TW201740202A - Photosensitive resin composition, photosensitive resin layer using the same and black column spacer - Google Patents

Abstract

Provided are a photosensitive resin composition including (A) an epoxy group-containing acryl-based binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant including a black organic colorant; and (E) a solvent, wherein the epoxy group-containing acryl-based binder resin is included in an amount of 1 wt% to 20 wt% based on a total amount of the photosensitive resin composition, a photosensitive resin layer manufactured using the photosensitive resin composition, and a black column spacer including the photosensitive resin layer.

Description

Photosensitive resin composition, photosensitive resin layer and black column spacer using same

The present invention relates to a photosensitive resin composition and a photosensitive resin layer and a black column spacer to which the same is applied.

It is necessary to use a photosensitive resin composition for producing a display device such as a color filter, a liquid crystal display material, an organic light emitting diode, or a display panel material. For example, a color filter such as a color liquid crystal display needs to have a black matrix at a boundary between colored layers such as red, green, blue, etc. to enhance display contrast or chromophore effect. This black matrix can be mainly formed of a photosensitive resin composition.

Recently, attempts have been made to use a black matrix material as a column spacer supporting two thin-film transistor (TFT) and color filter (C/F) substrates having a liquid crystal layer therebetween, and such column spacers It is called a black column spacer.

When the difference in pattern step and the basic characteristics such as compression displacement, elasticity recovery rate, breaking strength, etc. should be achieved by adjusting the exposure dose by the mask, the black column spacer can be Work properly.

However, the conventional photosensitive resin composition for black column spacers has only excellent light blocking properties but low ultraviolet (UV) transmittance and the like, and thus does not undergo internal curing before development, but only surface curing occurs, and thus It has the problem of serious deterioration of workability and low taper angle.

Therefore, research on the development of a novel photosensitive resin composition capable of solving this problem has been continued.

An embodiment of the present invention provides a photosensitive resin composition having improved process margin and high reliability.

Another embodiment of the present invention provides a photosensitive resin layer produced by applying the photosensitive resin composition.

A further embodiment of the present invention provides a black column spacer comprising the photosensitive resin layer.

An embodiment of the present invention provides a photosensitive resin composition comprising: (A) an epoxy group-containing acrylic binder resin; (B) a photopolymerizable monomer; (C) photopolymerization a starter; (D) a black colorant comprising a black organic colorant; and (E) a solvent, wherein the amount of the photosensitive resin composition is from 1% by weight to 20% by weight, based on the total amount of the photosensitive resin composition An epoxy-based acrylic adhesive resin.

The epoxy group-containing acrylic binder resin may comprise an epoxy group-containing acrylic repeating unit, and may comprise from 1% by weight to 40% by weight based on the total of the epoxy group-containing acrylic binder resin. The amount of the epoxy group-containing acrylic repeating unit in %.

The epoxy group-containing acrylic binder resin may comprise an epoxy group-containing acrylic repeating unit, and may comprise 10% by weight to 30% by weight based on the total of the epoxy group-containing acrylic binder resin. The amount of the epoxy group-containing acrylic repeating unit in %.

The epoxy group-containing acrylic binder resin may comprise at least two selected from the group consisting of epoxy group-containing acrylic binder resins (A-1), and the epoxy group-containing acrylic binder 15% by weight to 22% by weight of the epoxy group-containing acrylic repeating unit; the epoxy group-containing acrylic binder resin (A-2), and the epoxy group-containing acrylic acid The epoxy resin-containing acrylic repeating unit; and the epoxy group-containing acrylic adhesive resin (A-3), in the total amount of the binder resin, comprising the epoxy group-containing acrylic resin The total amount of the acrylic adhesive resin is from 28% by weight to 35% by weight based on the epoxy group-containing acrylic repeating unit.

The epoxy group-containing acrylic repeating unit may include at least one selected from the group consisting of the repeating units represented by Chemical Formula 1 to Chemical Formula 4. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4]

In Chemical Formula 1 to Chemical Formula 4, R ¹ to R ^{4 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ , L ² , L ⁴ and L ^{6 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene, substituted or unsubstituted C3 to C20 cycloalkyl extending alkyl, substituted or unsubstituted C6-C20 arylene group, or combinations thereof, L ³ and L ⁵ independently a substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 extended aryl, or a combination thereof X is a substituted or unsubstituted C3 to C20 alicyclic ring or a substituted or unsubstituted C6 to C20 aromatic ring, and * represents a point connecting the same or different atoms or formulas.

The epoxy group-containing acrylic binder resin may have a weight average molecular weight of from 2,000 g/m to 20,000 g/mol.

The black colorant may have a maximum transmittance in a wavelength region of 300 nm to 400 nm.

The black organic colorant may include a red pigment, a violet pigment, and a blue pigment.

The black colorant may further comprise a black inorganic colorant.

The black colorant may include the black organic colorant and the black inorganic colorant in a weight ratio of 10:1 to 30:1.

The photosensitive resin composition may include: 1% by weight to 20% by weight of (A) the epoxy group-containing acrylic adhesive resin; 0.1% by weight based on the total amount of the photosensitive resin composition Up to 10% by weight of (B) the photopolymerizable monomer; 0.1% by weight to 5% by weight of (C) the photopolymerization initiator; 30% to 60% by weight of (D) the black coloration And the balance of (E) the solvent.

The photosensitive resin composition may further comprise the following additives: malonic acid, 3-amino-1,2-propanediol, decane-based coupling agent, leveling agent, fluorine-based surfactant, radical polymerization Starting agent or a combination thereof.

Another embodiment of the present invention provides a photosensitive resin layer produced by applying the photosensitive resin composition.

The photosensitive resin layer may have a taper angle of greater than or equal to 20°.

A further embodiment of the present invention provides a black column spacer comprising the photosensitive resin layer.

Other embodiments of the invention are included in the detailed description which follows.

The photosensitive resin composition according to an embodiment contains a predetermined amount of the epoxy group-containing acrylic adhesive resin and thus a high taper angle can be achieved, and in addition, the use of the photosensitive resin composition according to an embodiment can be guaranteed The color shifting agent in the specific wavelength region and thus the optical density (OD) suitable for the black column spacer can be achieved.

In the following, embodiments of the invention are explained in detail. However, the embodiments are exemplary, and the invention is not limited thereto, and the invention is defined by the scope of the claims.

In the present specification, when no specific definition is provided, "alkyl" means C1 to C20 alkyl, the term "alkenyl" means C2 to C20 alkenyl, and the term "cycloalkenyl" means C3 to C20. Alkenyl, the term "heterocycloalkenyl" refers to C3 to C20 heterocycloalkenyl, the term "aryl" refers to C6 to C20 aryl, and the term "arylalkyl" refers to C6 to C20 arylalkyl, The term "alkylene" refers to C1 to C20 alkyl, the term "extended aryl" refers to C6 to C20 extended aryl, and the term "alkyl extended aryl" refers to C6 to C20 alkyl extended aryl, the term "extension" "Heteroaryl" means a C3 to C20 heteroaryl group, and the term "alkyleneoxy" means a C1 to C20 alkylene group.

In the present specification, the term "substituted", when not specifically defined otherwise, is substituted with at least one hydrogen substituted with a substituent selected from the group consisting of halogen (F, Cl, Br or I), hydroxyl group, C1 to C20. Alkoxy, nitro, cyano, amine, imine, azide, sulfhydryl, fluorenyl, hydrazono group, carbonyl, amine carbaryl, thiol, ester, ether a base, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group, or a combination thereof.

In the present specification, the term "hetero" means that at least one hetero atom selected from N, O, S and P is contained in the chemical formula when a specific definition is not additionally provided.

In the present specification, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic acid" when no specific definition is provided. And "methacrylic acid".

In the present specification, the term "combination" means mixing or copolymerization when a specific definition is not additionally provided.

In the present specification, when a specific definition is not additionally provided, an unsaturated bond means a bond containing another atom, such as a carbonyl bond, an azo bond, and a multiple bond between carbon-carbon atoms.

In the present specification, when a specific definition is not additionally provided, the maximum transmittance means a range of a range of 300 nm to 700 nm, regardless of a range of less than 300 nm and a range of more than 700 nm.

In the present specification, a "*" table refers to a point connecting the same or different atoms or chemical formulas when no specific definition is provided.

The photosensitive resin composition according to an embodiment comprises: (A) an epoxy group-containing acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant a black organic colorant; and (E) a solvent, wherein the epoxy group-containing acrylic adhesive resin is contained in an amount of from 1% by weight to 20% by weight based on the total of the photosensitive resin composition .

The photosensitive resin composition according to an embodiment can increase the crosslinking density of the binder resin and can achieve a high taper angle and an excellent process margin during the color filter process, because the total of the photosensitive resin composition The content of the epoxy group-containing acrylic binder resin is from 1% by weight to 20% by weight.

Hereinafter, each component will be specifically described.

( A Adhesive resin

The photosensitive resin composition according to an embodiment includes an acrylic binder resin, and the acrylic binder resin contains an epoxy group. The acrylic adhesive resin contains an epoxy group, and thus the crosslinking density of the acrylic adhesive resin can be improved, and an excellent process margin can be achieved.

Specifically, the epoxy group-containing acrylic adhesive resin according to an embodiment is contained in an amount of from 1% by weight to 20% by weight based on the total of the photosensitive resin composition. When the epoxy group-containing acrylic adhesive resin is contained in an amount of less than 1% by weight based on the total amount of the photosensitive resin composition, the amount of the epoxy group to be used is too small and thus may not be improved. The crosslinking density of the binder resin, and the relatively large amount of the photopolymerizable monomer contained, so that an excellent process margin may not be achieved, but when it contains more than 20 based on the total amount of the photosensitive resin composition When the epoxy group-containing acrylic adhesive resin is used in an amount of % by weight, the process margin is not sufficient, and the taper angle or the anti-aging stability may be deteriorated, and the photosensitive resin composition contains relatively few color formers. Therefore, the proper optical density (OD) of the black column spacer may not be achieved. The appropriate optical density of the black column spacer should be greater than or equal to 1 per 1 micron.

The epoxy group-containing acrylic binder resin contains an epoxy group-containing acrylic repeating unit, and may include 1% by weight to 40% by weight, for example, based on the total of the epoxy group-containing acrylic binder resin. An epoxy group-containing acrylic repeating unit in an amount of from 10% by weight to 30% by weight. When the epoxy group-containing acrylic repeating unit in the range is contained in the total amount of the epoxy group-containing acrylic binder resin, the taper angle of 20° or more can be maintained while applying The photosensitive resin layer produced by the photosensitive resin composition of one embodiment is stably patterned. For example, when the epoxy resin-containing acrylic repeating unit is contained in an amount of less than 1% by weight in the binder resin, the photosensitive resin layer may have a low taper angle of less than or equal to 20°, and thus may not be stable The pattern is patterned, and when the epoxy group-containing acrylic repeating unit is contained in an amount of more than 40% by weight, the photosensitive resin layer may not be stably patterned due to an increase in critical dimension (CD) deviation.

The epoxy group-containing acrylic adhesive resin (A) may contain at least two selected from the group consisting of epoxy group-containing acrylic binder resins (A-1), and the epoxy group-containing acrylic resin. 10% by weight to 22% by weight, for example, 15% by weight to 22% by weight, based on the total amount of the binder resin, of the epoxy group-containing acrylic repeating unit; the epoxy group-containing acrylic binder resin (A-2) , comprising from 23% by weight to 27% by weight, based on the total of the epoxy group-containing acrylic binder resin, of an epoxy group-containing acrylic repeating unit; and an epoxy group-containing acrylic binder resin (A) And -3) comprising 28% by weight to 35% by weight, for example 28% by weight to 30% by weight, based on the total of the epoxy group-containing acrylic binder resin, of the epoxy group-containing acrylic repeating unit. When the acrylic adhesive resin according to an embodiment includes more than two acrylic adhesive resins each containing various amounts of epoxy group-containing acrylic repeating units, both process margin and taper angle can be simultaneously improved.

For example, the epoxy group-containing acrylic repeating unit may include at least one selected from the group consisting of the repeating units represented by Chemical Formula 1 to Chemical Formula 4, but is not limited thereto. [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4]

In Chemical Formula 1 to Chemical Formula 4, R ¹ to R ^{4 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ , L ² , L ⁴ and L ^{6 are} independently a single bond, a substituted or unsubstituted C1 to C10 alkylene, substituted or unsubstituted C3 to C20 cycloalkyl extending alkyl, substituted or unsubstituted C6-C20 arylene group, or combinations thereof, L ³ and L ⁵ independently a substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 extended aryl, or a combination thereof And X is a substituted or unsubstituted C3 to C20 alicyclic ring or a substituted or unsubstituted C6 to C20 aromatic ring.

For example, the substituted or unsubstituted C3 to C20 cycloaliphatic ring may be a substituted or unsubstituted C3 to C20 cycloalkane, a substituted or unsubstituted bicyclohexane, and the like.

For example, X may be one selected from the group consisting of Chemical Formula 5-1 to Chemical Formula 5-7. [Chemical Formula 5-1] [Chemical Formula 5-2] [Chemical Formula 5-3] [Chemical Formula 5-4] [Chemical Formula 5-5] [Chemical Formula 5-6] [Chemical Formula 5-7]

For example, the epoxy group-containing acrylic repeating unit may be a repeating unit derived from an epoxy group-inducing monomer, for example, (meth) Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxy butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Glycidyl ether, etc., but not limited to this.

The epoxy group-containing acrylic adhesive resin according to an embodiment may be a copolymer of an epoxy group-inducing monomer and an ethylenic unsaturated monomer not containing an epoxy group.

The ethylenically unsaturated monomer not containing an epoxy group may be, for example, an ethylenically unsaturated compound containing at least one carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or the like; An aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl methyl ether or the like; an unsaturated carboxylate compound such as methyl (meth)acrylate, (methyl) Ethyl acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclomethacrylate Ester, phenyl (meth) acrylate, etc.; unsaturated carboxylic acid aminoalkyl ester compound, such as 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, etc. a vinyl carboxylate compound such as vinyl acetate, vinyl benzoate or the like; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl (meth)acrylate or the like; a vinyl cyanide compound such as (methyl) Acrylonitrile or the like; unsaturated guanamine compound, such as (meth) acrylamide, etc.; . These compounds may be used singly or in the form of a mixture of two or more.

The epoxy-containing acrylic adhesive resin may have from 1,000 g/m to 100,000 g/mole, for example from 2,000 g/m to 50,000 g/mole, for example from 2,000 g/m to 20,000 g/mole Weight average molecular weight. When the epoxy group-containing acrylic binder resin has a weight average molecular weight within the above range, properties such as chemical resistance, development margin, and the like of the black column spacer can be greatly optimized.

On the other hand, the photosensitive resin composition according to an embodiment contains only an acrylic binder resin as a binder resin and does not contain a cardo binder resin. When the photosensitive resin composition according to an embodiment contains a card-based adhesive resin, the taper angle of the pattern may be drastically lowered, and the process margin may be deteriorated.

( B ) photopolymerizable monomer

The photopolymerizable monomer may be a monofunctional ester or a polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

The photopolymerizable monomer can cause sufficient polymerization during exposure during the pattern forming process due to the ethylenically unsaturated double bond and form a pattern having excellent heat resistance, light resistance, and chemical resistance.

Specific examples of the photopolymerizable monomer may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A (meth) acrylate, pentaerythritol di(meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (methyl) Acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl Ether (meth) acrylate, trimethylolpropane tri(meth) acrylate, tris(meth) propylene decyl oxyphosphate, novolac epoxy (meth) acrylate, and the like.

Commercially available examples of photopolymerizable monomers are as follows. Monofunctional (meth) acrylates may include: Aronix M-101 ^® , M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.); KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic) Chemical Ind., Ltd.)). Examples of difunctional (meth) acrylates may include: Aronix M-210 ^® , M-240 ^® , M-6200 ^® (East Asia Synthetic Chemical Co., Ltd.), KAYARAD HDDA ^® , HX-220 ^® , R-604 ^® ( Nippon Kayaku Co., Ltd.), V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Co., Ltd.), etc. Examples of trifunctional (meth) acrylates may include: Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-7100 ^® , M-8030 ^® , M-8060 ^® (East Asia Synthetic Chemical Co., Ltd.), KAYARAD TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (Nippon Chemical Co., Ltd.), V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Yuki Kayaku Kogyo Co. Ltd.). These products may be used singly or in the form of a mixture of two or more.

The photopolymerizable monomer can be treated with an acid anhydride to improve developability.

The photopolymerizable monomer may be contained in an amount of 0.1% by weight to 10% by weight, for example, 1% by weight to 5% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer in the range is contained, the photopolymerizable monomer is sufficiently cured during exposure in the pattern forming process and has excellent reliability, and the developability of the alkaline developing solution is improved.

( C Photopolymerization initiator

The photopolymerization initiator may be a photopolymerization initiator commonly used in a photosensitive resin composition, such as an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, an anthraquinone compound, or Its combination.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and a third butyl group. Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-( 4-(Methylthio)phenyl)-2-morpholinylpropan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine 4-yl-phenyl)-butan-1-one and the like.

Examples of the benzophenone-based compound may be benzophenone, benzhydryl benzoate, benzhydryl methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated Benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylamino Benzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and the like.

Examples of the thioxanthone-based compound may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone and the like.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal or the like.

Examples of the triazine-based compound may be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloro) Methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-double (trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s -triazine, 2-(naphthol 1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthol-1-yl)-4,6- Bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperidinyl-s-triazine, 2-4-bis(trichloromethyl)-6-( 4-methoxystyryl)-s-triazine or the like.

An example of the lanthanoid compound may be an O-mercapto lanthanide compound, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1 -(O-ethylhydrazinyl)-1-[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]ethanone, O-ethoxycarbonyl- Α-oxyamino-1-phenylpropan-1-one and the like. A specific example of the O-mercapto lanthanide compound may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4- -Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-indole-O-benzoate, 1-(4- Phenylthiophenyl)-octane-1,2-dione-2-indole-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-B An acid ester, 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate or the like.

The photopolymerization initiator may further contain an oxazole compound, a diketone compound, a lanthanum borate compound, an azide compound, an imidazole compound, a biimidazole compound or the like in addition to the above compound.

The photopolymerization initiator can be used together with a photosensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transmitting its energy.

Examples of the photosensitizer may be tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-mercaptopropionate, dipentaerythritol tetrakis-mercaptopropionate or the like.

The photopolymerization initiator may be contained in an amount of 0.1% by weight to 5% by weight, for example, 0.1% by weight to 3% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator in the range is contained, excellent reliability can be ensured due to sufficient curing during exposure in the pattern forming process, and the pattern can have excellent resolution and close contact properties as well as excellent heat resistance. It has light resistance and chemical resistance, and can prevent the transmittance from deteriorating due to the non-reactive starter.

( D ) black colorant

The photosensitive resin layer formed by exposing, developing, and curing the photosensitive resin composition should have a high optical density to be used as a black column spacer. When the photosensitive resin composition contains only a black inorganic colorant as a black colorant, light in a wavelength region of 400 nm may not be used, and thus the process margin may be seriously deteriorated, and thus, according to an implementation The photosensitive resin composition of the example contains a black organic colorant as a colorant. The black organic colorant may be, for example, an intrinsic amine organic black, RGB black, RVB black or the like. The black colorant may contain, in addition to the black organic colorant, a black inorganic colorant or a combination thereof, such as nigrosine, phthalocyanine, titanium black, cyanine black, lignin black, carbon black, or a combination thereof.

RGB black, RVB black, or the like means a black pigment by mixing at least two color pigments of a red pigment, a green pigment, a blue pigment, a violet pigment, a yellow pigment, a violet pigment, and the like.

For example, the black organic colorant may include RVB black or the like including a red pigment, a violet pigment, and a blue pigment, and the black inorganic colorant may include carbon black or the like.

The black colorant may comprise a black organic colorant and a black inorganic colorant in a weight ratio of from 20:1 to 30:1, for example from 20:1 to 25:1.

As described above, when the black colorant contains only a black inorganic colorant such as carbon black, a high optical density can be obtained due to excellent light blocking properties, but a black inorganic colorant such as carbon black has an ultraviolet transmittance of 0%. Therefore, the photosensitive resin composition only undergoes surface curing during exposure without internal solidification, and thus the manufacturing margin can be deteriorated during subsequent development. Therefore, the photosensitive resin composition according to an embodiment may contain a black colorant capable of ensuring light blocking properties in the visible light region while ensuring transmittance in a region of 300 nm to 400 nm and thus sufficiently photocuring .

In other words, the black colorant in the photosensitive resin composition according to an embodiment can have the maximum transmittance in a wavelength region of 300 nm to 400 nm.

When a black organic colorant is used with a black inorganic colorant such as carbon black, specifically, a weight ratio of 10:1 to 30:1, for example 20:1 to 30:1, and for example 20:1 to 25:1 When used as a black colorant, the black colorant in the form of a mixture of a black organic colorant and a black inorganic colorant can be adjusted to have a maximum transmittance in a wavelength region of 300 nm to 400 nm.

On the other hand, the black colorant can be used together with a color calibrator such as an anthraquinone pigment, an anthraquinone pigment, an indigo pigment, an azo pigment, or the like.

Dispersing agents can be used together to improve the dispersion of black colorants such as pigments or color aligners. Specifically, a black colorant such as a pigment or a color aligner may be subjected to surface pretreatment with a dispersant, or a black colorant such as a pigment or a color aligner and a dispersant may be added together during preparation of the photosensitive resin composition.

The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant or the like. Specific examples of the dispersant may be a polyalkylene glycol and an ester thereof, a polyoxyalkylene group, a polyol ester alkylene oxide addition product, an alcohol alkylene oxide addition product, a sulfonate, a sulfonate, a carboxylate A carboxylate, an alkylguanamine alkylene oxide addition product, an alkylamine or the like, and may be used singly or in the form of a mixture of two or more.

Commercially available examples of dispersants may include DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, manufactured by BYK Co., Ltd. DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, etc.; by EFKA Chemicals Co., manufactured by EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc.; manufactured by Zeneka Co. Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, etc.; or PB711 or PB821 manufactured by Ajinomoto Inc. .

The dispersant may be contained in an amount of from 0.1% by weight to 15% by weight based on the total mass of the photosensitive resin composition. When the dispersant in the range is contained, the resin composition has excellent dispersion properties, and thus can have excellent stability, developability, and pattern forming ability during the manufacture of the black column spacer.

A black colorant such as a pigment can be pretreated with a water-soluble inorganic salt and a wetting agent. When a black pigment such as a pigment is pretreated, the primary particles of the pigment may become finer.

The pretreatment can be carried out by kneading a black colorant such as a pigment with a water-soluble inorganic salt and a wetting agent, and then filtering and washing the kneaded pigment.

Kneading can be carried out at a temperature ranging from 40 ° C to 100 ° C, and filtration and washing can be carried out by filtering the pigment after washing off the inorganic salt with water or the like.

Examples of the water-soluble inorganic salt may be sodium chloride, potassium chloride or the like, but are not limited thereto. The humectant can uniformly and pulverize the black colorant such as a pigment uniformly mixed with the water-soluble inorganic salt. Examples of the wetting agent include alkanediol monoalkyl ethers such as ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like; and alcohols such as ethanol, isopropanol, butanol, hexanol, Cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol polyethylene glycol, and the like. These humectants may be used singly or in the form of a mixture of two or more.

Specifically, a black colorant such as a pigment may be used in the form of a pigment dispersion containing a dispersant and an organic solvent, and the pigment dispersion may contain a solid pigment (black colorant), a dispersant, and an organic solvent. Herein, the solid pigment (black colorant) may be contained in an amount of from 8 to 30% by weight based on the total amount of the pigment dispersion. The pigment dispersion may be contained in an amount of from 5% by weight to 30% by weight, for example from 5% by weight to 20% by weight, for example from 5% by weight to 10% by weight, based on the total of the photosensitive resin composition. When the pigment dispersion in the range is included, the resolution and pattern linearity are improved.

A black colorant (for example, a pigment dispersion) may be contained in an amount of 30% by weight to 60% by weight, for example, 40% by weight to 55% by weight based on the total amount of the photosensitive resin composition. When a coloring agent (for example, a pigment dispersion) within the range is contained, brightness, color reproducibility, pattern curability, heat resistance, and close contact force are improved.

( E Solvent

The solvent is compatible with a pigment dispersion liquid containing a black colorant, an epoxy group-containing acrylic binder resin, a photopolymerizable monomer, and a photopolymerization initiator, but not with a pigment dispersion containing a black colorant. A material which reacts with an epoxy group-containing acrylic binder resin, a photopolymerizable monomer, and a photopolymerization initiator.

Examples of the solvent may include an alcohol such as methanol, ethanol, etc.; an ether such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran or the like; a glycol ether such as ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, etc.; cellosolve acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, etc.; Alcohol, such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, two Ethylene glycol diethyl ether or the like; propylene glycol alkyl ether acetate, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; ketones, such as methyl ethyl ketone, cyclohexanone , 4-hydroxy-4-methyl-2-pentanone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, 2-heptanone, etc.; saturated aliphatic monocarboxylic acid alkyl Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc.; lactates such as methyl lactate, ethyl lactate, etc.; alkyl oxyacetates, such as methyl oxyacetate, Ethyl oxyacetate, butyl oxyacetate, etc.; alkyl alkoxyacetate, such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate or the like; alkyl 3-oxopropionate such as methyl 3-oxypropionate, ethyl 3-oxypropionate or the like; alkyl 3-alkoxypropionate, for example Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.; alkyl 2-oxopropionate For example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.; alkyl 2-alkoxypropionate, such as 2-methoxypropionic acid Ester, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc.; 2-oxy-2-methylpropionate, such as 2-oxo Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, etc.; 2-alkoxy-2-methylpropanoic acid alkyl of monooxymonocarboxylic acid alkyl ester Esters such as methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.; esters such as 2-hydroxyethyl propionate, 2-hydroxyl propionate -2-methylethyl ester, hydroxyl acetate Butyrate, methyl 2-hydroxy-methyl and the like; ketones esters, such as acetone and ethyl. In addition, high boiling solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-di can also be used. Methylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetamidine, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1 - decyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, benzene Cellulose acetate and the like.

In view of miscibility and reactivity, a glycol ether such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether or the like can be preferably used; Ethyl acetate, such as ethyl cellosolve acetate; esters, such as 2-hydroxyethyl propionate; carbitol, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetate For example, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.

The solvent is used in the balance (for example, 20% by weight to 90% by weight) based on the total amount of the photosensitive resin composition. When a solvent in the range is contained, the photosensitive resin composition may have an appropriate viscosity, thereby improving the coating characteristics of the black column spacer.

( F Other additives

The photosensitive resin composition may further comprise the following additives: malonic acid; 3-amino-1,2-propanediol; a decane-based coupling agent; a leveling agent; a fluorine-based surfactant; a radical polymerization initiator; combination.

The decane coupling agent may have the following reactive substituents to improve the intimate contact properties with the substrate: vinyl, carboxyl, methacryloxy, isocyanate, epoxy, and the like.

Examples of the decane coupling agent may include trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate. Propyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These decane-based coupling agents may be used singly or in the form of a mixture of two or more.

The decane-based coupling agent may be contained in an amount of from 0.01 part by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the decane-based coupling agent in the range is contained, the close contact property, the storage property, and the like can be improved.

The photosensitive resin composition may further contain a fluorine-based surfactant or a leveling agent to improve coating properties and prevent defects as necessary.

The fluorine-based surfactant or leveling agent may be a commercially available fluorine-based surfactant or leveling agent, such as BM-1000 ^® , BM-1100 ^{® ,} etc. (BM Chemie Inc.); MEGAFACE ) F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^{® ,} etc. (Dainippon Ink Kagaku Kogyo Co., Ltd.); FULORAD FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^{® ,} etc. (Sumitomo 3M Co., Ltd.); SURFLON S-112 ^® , S-113 ^® , S -131 ^® , S-141 ^® , S-145 ^{® ,} etc. (Asahi Glass Co., Ltd.); SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® and SF-8428 ^®, etc. (manufactured by Toray Silicone Co., Ltd. -one (Toray Silicone Co., Ltd.)) .

The fluorine-based surfactant or leveling agent may be used in an amount of from 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When a fluorine-based surfactant or leveling agent in the range is included, excellent wetting and coating uniformity on an indium zinc oxide (IZO) substrate or a glass substrate can be ensured, and no generation can be caused. stain.

Further, the photosensitive resin composition may contain a predetermined amount of other additives (for example, an antioxidant, a stabilizer, etc.) unless other additives deteriorate the properties of the photosensitive resin composition.

Another embodiment of the present invention provides a photosensitive resin layer produced by applying the photosensitive resin composition.

The pattern of the photosensitive resin layer (for example, the photosensitive resin layer) may have a taper angle of greater than or equal to 20 (for example, greater than or equal to 20 and less than or equal to 60).

Another embodiment of the present invention provides a black column spacer manufactured by exposing and developing (for example, exposing, developing, and curing) a photosensitive resin composition.

A method of manufacturing a black column spacer is as follows.

(1) Coating and film formation

The photosensitive resin composition is coated on a substrate (for example, a glass substrate or an indium zinc oxide substrate) subjected to a predetermined pretreatment by a spin coating or a slit coating method, a roll coating method, a screen printing method, a coater method, or the like. The photosensitive resin composition is heated at 70 ° C to 100 ° C for 1 minute to 10 minutes by a vacuum dry (VCD) process to remove the solvent, thereby forming a photosensitive resin layer. .

(2) exposure

The photosensitive resin film is patterned by: arranging a mask composed of a half tone portion for achieving a black matrix pattern and a full tone for achieving a pillar spacer pattern, and then Irradiating actinic ray in the range of 200 nm to 500 nm. Irradiation is performed by using, for example, a mercury lamp having a low pressure, a high pressure, or an ultrahigh pressure, a metal halide lamp, an argon laser, or the like. X-rays, electron beams, and the like can also be used.

When a high pressure mercury lamp is used, the exposure process uses, for example, a light dose of about 500 millijoules per square centimeter or less than 500 millijoules per square centimeter (using a 365 nanometer sensor). However, the light dose may vary depending on the kind of each component, the combination ratio thereof, and the dry film thickness.

(3) Development

After the exposure process, the exposed film is developed using an alkaline aqueous solution by dissolving and removing excess portions other than the exposed portion to form a pattern.

(4) Post processing

The developed image pattern can be post-heated to achieve excellent quality in terms of heat resistance, photoresist, close contact properties, crack resistance, chemical resistance, high strength, storage stability, and the like.

Another embodiment of the present invention provides a color filter including a black pillar spacer.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the examples are not to be construed as limiting the scope of the invention in any way. (example)

(Preparation of photosensitive resin composition)

Instance 1 To instance 4 And comparative examples 1 To comparative example 5

Each of the photosensitive resin compositions according to Examples 1 to 4 and Comparative Examples 1 to 5 was prepared to have the compositions shown in Table 1 by using the following components, respectively.

Specifically, the amount of the photopolymerization initiator is accurately weighed, a solvent is added thereto, and the mixture is sufficiently stirred until the photopolymerization initiator is completely dissolved in the solvent (greater than or equal to 30 minutes). . Then, a binder resin and a photopolymerizable monomer were sequentially added thereto, and the obtained mixture was stirred again for 1 hour. Subsequently, a coloring agent (pigment dispersion) was placed therein, other additives were added thereto, and finally the obtained mixture was stirred for 2 hours or more to prepare a photosensitive resin composition.

Each component used in the photosensitive resin composition is as follows.

( A ) Adhesive Resin (A-1) an epoxy-based acrylic adhesive resin (weight average molecular weight: 6,000 g/mole, RY-20, Showa Denko KK), as described The epoxy resin-containing repeating unit derived from glycidyl methacrylate was contained in an amount of 20% by weight based on the total amount of the binder resin. (A-2) an epoxy-based acrylic adhesive resin (weight average molecular weight: 6,500 g/mole, RY-48, Showa Denko Co., Ltd.), containing 30 parts by weight based on the total amount of the binder resin The amount of the epoxy group-containing acrylic acid repeating unit (A-3) induced by Cyclomer M100 (3,4-epoxycyclohexylmethyl (meth) acrylate) contains an epoxy group. Acrylic binder resin (weight average molecular weight: 5,500 g/mole, RY-20-6, Showa Denko Co., Ltd.), containing 25% by weight of the total amount of the binder resin Epoxy-containing repeating unit (A-4) card-based adhesive resin (V259ME, Nippon Steel & Sumikin Chemical (NSSC) Co., Ltd.)

( B ) Photopolymerizable monomer Dipentaerythritol hexa(meth)acrylate (DPHA, Nippon Chemical Co., Ltd.)

( C ) Photopolymerization initiator lanthanide initiator 1 (NCI-831, ADEKA Corp.)

( D ) Black colorant (D-1) red mill base (CI-IM-R179) dispersion (SAKATA Corp.) (D-2) violet paint paste (CI-IM- R29) Dispersion (Sakada Co., Ltd.) (D-3) Blue lacquer (CI-IM-R15:6) dispersion (Sakada Co., Ltd.) (D-4) Carbon black lacquer (CI-IM-R179) dispersion (TOKUSIKI Co., Ltd.)

( E ) Solvent (E-1) Propylene Glycol Monomethyl Ether Acetate (PGMEA) (E-2) Diethylene Glycol Methyl Ether

( F ) Other additives Leveling agent (F-554 (10% diluted solution), DIC Co., Ltd.) [Table 1] (Unit: gram)

(assessment)

Process margin and cone angle

According to the coating machine (MIKASA Co., Ltd.), the spin coating method, the slit coating method, the roll coating method, the screen printing method, the coater method, and the like are used on the glass substrate according to Example 1 to The photosensitive resin compositions of Example 4 and Comparative Example 1 to Comparative Example 5 were respectively coated to have a predetermined thickness, and the photosensitive resin composition was heated on a hot plate at 70 ° C to 100 ° C for 1 minute to 10 minutes. (drying) to remove the solvent and obtain a film. The film was exposed by using an exposure device (HB-50110AA, Ushio Inc.) and a halftone mask having an exposure dose of 50 mJ/cm 2 . Subsequently, the film was developed in a 0.2% aqueous KOH solution using a developing device (SSP-200, SVS Corp.) for 150 seconds, and hard-bake in an oven at 230 ° C. (or post-baking) for 30 minutes to obtain a patterned photosensitive resin film sample. Regarding the patterned sample, the taper angle thereof was measured by using a scanning electron microscope (SEM), and the results are shown in Table 2 and FIGS. 1 to 6.

In addition, the process margin was evaluated by measuring the height of the halftone region before and after the exposure in the exposure using the halftone mask, and the results are shown in Table 3. [Table 2] [table 3]

Referring to Tables 2 and 3 and FIGS. 1 to 6, according to an embodiment, the epoxy group-containing acrylic adhesive resin is contained in an amount of from 1% by weight to 20% by weight based on the total amount of the photosensitive resin composition (but not The photosensitive resin composition of the card-based adhesive resin) provides a patterned photosensitive resin layer having a taper angle of 20 or more, and exhibits an excellent process margin compared to other photosensitive resin compositions. .

Since the epoxy group-containing acrylic binder resin further contains an epoxy group, the pattern of the patterned photosensitive resin layer has a higher taper angle.

Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not to be construed as limited Various modifications and equivalent configurations. Therefore, the above embodiments are to be considered as illustrative and not restrictive.

no

1 to 6 are scanning electron microscope (SEM) photographs of photosensitive resin layers produced by using the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2, respectively.

Claims (15)

A photosensitive resin composition comprising (A) an epoxy group-containing acrylic binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a black colorant comprising a black organic a colorant; and (E) a solvent, wherein the epoxy group-containing acrylic binder resin is contained in an amount of from 1% by weight to 20% by weight based on the total of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the epoxy group-containing acrylic binder resin comprises an epoxy group-containing acrylic repeating unit, and the epoxy group-containing acrylic resin The epoxy group-containing acrylic repeating unit is contained in an amount of from 1% by weight to 40% by weight based on the total of the binder resin. The photosensitive resin composition according to claim 1, wherein the epoxy group-containing acrylic binder resin comprises an epoxy group-containing acrylic repeating unit, and the epoxy group-containing acrylic resin The epoxy group-containing acrylic repeating unit is contained in an amount of 10% by weight to 30% by weight based on the total amount of the binder resin. The photosensitive resin composition according to claim 2, wherein the epoxy group-containing acrylic binder resin comprises at least two selected from the group consisting of epoxy group-containing acrylic binder resins ( A-1), comprising 15% by weight to 22% by weight, based on the total amount of the epoxy group-containing acrylic binder resin, of an epoxy group-containing acrylic repeating unit, an epoxy group-containing acrylic binder The resin (A-2), comprising 23% by weight to 27% by weight, based on the total amount of the epoxy group-containing acrylic binder resin, of an epoxy group-containing acrylic repeating unit, and an epoxy group-containing acrylic acid The binder resin (A-3) contains 28% by weight to 35% by weight of the epoxy group-containing acrylic repeating unit based on the total of the epoxy group-containing acrylic binder resin. The photosensitive resin composition according to claim 2, wherein the epoxy group-containing acrylic repeating unit contains at least one selected from the group consisting of the repeating units represented by Chemical Formula 1 to Chemical Formula 4: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] Wherein, in Chemical Formula 1 to Chemical Formula 4, R ¹ to R ^{4 are} independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group, and L ¹ , L ² , L ⁴ and L ^{6 are} independently a single bond. , substituted or unsubstituted C1 to C10 alkylene, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 extended aryl, or a combination thereof, L ³ And L ^{5 are} independently substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C3 to C20 cycloalkyl, substituted or unsubstituted C6 to C20 extended aryl, or In combination, X is a substituted or unsubstituted C3 to C20 alicyclic ring or a substituted or unsubstituted C6 to C20 aromatic ring, and * represents a point linking the same or different atoms or formulas. The photosensitive resin composition according to claim 1, wherein the epoxy group-containing acrylic binder resin has a weight average molecular weight of from 2,000 g/mol to 20,000 g/mol. The photosensitive resin composition according to claim 1, wherein the black colorant has a maximum transmittance in a wavelength region of from 300 nm to 400 nm. The photosensitive resin composition according to claim 1, wherein the black organic colorant comprises a red pigment, a violet pigment, and a blue pigment. The photosensitive resin composition according to claim 1, wherein the black colorant further comprises a black inorganic colorant. The photosensitive resin composition according to claim 9, wherein the black colorant comprises the black organic colorant and the black inorganic colorant in a weight ratio of 10:1 to 30:1. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition contains 1% by weight to 20% by weight of (A) based on the total amount of the photosensitive resin composition. The epoxy group-containing acrylic binder resin; 0.1% by weight to 10% by weight of (B) the photopolymerizable monomer; 0.1% by weight to 5% by weight of the (C) photopolymerization initiator; 30% by weight to 60% by weight of (D) the black colorant; and the balance of (E) the solvent. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises the following additives: malonic acid, 3-amino-1,2-propanediol, decane coupling agent, and adjustment A flat agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof. A photosensitive resin layer produced by using the photosensitive resin composition according to any one of claims 1 to 12. The photosensitive resin layer according to claim 13, wherein the photosensitive resin layer has a taper angle of 20 or more. A black column spacer comprising the photosensitive resin layer as described in claim 14.