-20 carbon atoms with or without a heteroatom;

The R 1 and R 2 may be independently substituted with a hydroxy group.

The monomer represented by the formula (1) may be contained in an amount of 40 to 95% by weight based on the total weight of the alkali binder resin, more preferably 70 to 90% by weight.

The alkali-soluble resin (A) of the present invention is not particularly limited to the other constituents except for the monomer represented by the above formula (1).

That is, it is not particularly limited as long as it is a resin soluble in the solvent of the present invention and reactive to the action of light or heat and soluble in an alkaline developing solution. Specifically, a copolymer of the monomer of the above formula (1) and a carboxyl group- A copolymer of the monomer of Formula 1, a carboxyl group-containing monomer, and other copolymerizable monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid. These may be used alone or in combination of two or more. Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid and the like.

In the present specification, (meth) acrylic acid refers to at least one member selected from the group consisting of acrylic acid and methacrylic acid, and (meth) acryloyl refers to at least one member selected from the group consisting of acryloyl and methacryloyl . Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated carboxylic acid may also be mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated carboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. .

Specific examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- Aromatic vinyl compounds such as styrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether and p-vinyl benzyl methyl ether; 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, dicyclopentadiene Acrylate, dicyclopentadienyl 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; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether and vinyl ethyl 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; Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromonomers; A monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond; An alkali-soluble resin having 3,4-epoxytricyclo [5.2.1.02,6] decane ring, and a monomer having a dicyclopentane ring (tricyclo [5.2.1.02,6] -3-decene ring) . These may be used alone or in combination of two or more.

The molecular weight of the alkali-soluble resin (A) is not particularly limited and may be, for example, 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 50,000, in terms of polystyrene reduced weight average molecular weight have.

The content of the alkali-soluble resin (A) is not particularly limited and may be, for example, 5 to 60% by weight, preferably 20 to 50% by weight, based on the total weight of the solid content of the photosensitive resin composition have. When the content of the alkali-soluble resin (A) is within the above-mentioned range, solubility in a developing solution is sufficient, pattern formation is easy, and reduction of film in the pixel portion of the exposed portion is prevented during development, .

(B) Photopolymerization  compound

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

The photopolymerizable compound (B) 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, and surface problems 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 (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Of these, multifunctional monomers having two or more functional groups are preferably used.

When the photosensitive resin composition of the present invention is used as a column spacer, a black matrix, or a black column spacer, it may include an organic black pigment, a violet pigment, and a blue pigment as colorants, as described in detail below.

When such a colorant is used, the photopolymerizable compound uses a compound containing 4 to 12 functional groups, preferably a compound containing 6 to 10 functional groups, and the functional group is used in the art May be a commonly used (meth) acrylate group.

The photopolymerizable compound containing 6 to 10 functional groups specifically includes, for example, dipentaerythritol hexa (meth) acrylate tripentaerythritol octa (meth) acrylate and tetrapentaerythritol hepta (meth) acrylate And preferably a compound of the following formula (3), which is an 8-functional photopolymerizable compound, or a compound of the following formula (4), which is a 10-functional photopolymerizable compound.

(3)

[Chemical Formula 4]

The photopolymerizable compound may be contained in an amount of 1 to 50% by weight, preferably 5 to 40% by weight based on the total weight of the solid content of the photosensitive resin composition.

Such a content range is not particularly limited as long as the strength and smoothness of a pattern such as an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, a column spacer pattern and a black column spacer, If the content is less than the above range, the strength and smoothness are insufficient. On the contrary, if the content is in excess of the above range, patterning becomes difficult due to high strength. Is used.

(C) 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 solids in the 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.

(D) a compound represented by the formula Silane coupling agent

The silane coupling agent of the present invention is a silane coupling agent containing an acid anhydride as shown by the following formula (2). When the silane coupling agent represented by the following formula (2) is contained in the photosensitive resin composition of the present invention, the adhesiveness to the glass substrate is increased, and reliability and durability are improved, and the reactivity of the alkali-soluble resin (B) containing alicyclic epoxy group is increased The crosslinking reaction by the thermal process is promoted and the solvent resistance can be improved.

(2)

In this formula,

Wherein n is an integer of 1 to 8, X is an acid anhydride, Y is -CH ₂ - or an oxygen atom, and R is a methyl group or an ethyl group.

More preferably, the silane coupling agent is triethoxysilylpropyl succinic anhydride represented by the following formula (5) or a triethoxysilylpropyl succinic anhydride represented by the following formula (3 - ((3- (triethoxysilyl) propoxy) methyl) dihydrofuran-2,5-dione) Can be used.

[Chemical Formula 5]

[Chemical Formula 6]

The silane coupling agent is preferably contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin containing the monomer represented by the general formula (1) in terms of adhesion, development speed, and solvent resistance.

The silane coupling agent may be contained in an amount of 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 4% by weight based on the total weight of solids in the photosensitive resin composition.

If the content of the silane coupling agent is less than 0.01% by weight, the adhesion may be lowered and pattern peeling may occur. When the content of the silane coupling agent is more than 5% by weight, the developing speed is increased and the adhesion with the substrate is lowered So that the solvent resistance may be deteriorated.

(E) 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 in terms of coating property 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 an amount of 60 to 90% by weight, and preferably 70 to 85% by weight based on the total weight of the photosensitive resin composition. When the content of the solvent is within the above range, the dispersion stability and coating property of the composition may be good.

(F) Colorant

If necessary, the photosensitive resin composition of the present invention may further comprise a colorant, and the colorant may include a dye or a pigment.

The kind of the pigment is not particularly limited, and organic pigments or inorganic pigments generally used in the art can be used.

The above-mentioned pigments include various pigments used in printing ink, ink-jet ink and the like, and specifically include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments , Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments (for example, pyranthrone pigments, perynone pigments, perynone pigments, perynone pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Specific examples of the inorganic pigment include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, Oxide, carbon black and the like.

Particularly, the organic pigments and inorganic pigments may be compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specific examples thereof include pigments having a color index (CI) But are not limited to these.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58;

C.I. Pigment Brown 28;

C.I. Pigment Black 1 and 7 and the like.

The above-exemplified pigments may be used alone or in combination of two or more.

Further, carbon black, organic black pigment, titanium black, and black pigment mixed with red, blue and green can also be used.

The pigment may be used as a pigment dispersion having a uniform particle size distribution. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment by adding a pigment dispersant. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

The pigment dispersant is added to maintain the deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. An acrylate-based dispersant (hereinafter also referred to as an " acrylic dispersant ") containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) may be used. Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and DISPER BYK LPN-6919 are examples of commercially available acrylate dispersants. The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylic dispersant may be used.

The dye can be used without any particular limitation as long as it has solubility in an organic solvent. Preferably, the dye has solubility in an organic solvent and is capable of securing reliability such as solubility in alkali developer, heat resistance, solvent resistance, etc. It is good to do.

Examples of the dyes include acid dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo dyes, Phthalocyanine-based acid dyes and derivatives thereof can also be used.

Preferable examples of the dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and dyes described in dyeing notes (color dyeing).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163;

C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179;

C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62;

C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67 and 70;

C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49;

C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like.

The above-exemplified dyes may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention is used as a column spacer, a black matrix, or a black column spacer, the colorant preferably includes an organic black pigment, a violet pigment and a blue pigment.

The organic black pigment includes at least one member selected from the group consisting of lactam black, aniline black and perylene black, and preferably includes lactam black. The organic black pigment is 100 CF (manufactured by Basf Co.), and the optical density can be improved by including an organic black pigment, which is advantageous in terms of dielectric constant and transmittance.

The violet pigment serves to improve the optical density (O.D.) by reducing the transmittance in the region of 400 to 600 nm. In addition, the content of the organic black pigment can be reduced through the use of the violet pigment, and the reliability of the colored photosensitive resin composition can be improved. The type of the violet pigment is not particularly limited, but C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 31, C.I. Pigment Violet 37, and the like. Of these, C.I. Pigment violet 29 can be more preferably used.

 The blue pigment is a compound which does not contain a center metal. By using a blue pigment which does not include the center metal, it does not cause a problem in contact with the liquid crystal used in the process, have. In the present invention, the type of the blue pigment is not particularly limited as long as it is a compound that does not include a center metal. Pigment Blue 16, Pigment Blue 60, C.I. Pigment Blue 63, C.I. Pigment Blue 66, and the like, and more preferably at least one selected from the group consisting of C.I. Pigment Blue 60 may be used.

More specifically, the colorant is a mixture of an organic black pigment, a violet pigment and a blue pigment at a weight ratio of 1: 0.1 to 3.75: 0.25 to 5.0, preferably 1: 0.3 to 1.2: 0.67 to 2.5, will be.

When the organic black pigment is contained in the above weight ratio, a colored photosensitive resin composition excellent in optical density and reliability can be obtained. The organic black pigment may be contained in an amount of 4 to 20% by weight, and preferably 8 to 15% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

When the violet pigment is contained in the above weight ratio, a colored photosensitive resin composition excellent in optical density and reliability can be obtained. In addition, the violet pigment may be contained in an amount of 2 to 15% by weight, preferably 4 to 10% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

When the blue pigment is contained in the above weight ratio, a colored photosensitive resin composition having an excellent optical density can be obtained. The blue pigment may be contained in an amount of 5 to 20% by weight, and preferably 10 to 20% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

In addition, the colored photosensitive resin composition of the present invention may further contain carbon black as an additional colorant. When the colored photosensitive resin composition further contains carbon black, the colored photosensitive resin composition heavy oil black pigment, the violet pigment, the blue pigment and the carbon black are mixed at a weight ratio of 1: 0.1 to 3.75: 0.25 to 5.0: 0.15 to 2.5 . Further, it may preferably be mixed at a weight ratio of 1: 0.3 to 1.2: 0.67 to 2.5: 0.27 to 0.88. The carbon black may be contained in an amount of 3 to 10% by weight, and preferably 4 to 7% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

When the carbon black is contained in the above weight ratio, a colored photosensitive resin composition having an excellent optical density can be obtained.

In the present invention, the colorant is contained in an amount of 11 to 55% by weight, preferably 25 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is included in an amount of 11 to 55% by weight, an effect of improving the optical density can be obtained.

The colorant is preferably a pigment dispersion in which the particle size of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a1) by containing the pigment dispersant (a1), and a method of obtaining a pigment dispersion in which the pigment is uniformly dispersed in the solution have.

(a1) pigment dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and the like may be used as the acrylate-based dispersing agent, The rate-based dispersing agents may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of more than 0 to 1 part by weight, preferably 0.05 to 0.5 part by weight based on 1 part by weight of the colorant. When the pigment dispersant is contained in an amount exceeding 0 to 1 part by weight, the uniformly dispersed pigment can be obtained.

(F) Additive

The photosensitive resin composition of the present invention includes other additives according to needs of those skilled in the art as long as the objects of the present invention are not impaired, in addition to the above-mentioned components.

The additive may specifically include, for example, at least one additive selected from the group consisting of another polymer compound, a thermal initiator, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti- In the invention, it is preferable to include a thermal initiator as an additive.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane.

The thermal initiator causes a curing reaction by heat to maximize the initiation efficiency. The thermal initiator may be a peroxide compound, and the thermal initiator is characterized by improving the physical properties of the coating film at low temperatures.

Specific examples of the thermal initiator include, but are not limited to, tetramethyl butyl peroxyneodecanoate (eg Perocta ND, NOF), bis (4-butylcyclohexyl) peroxydicarbonate (eg Peroyl TCP Perfluoroalkane (ex. Perbutyl ND, manufactured by NOF), dipropyl peroxydicarbonate (ex. Peroyl NPP, manufactured by NOF Corporation), di (2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate , NOF Corp.), diisopropyl peroxy dicarbonate (e.g., Peroyl IPP, NOF), diethoxyethyl peroxydicarbonate (e.g., Peroyl EEP, NOF), diethoxy (Peroyl OEP, NOF), hexyl peroxydicarbonate (e.g., Perhexyl ND, NOF), dimethoxybutyl peroxydicarbonate (e.g. Peroyl MBP, NOF Peroyl SOP, NOF), dibutyl peroxydicarbonate, dicetyl peroxy dicyclohexylcarbodiimide, bis (3-methoxy-3-methoxybutyl) peroxydicarbonate Dicabo Peroxypivalate, hexyl peroxypivalate (ex. Perhexyl PV, NOF), and the like. Perbutyl (NOF), trimethyl hexanoyl peroxide (e.g., Peroyl 355, NOF), dimethylhydroxybutyl peroxyneodecanoate (ex Luperox 610M75) , Atofina (manufactured by Atofina), amyl peroxyneodecanoate (ex Luperox 546M75, Atofina), butyl peroxyneodecanoate (ex Luperox 10M75, Atofina), t-butyl peroxy (Luperox 546M75, Alofina), t-butyl peroxypivalate, t-amylperoxy-2-ethylhexanoate, lauryl peroxide , Dilauroyl peroxide, didecanoyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 2,2-bis (tert-butylperoxy) butane, 1,1- Butyl peroxy) -2,5-dimethylhexane, 2,5-bis (tert-butylperoxy) -1-methylethyl) benzene, 1,1- Butyl peroxy) -3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, Peracetic acid, and potassium persulfate, which may be used alone or in combination with one or more of the following: ). ≪ / RTI >

With respect to the thermal initiator content, it is preferably contained in an amount of 1 to 10% by weight, and more preferably 1 to 5% by weight based on the total solid content of the photosensitive resin composition. When it is contained in the above-mentioned contents, it is more preferable for fairness and undercut.

The curing agent is used for increasing the curing depth and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used together with a curing assistant compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agents include commercial products such as ADEKA HARDONA EH-700 (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (manufactured by New Japan Chemical Co., Ltd.) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film-forming property of the photosensitive resin composition, and a silicone surfactant or a fluorine surfactant may be preferably used.

TS-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4400 of GE Toshiba Silicones such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., 4460 and TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 (Dainippon Ink Chemical Industries, Ltd.), BM- Chemie) and Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.). The above-exemplified surfactants may be used alone or in combination of two or more.

The adhesion promoter is an additive which is used for improving coatability and adhesion to a substrate, and is a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, . Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, r- Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The additive is contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 4% by weight based on the total weight of the solid content in the photosensitive resin 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 photocurable pattern may be a photocurable pattern selected from the group consisting of an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, a column spacer pattern and a black column spacer.

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

The present invention is also characterized in that the above-mentioned photosensitive resin composition exhibits a light transmittance of 0.1% or less with respect to a wavelength in the range of 400 to 600 nm when formed into a cured film having a thickness of 3.0 탆; Exhibits a light transmittance of less than 10% for wavelengths in the range of 700 nm to 750 nm; And exhibits a light transmittance of 15% or more with respect to a wavelength in the range of 950 nm to 950 nm.

In particular, the black photosensitive resin composition of the present invention can be preferably used for producing a black column spacer (black matrix integrated spacer), and the black column spacer does not form a black matrix and a column spacer, Means that the matrix and the column spacer are integrally formed.

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

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

A typical patterning process for forming a black matrix, column spacer or black column spacer according to the photolithography method

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.

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 performed for the purpose of removing the black photosensitive resin composition of 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. In particular, by using a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate in a temperature range of 10 to 50, preferably 20 to 40 ° C, using a developing machine or an ultrasonic cleaner .

The post-baking is performed in order to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 DEG C for 10 to 120 minutes. Post-baking is performed by using an oven, a hot plate, or the like as in pre-baking.

In this case, 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 column spacer is preferably 0.1 탆 to 8 탆, more preferably 0.1 탆 to 6 탆, and particularly preferably 0.1 탆 to 4 탆.

The black matrix, the column spacer or the black column spacer made of 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.

Production Example 1: Preparation of alkali binder resin (A)

≪ Preparation Example 1 &

277 g of propylene glycol monomethyl ether acetate (hereinafter referred to as " PGMEA ") was charged into a 1-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, A mixture of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate , A mixed solution prepared by dissolving 301 g of [50:50 (molar ratio)], 49 g of methacrylic acid, and 23 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate was added dropwise over 5 hours and aged for 3 hours To obtain a copolymer solution (solid concentration 35.0%). The acid value (dry) of the obtained copolymer was 69.8 KOH mg / g, and the weight average molecular weight (Mw) was 9,300.

≪ Preparation Example 2 &

A separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 58 parts by weight of methyl methacrylate, 28 parts by weight of acrylic acid, propylene glycol monomethyl ether acetate (hereinafter referred to as " PGMEA & 5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) was added to the total amount of the monomers (100 parts by weight) in an amount of 2 parts by weight based on the total amount and dissolved homogeneously. Thereafter, the mixture was stirred at 85 DEG C for 2 hours under a nitrogen stream, and then reacted at 100 DEG C for 1 hour. To the obtained solution, 15 parts by weight of glycidyl methacrylate, 10 parts by weight of triethylamine with respect to glycidyl methacrylate, and 10 parts by weight of hydroquinone with respect to the total amount of the above monomers (100 parts by weight) And PGMEA were further added so that the combined weight of the injected monomer and glycidyl methacrylate became 35% by weight, and the mixture was stirred at 100 캜 for 5 hours to obtain a target copolymer solution (solid content concentration: 31.5% ).

The weight average molecular weight (Mw) of the obtained copolymer was 11,000 and the acid value (dry) thereof was 84 mgKOH / g.

Examples 1 to 5 and Comparative Examples 1 to 4: Preparation of Photosensitive Resin Composition

The components shown in Table 1 were mixed according to the indicated contents to prepare a photosensitive resin composition.

[Table 1]

Note) Binder resin (B-1): Production example 1 Production

Binder resin (B-2): Production example 2 Production

Photopolymerizable compound (M1): Viscoat # 802 (octa-functional, Osaka Organic Chemical)

Photopolymerizable compound (M2): DIPENTAERYTHRITOL HEXAACRYLATE (DPHA) (Nippon Kayaku Co., Ltd.)

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

Additive (D): F554 (DIC)

Silane coupling agent (A-1): X-12-967C (Shin-Etsu Silicone Co., Ltd.) 3- (trimethoxysilyl) propylsuccinic anhydride

Silane coupling agent (A-2): KBM-403 (Shin-Etsu Silicone Co., Ltd.) 3-glycidoxypropyl trimethoxysilane

Silane coupling agent (A-3): KBM-503 (Shin-Etsu Silicone Co., Ltd.) 3-methacryloxypropyl trimehoxysilane

Solvent (S): Propylene glycol monomethyl ether acetate

Example  6 to 17 and Comparative Example  5 to 8: Preparation of black photosensitive resin composition

A mixture of a colorant, an alkali-soluble resin, a dispersant and a solvent was dispersed in a paint shaker at room temperature for 8 hours. Dispersion was carried out using 0.1 mm zirconia beads, followed by dispersion and filtration to prepare a colored dispersion.

A black photosensitive resin composition was prepared by mixing the above colored dispersion with an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the content thereof is shown in Table 2 below.

[Table 2]

Note) OBP: Irgaphor Black S 0100CF (manufactured by Basf)

Details of the components except for the colorant are the same as those in Table 1 above.

Test Example  1: Board fabrication and evaluation

(1) Substrate fabrication

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the 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 . Then, exposure was performed at an exposure amount of 25 to 35 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) Developability  And developing speed

The substrate was cleaned with a 5 cm x 5 cm glass substrate (Corning # 1737) with a neutral detergent and water, and dried. The black photosensitive resin composition was coated on the glass substrate by spin coating and then placed on a heating plate and dried at a temperature of 80 to 120 DEG C for 1 to 2 minutes to remove the solvent. Then, the thin film from which the solvent was removed was immersed in a KOH aqueous solution developing solution of pH 10.5 at 20 ° C to observe the developing behavior of the coating film. The time when the coating was completely developed was measured and the experiment was conducted based on the measured time, and it is shown in Table 2 below.

(3) Solvent resistance  evaluation

The solvent resistance was measured by immersing a coating film (3 cm x 3 cm) in 18 g of a solvent NMP at room temperature for 60 minutes, extracting the NMP solvent, and measuring the absorbance at the visible light wavelength of the immersed NMP solvent using a shimadzu UV- The peak absorbance of the NMP solvent is shown in Table 3 below.

(4) Evaluation of adhesion

The prepared sheet was cut into 100 matrix structures in an area of 10 mm x 10 mm, and then the tape was adhered thereon, and the number of unetched matrices (number of not peeled / 100) .

◎: No pattern peeling

ㅇ: 1 to 2 patterns

△: 3 to 4 pattern peeling

×: 5 to 9 patterns

××: more than 10 pieces

[Table 3]

Referring to Table 3, the coating films prepared from the compositions of Examples 1 to 17 including the silane coupling agent represented by Chemical Formula 2 in the results of the measurement of the wavelength of the NMP solvent exhibited excellent adhesion, The elution of the dye hardly occurred. On the other hand, in the case of the coating film prepared from the composition of Comparative Examples 1 to 6 and Comparative Example 8, which did not contain the silane coupling agent represented by the formula 2, the adhesion was poor and a large amount of pigment or dye The elution of

As a result, it was confirmed that the compositions of Examples 1 to 17 had excellent adhesion due to the reactivity between the silane coupling agent represented by the formula (2) and the epoxy resin, and also the reliability by solvent resistance was excellent.

Test Example  2: Measurement of physical properties of black photosensitive resin composition

Optical properties, reliability and compression characteristics of the compositions of Examples 6, 9, 10 to 14, 17, and 7 were evaluated.

(One) Optical property  Measure

A 5 cm x 5 cm glass substrate (Corning) was cleaned with neutral detergent and water and dried. Each of the black photosensitive resin compositions prepared in Example 6, Example 8, Examples 9 to 14, Example 15 and Example 16, and Example 17 was coated on the glass substrate with a final film thickness of 3.0 (± 0.2 ), Followed by pre-baking at 80 to 120 ° C and drying for 1 to 2 minutes to remove the solvent to form a pre-cured film.

Thereafter, the resist was exposed to light at an exposure dose of 25 to 35 mJ / cm ² to form a pattern, and an unexposed area was removed using an aqueous alkali solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

The resulting cured film was evaluated for its optical characteristics using a UV-vis (UV-2550; Shimadzu). The evaluation criteria were as follows, and the results are shown in Table 3 below.

≪ Criteria for evaluating optical characteristics 1: within a wavelength range of 400 to 600 nm >

Good: Excellent, 0.1% light transmittance or less

[Delta]: insufficient, 0.3% light transmittance or less

X: worsening, 0.5% light transmission abnormality

≪ Optical characteristic evaluation standard 2: Within 700 to 750 nm wavelength range >

○: excellent, 10% light transmittance or less

?: Insufficient, 12% light transmittance or less

X: worsening, 14% light transmission abnormality

≪ Evaluation criterion of optical characteristics 3: within 950 nm wavelength range >

○: excellent, 15% light transmittance or more

DELTA: insufficient, 13% light transmissive or more

X: worse, 13% less light transmittance

(2) Reliability measurement

The glass substrate on which the cured film formed by the above method (1) was cut was cut to 3 x 3 cm, and then immersed in an NMP solution, followed by heating at 100 ° C for 60 minutes. Thereafter, only the NMP solution was extracted, and the degree of elution in the NMP solvent was measured using a UV-vis spectrometer. The results are shown in Table 3 below.

<Reliability Evaluation Standard>

○: Excellent, 0.5 or less

?: Good, 0.8 or less

X: worse, 1.0 or higher

(3) Elastic recovery rate  Measure

A glass substrate coated with a cured film is fabricated in the same manner as in the above (1) except that a column spacer pattern is formed. The fabricated substrate is measured by SNU (SIS-2000, manufactured by SNU) and the thickness and height of the pattern in the reference state. Thereafter, using a hardness meter (Nano-indenter HM500, Fisher), the pattern is pressed to the point where it is deformed by 1 占 퐉. The hardness meter uses a flat indenter and presses at a rate of 2 mN / sec. Holding time is 5 seconds at the point of 1μm deformation. Thereafter, the thickness and line width of the pattern were measured using SNU (SIS-2000, SNU), and the elastic recovery rate was measured by the thickness change of the pattern before and after the pattern (percentage of the thickness of the pattern after deformation based on the thickness of the pre- do.

&Lt; Elasticity recovery rate evaluation standard &

○: Excellent, 97% or more

?: Good, less than 97%

X: worse, less than 95%

[Table 4]

As shown in Table 4, in Example 6, Examples 9 to 14, and Example 17, the light transmittance and elastic recovery were all excellent. Further, it was confirmed that when the silane coupling agent of the formula (2) was used from Example 9, even though the photoinitiator was relatively low, the adhesion was excellent and the solvent did not dissolve well in the pigment and there was no problem in reliability. On the other hand, Comparative Example 7 and Comparative Example 8 did not significantly deteriorate in optical characteristics, but they did not contain the alkali-soluble resin represented by Chemical Formula 1 or did not include the silane coupling agent represented by Chemical Formula 2, , And it was confirmed that the reliability and the elastic recovery rate were not good.

Claims (19)

(A) an alkali-soluble resin containing a monomer represented by the following formula (1), (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a silane coupling agent represented by the following formula Sensitive resin composition:
[Chemical Formula 1]

In this formula,
R1 is hydrogen or an alkyl or cycloalkyl group having 1-20 carbon atoms, with or without a heteroatom;
R2 is a single bond or an alkylene or cycloalkylene group having 1-20 carbon atoms with or without a heteroatom;
The R 1 and R 2 may be independently substituted with a hydroxy group.
(2)

In this formula,
Wherein n is an integer of 1 to 8, X is an acid anhydride, Y is -CH ₂ - or an oxygen atom, and R is a methyl group or an ethyl group. The method according to claim 1,
And X is succinic anhydride. The method of claim 2,
Wherein the compound of Formula 2 is represented by Formula 5 or Formula 6:
[Chemical Formula 5]

[Chemical Formula 6]

The method according to claim 1,
(D) the silane coupling agent represented by the general formula (2) is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the alkali-soluble resin containing the monomer represented by the general formula (1). The method according to claim 1,
(A) 5 to 60% by weight of an alkali-soluble resin containing a monomer represented by the formula (1), (B) 1 to 50% by weight of a photopolymerizable compound, (C) 0.01 to 100% by weight of a photopolymerization initiator 0.01 To 10% by weight, and (D) 0.01 to 5% by weight of a silane coupling agent represented by the general formula (2)
And (E) 60 to 90% by weight of a solvent based on the total weight of the total photosensitive resin composition. The method according to claim 1,
The photosensitive resin composition according to claim 1, further comprising a colorant. The method of claim 6,
Wherein the colorant comprises an organic black pigment, a violet pigment, and a blue pigment. The method of claim 7,
Wherein the organic black pigment comprises at least one selected from the group consisting of lactam black, aniline black, and perylene black. The method of claim 7,
Wherein the violet pigment comprises at least one selected from the group consisting of CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 31, CI Pigment Violet 37, and the like. Sensitive resin composition. The method of claim 7,
Wherein the blue pigment does not contain a center metal. 12. The method of claim 11, wherein the blue pigment is selected from the group consisting of C.I. Pigment Blue 16, Pigment Blue 60, C.I. Pigment Blue 63, C.I. Pigment Blue 66, and the like. The photosensitive resin composition according to claim 7, wherein the (B) photopolymerizable compound is a compound containing 4 to 12 functional groups. The photosensitive resin composition according to claim 7, wherein the organic black pigment, the violet pigment and the blue pigment in the colorant are mixed in a weight ratio of 1: 0.1 to 3.75: 0.25 to 5.0. The method of claim 7,
Wherein the colorant further comprises carbon black. [16] The photosensitive resin composition according to claim 14, wherein the organic black pigment, the violet pigment, the blue pigment and the carbon black in the colorant are mixed in a weight ratio of 1: 0.1 to 3.75: 0.25 to 5.0: 0.15 to 2.5. A photocurable pattern produced from the photosensitive resin composition according to any one of claims 1 to 15. 18. The method of claim 16,
Characterized in that the photocurable pattern is selected from the group consisting of an array planarizing film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, a black matrix pattern, a column spacer pattern and a black column spacer . A color filter comprising a color filter pattern or a black matrix pattern among the photocuring patterns of claim 17. An image display device comprising the color filter of claim 18.

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