KR102025359B1 - Photosensitive resin composition, black column spacerusing the same and color filter - Google Patents

Abstract

(A) a colorant having a maximum transmittance from 360 nm to 410 nm; (B) a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm; (C) photopolymerizable monomer; And (D) a photosensitive resin composition comprising a solvent, a black column spacer prepared using the photosensitive resin composition, and a color filter including the black column spacer.

Description

Photosensitive resin composition, black column spacer and color filter using same {PHOTOSENSITIVE RESIN COMPOSITION, BLACK COLUMN SPACERUSING THE SAME AND COLOR FILTER}

The present disclosure relates to a photosensitive resin composition, a black column spacer manufactured using the same, and a color filter including the black column spacer.

The photosensitive resin composition is an essential material for the production of display elements such as color filters, liquid crystal display materials, organic light emitting elements, and display panel materials. For example, a color matrix such as a color liquid crystal display requires a black matrix at a boundary between colored layers such as red, green, and blue in order to increase display contrast and color development effects. The black matrix is mainly formed of the photosensitive resin composition.

Recently, efforts have been made to use the black matrix material as a column spacer for supporting between two TFTs and a C / F substrate which exist with a liquid crystal layer interposed therebetween. The column spacer is called a black column spacer.

In the case of the black column spacer, a pigment is selected to have a high optical density (OD) for the purpose of light shielding, but in this case, UV transmittance is also lowered, which is disadvantageous for photocuring. In particular, carbon black, which is the most common pigment of black column spacer, has excellent light blocking property, but has a UV transmittance of 0, resulting in only black surface curing and developing process without internal curing. There is this.

Therefore, studies to develop a photosensitive resin composition for a black column spacer that can solve the above disadvantages continue.

One embodiment is to provide a photosensitive resin composition that can ensure the light-shielding properties in the visible light region and at the same time secure the transmittance in the ultraviolet region.

Another embodiment is to provide a black column spacer prepared using the photosensitive resin composition.

Another embodiment is to provide a color filter including the black column spacer.

One embodiment includes (A) a colorant having a maximum transmittance from 360 nm to 410 nm; (B) a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm; (C) photopolymerizable monomer; And (D) provides a photosensitive resin composition comprising a solvent.

The colorant may comprise a pigment, a dye or a combination thereof.

The pigment may be an organic pigment.

The organic pigment may be a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment.

The photopolymerization initiator may have a maximum absorbance at 370 nm to 410 nm.

The photopolymerization initiator may be an oxime compound.

The photosensitive resin composition may further include a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm.

The photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be a triazine compound or an acetophenone compound.

The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm and the photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be included in a weight ratio of 1: 4 to 4: 1, respectively.

The photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be included in an amount of 0.01 wt% to 5 wt% based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further include (E) binder resin.

The binder resin may include an acrylic binder resin, a cardo binder resin, or a combination thereof.

The photosensitive resin composition, 5% by weight to 50% by weight of the colorant relative to the total amount of the photosensitive resin composition; 0.1 wt% to 5 wt% of the photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm; 1 wt% to 10 wt% of the photopolymerizable monomer; 5 wt% to 20 wt% of the binder resin; And the balance of the solvent.

The photosensitive resin composition may further include an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

Another embodiment provides a black column spacer manufactured by exposing and developing the photosensitive resin film.

Yet another embodiment provides a color filter including the black column spacer.

Other details of aspects of the invention are included in the following detailed description.

The photosensitive resin composition according to an embodiment has both light blocking properties in the visible region and light transmittance in the ultraviolet region, thereby providing a black column spacer having excellent light blocking properties and process margins in the visible region and a color filter including the same. do.

1 is a graph showing the absorbance according to the wavelength of NCI831, a photopolymerization initiator.
2 is a graph showing the absorbance according to the wavelength of TEB, a photopolymerization initiator.
Figure 3 is a graph showing the absorbance according to the wavelength of the photopolymerization initiator OXE01.
Figure 4 is a graph showing the transmittance according to the wavelength of the pigment dispersion containing all 849R, 100Y and 614B.
Figure 5 is a graph showing the transmittance according to the wavelength of the colorant containing a pigment dispersion and a dye containing all 849R, 100Y and 614B.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, and "cycloalkenyl group" means a C3 to C20 cycloalkenyl group. , "Heterocycloalkenyl group" means a C3 to C20 heterocycloalkenyl group, "aryl group" means a C6 to C20 aryl group, "arylalkyl group" means a C6 to C20 arylalkyl group, "alkylene group" Is a C1 to C20 alkylene group, and "arylene group" refers to a C6 to C20 arylene group, and "alkylarylene group" refers to a C6 to C20 alkylarylene group, and a "heteroarylene group" to C3 to C20 hetero It means an arylene group and a "alkoxy group" means a C1-C20 alkoxylene group.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group, Azido, amidino, hydrazino, hydrazono, carbonyl, carbamyl, thiol, ester, ether, carboxyl or salts thereof, sulfonic acid or salts thereof, phosphoric acid or salts thereof, C1 To C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C20 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, C2 to C20 heterocycloalkyl group, C2 To C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C20 heteroaryl group, or a combination thereof.

In addition, unless otherwise specified in the present specification, "hetero" means that at least one hetero atom of N, O, S, and P is included in a chemical formula.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

Unless otherwise stated herein, "combination" means mixed or copolymerized.

Unless stated otherwise in the present specification, unsaturated bonds include not only multiple bonds between carbon and carbon atoms, but also include other molecules such as carbonyl bonds, azo bonds, and the like.

In the present specification, the cardo-based resin refers to a resin in which at least one functional group selected from the group consisting of Chemical Formulas 1-1 to 1-11 is included in the backbone of the resin.

Unless otherwise specified herein, the maximum transmittance and maximum absorbance ranges refer to a range within the 300 nm to 700 nm range, and the ranges below 300 nm and above 700 nm are not considered.

Also, unless stated otherwise in the present specification, "*" means a part connected with the same or different atoms or formulas.

The photosensitive resin composition according to one embodiment includes (A) a colorant; (B) photoinitiator; (C) photopolymerizable monomer; And (D) a solvent, wherein the colorant has a maximum transmittance at 360 nm to 410 nm, and the photopolymerization initiator has a maximum absorbance at 360 nm to 410 nm.

The photosensitive resin composition used for manufacturing a conventional black matrix or black column spacer includes a black pigment having a high optical density, such as carbon black, which is an inorganic pigment, in order to have excellent light blocking property. However, black pigments such as carbon black have excellent light shielding properties, but have a problem in that the process margin cannot be large because the transmittance in the ultraviolet region is remarkably poor.

However, the photosensitive resin composition according to the embodiment includes a colorant having a maximum transmittance at 360 nm to 410 nm and a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm, thereby providing a black column spacer having both photosensitivity and light blocking properties. Can provide.

Each component is demonstrated concretely below.

(A) colorant

The colorant may include a pigment, a dye, or a combination thereof having high transmittance in the ultraviolet region and at the same time high light shielding in the visible region.

For example, the colorant has a maximum transmittance at 300 nm to 410 nm, such as 360 nm to 410 nm.

In the preparation of the photosensitive resin composition, when the colorant is used together with a photoinitiator having a maximum absorbance at 300 nm to 410 nm, for example, 360 nm to 410 nm, which is described later, excellent light shielding property is realized in the visible region and at the same time, Mars can also be implemented.

For example, the colorant may include an organic pigment, a dye, or a combination thereof.

For example, the organic pigment may be a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment, and a yellow pigment. For example, the organic pigment may be a combination of red pigment, green pigment and blue pigment. For example, the organic pigment may be a combination of red pigment, blue pigment and yellow pigment.

Inorganic pigments such as aniline black, perylene black, titanium black, and carbon black can be used as colorants, but excellent light shielding properties can be achieved, but the development process is performed under surface hardening without internal hardening, thereby maximizing process margin. Can not.

The red pigment is CI red pigment 179, CI red pigment 254, CI red pigment 255, CI red pigment 264, CI red pigment 270, CI red pigment 272, CI red pigment 177, CI red pigment within the Color Index. 89 and the like, and these may be used alone or in combination of two or more, but is not necessarily limited thereto.

The green pigment is obtained by C.I. Green pigment 59, C.I. Green pigment 58, C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 may be used, and these may be used alone or in combination of two or more, but is not necessarily limited thereto.

The blue pigment has a color index of C.I. Blue pigment 15: 6, C.I. Blue pigment 15: 0, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I blue pigment 15: 6, C.I. Blue pigment 16 and the like can be used, these may be used alone or in combination of two or more, but is not necessarily limited thereto.

The yellow pigment is a C.I. Isoindolin pigments such as yellow pigment 139 and the like, C.I. Quinophthalone pigments such as yellow pigment 138 and the like, C.I. Nickel complex pigments such as yellow pigment 150 and the like, C.I. Yellow pigment 100 and the like can be used, these may be used alone or in combination of two or more, but is not necessarily limited thereto.

When using a pigment as the colorant, a dispersant may be used together to disperse the pigment. Specifically, the pigment may be used by surface treatment with a dispersant in advance, or may be used by adding a dispersant together with the pigment when preparing the composition.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonates, carboxylic acid esters, and carboxylates. , Alkyl amide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more thereof.

Examples of commercially available products of the dispersant include, for example, DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. of EFKA Chemical Co., Ltd .; Zenspera Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like; Or PB711, PB821 from Ajinomoto.

The dispersant may be included in an amount of 0.1 wt% to 15 wt% based on the total amount of the photosensitive resin composition. When the dispersant is included in the above range, according to the excellent dispersibility of the composition, it is excellent in stability, developability and patternability when preparing the black column spacer.

The pigment may be used after pretreatment using a water-soluble inorganic salt and a humectant. When the pigment is used after the pretreatment, the average particle diameter of the pigment can be refined.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 ° C to 100 ° C, and the filtration and washing may be performed by washing the inorganic salt with water and the like followed by filtration.

Examples of the water-soluble inorganic salts include sodium chloride and potassium chloride, but are not limited thereto. The wetting agent serves as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed so that the pigment can be easily pulverized. Examples thereof include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and the like. Alkylene glycol monoalkyl ethers; Alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol, and the like, and the like, and these may be used alone or in combination of two or more thereof.

The pigment passed through the kneading step may have an average particle diameter of 5 nm to 200 nm, such as 5 nm to 150 nm. When the average particle diameter of a pigment is in the said range, stability in a pigment dispersion liquid is excellent and there is no fear of the resolution fall of a pixel.

Specifically, the pigment may be used in the form of a pigment dispersion containing the dispersant and the solvent described later, the pigment dispersion may include a solid pigment, a dispersant and a solvent. The solid pigment may be included in an amount of 5 wt% to 20 wt%, such as 8 wt% to 15 wt%, based on the total amount of the pigment dispersion.

The colorant may be included in an amount of 5 wt% to 50 wt%, such as 5 wt% to 45 wt%, based on the total amount of the photosensitive resin composition. When the colorant is included in the above range, the coloring effect and the developing performance is excellent.

(B) Photopolymerization Initiator

The photopolymerization initiator has a maximum absorbance at 360 nm to 410 nm. For example, the photopolymerization initiator may have a maximum absorbance at 370 nm to 410 nm.

In preparing the photosensitive resin composition, when the photopolymerization initiator is used together with the above-described colorant, internal curing may be efficiently performed while showing black color, thereby maximizing process margins.

In addition, the photosensitive resin composition according to an embodiment may further include a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm, together with the photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm.

The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm and the photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm each have a weight ratio of 1: 4 to 4: 1, such as a weight ratio of 1: 3 to 3: 1. May be included. When the photopolymerization initiator having the maximum absorbance in different ranges is included in the weight ratio range, the wavelength band of the exposure machine can be used more broadly, which is advantageous for photocuring.

As the photopolymerization initiator, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, an acetophenone compound or a combination thereof can be used.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone compound include thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2- Chlorothioxanthone etc. are mentioned.

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

Examples of the triazine-based compound include 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 (trichloromethyl) -s-triazine , 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine , 2-biphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4 -Bis (trichloromethyl) -6-piperonyl-s-triazine, 2-4-bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, 2- [4 -(4-ethylphenyl) -phenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine etc. are mentioned.

Examples of the oxime compound include O-acyl oxime compound, 2- (O-benzoyl oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyl oxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one and the like Can be used. Specific examples of the O-acyl oxime compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane- 1-one, 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butane-1-one oxime- O-acetate can be used.

For example, the photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm may be an oxime compound. For example, the photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm may be an O-acyl oxime compound, but is not limited thereto.

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt -Butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

For example, the photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm may be a triazine compound or an acetophenone compound, but is not limited thereto.

In addition to the above compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator may be used together with a photosensitizer which causes a chemical reaction by absorbing light and transferring energy after being excited.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3 mercaptopropionate, and the like. Can be mentioned.

The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm may be included in an amount of 0.1 wt% to 5 wt%, such as 0.1 wt% to 3 wt%, based on the total amount of the photosensitive resin composition, and maximum absorbance at 310 nm to 360 nm. The photopolymerization initiator having may be included in an amount of 0.01 wt% to 5 wt%, such as 0.01 wt% to 3 wt%, based on the total amount of the photosensitive resin composition. For example, the photosensitive resin composition according to one embodiment may include 0.11 wt% to 10 wt%, such as 0.11 wt% to 6 wt%, of the photopolymerization initiator. When the photopolymerization initiator is included in the above range, curing occurs during exposure in the pattern forming process to obtain excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, excellent resolution and adhesion, and unreacted initiator. The fall of the transmittance | permeability can be prevented.

(C) Photopolymerizable  Monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may cause sufficient polymerization during exposure in the pattern forming process to form a pattern having excellent heat resistance, light resistance, and chemical resistance.

The photopolymerizable monomer is, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di ( Meta) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth) arc Acrylate, trimethylolpropane may be a tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a combination thereof.

Examples of commercially available products of the photopolymerizable monomer are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, doah Gosei cultivating the T (weeks)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®, and the like; Nihon Kayaku Co., Ltd., KAYARAD TC-110S ^® , TC-120S ^®, etc .; Osaka yukki cultivate may be a T (weeks)社of ^{V-158 ®, V-2311} ® and the like. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei cultivating the T (weeks)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; The V-260 ^® , V-312 ^® and V-335 HP ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei the cultivating T (weeks)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nihon Kayaku Co., Ltd. KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. The above products can be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 1 wt% to 10 wt%, such as 1 wt% to 8 wt%, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the above range, curing occurs sufficiently during exposure in the pattern forming process, thereby providing excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion.

(E) Binder Resin

The photosensitive resin composition according to one embodiment may further include a binder resin. For example, the binder resin may include cardo-based binder resin, acrylic binder resin, or a combination thereof.

When the binder resin in the photosensitive resin composition is a cardo-based binder resin, the developability of the composition is excellent, the sensitivity at the time of photocuring is good, and the fine pattern formability is excellent. In addition, when the cardo-based binder resin is used, the reliability of the black column spacer can be ensured.

The cardo-based binder resin may include a repeating unit represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

R ¹¹ and R ¹² are each independently a hydrogen atom or a substituted or unsubstituted (meth) acryloyloxyalkyl group,

R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom or a substituted or unsubstituted C1 to C20 alkyl group,

Z ¹ is a single bond, O, CO, SO ₂ , CR ⁷ R ⁸ , SiR ⁹ R ¹⁰ , wherein R ⁷ to R ¹⁰ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group, or Any one of the linking groups represented by Formula 1-1 to Formula 1-11,

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

(In Chemical Formula 1-5,

R ^a is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ or a phenyl group.)

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

Z ² is an acid dianhydride residue,

m1 and m2 are each independently an integer of 0-4.

The cardo-based binder resin may include a functional group represented by Formula 2 at at least one of both ends.

[Formula 2]

In Chemical Formula 2,

Z ³ may be represented by the following Chemical Formulas 2-1 to 2-7.

[Formula 2-1]

(In Formula 2-1, R ^b and R ^c are each independently a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, ester group or ether group.)

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

(In Formula 2-5, R ^d is O, S, NH, substituted or unsubstituted C1 to C20 alkylene group, C1 to C20 alkylamine group or C2 to C20 alkenylamine group.)

[Formula 2-6]

[Formula 2-7]

The cardo-based binder resin may be, for example, a fluorene-containing compound such as 9,9-bis (4-oxyranylmethoxyphenyl) fluorene; Benzene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid anhydride, biphenyl tetracarboxylic acid anhydride, benzophenone tetracarboxylic acid anhydride, pyromellitic di anhydride, cyclobutanetetracarboxylic acid anhydride, perylene tetracarboxylic acid anhydride Anhydride compounds, such as tetrahydrofuran tetracarboxylic acid anhydride and tetrahydrophthalic anhydride; Glycol compounds such as ethylene glycol, propylene glycol and polyethylene glycol; Alcohol compounds such as methanol, ethanol, propanol, n-butanol, cyclohexanol and benzyl alcohol; Solvent compounds such as propylene glycol methyl ethyl acetate and N-methylpyrrolidone; Phosphorus compounds such as triphenylphosphine; And amine or ammonium salt compounds such as tetramethylammonium chloride, tetraethylammonium bromide, benzyldiethylamine, triethylamine, tributylamine, benzyltriethylammonium chloride, and the like.

The weight average molecular weight of the cardo-based binder resin may be 500 g / mol to 50,000 g / mol, such as 1,000 g / mol to 30,000 g / mol. When the weight average molecular weight of the cardo-based binder resin is within the above range, the pattern is well formed without a residue when the black column spacer is manufactured, there is no loss of the film thickness during development, and a good pattern may be obtained.

The cardo-based binder resin may be included in an amount of 5 wt% to 20 wt%, such as 5 wt% to 15 wt%, based on the total amount of the photosensitive resin composition. When the cardo-based binder resin is included in the above range, excellent sensitivity, developability, resolution, and straightness of the pattern may be obtained.

The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin including one or more acrylic repeating units.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, such as 10 wt% to 40 wt%, based on the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the acrylic binder resin include acrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited to these, alone or two or more thereof. It can also mix and use.

The acrylic binder resin may be included in an amount of 1 wt% to 20 wt%, such as 1 wt% to 15 wt%, such as 1 wt% to 10 wt%, based on the total amount of the photosensitive resin composition. When the acrylic binder resin is included in the above range, excellent sensitivity, developability, resolution, and straightness of the pattern may be obtained.

On the other hand, the photosensitive resin composition according to an embodiment includes only the cardo-based binder resin as a binder resin, and may not include the acrylic binder resin.

(D) solvent

The solvent may be used materials having compatibility with the colorant, the photopolymerization initiator, the photopolymerizable monomer, and the binder resin, but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether (EDM); Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; 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 and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Alkoxy acetate alkyl esters, such as methyl oxy acetate, ethyl oxy acetate, and butyl oxy acetate; Alkoxy acetate alkyl esters, such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy acetate; 3-oxypropionic acid alkyl esters, such as 3-oxy methyl propionate and 3-oxyethyl ethyl propionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxy propionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionic acid esters, such as methyl 2-oxy-2-methyl propionate and ethyl 2-oxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, and 2-ethoxy-2- Monooxy monocarboxylic acid alkyl esters of alkyl 2-alkoxy-2-methylpropionic acids such as methyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate and the like, and N-methylformamide, N, N-dimethylformamide, N-methylformanilade, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid High boiling point solvents, such as ethyl, diethyl oxalate, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, a propylene carbonate, and phenyl cellosolve acetate, are mentioned.

Among them, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc. in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be included in a balance, such as 30% by weight to 90% by weight, such as 40% by weight to 85% by weight, based on the total amount of the photosensitive resin composition. When the solvent is included within the above range, as the photosensitive resin composition has an appropriate viscosity, processability is excellent in manufacturing a black column spacer.

(F) other additives

Meanwhile, the photosensitive resin composition may further include additives of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.

The silane coupling agent may have a reactive substituent such as a vinyl group, a carboxyl group, a methacryloxy group, an isocyanate group, an epoxy group, or the like to improve adhesion to a substrate.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycol. Cidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included in the above range, it is excellent in adhesion, storage property and the like.

In addition, the photosensitive resin composition may further include a surfactant, for example, a fluorine-based surfactant, in order to improve coating properties and prevent defects.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like from BM Chemie Co .; Mechapack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^®, etc. from Dai Nippon Inki Chemical Co., Ltd .; Sumitomo M. (Note)社Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^{® from} Asahi Glass Co., Ltd .; Toray Silicone ^® (Note)社SH-28PA, the same -190 ^®, may be used a fluorine-containing surfactants commercially available under the name such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The fluorine-based surfactant may be used in an amount of 0.001 part by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the above range, coating uniformity is secured, staining does not occur, and wetting of the IZO substrate or the glass substrate is excellent.

In addition, the photosensitive resin composition may be added a certain amount of other additives such as antioxidants, stabilizers, etc. within a range that does not impair the physical properties.

Another embodiment provides a black column spacer prepared by exposing, developing, and curing the photosensitive resin composition described above.

The pattern in the black column spacer may have a taper angle of 5 ° or more, such as 5 ° or more and 60 ° or less.

The black column spacer manufacturing method is as follows.

(1) application and coating film forming step

After applying the photosensitive resin composition to a desired thickness on a substrate such as a glass substrate or an IZO substrate subjected to a predetermined pretreatment using a method such as spin or slit coating, roll coating, screen printing, or applicator, VCD The photosensitive resin film is formed by heating at 70 degreeC-100 degreeC for 1 minute-10 minutes through a process etc., and removing a solvent.

(2) exposure step

In order to form a pattern required for the obtained photosensitive resin film, a half tone portion for implementing a black matrix pattern and a full tone portion for implementing a column spacer pattern are interposed therebetween, and then 200 nm to 500 nm of active lines are irradiated. As a light source used for irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and X-rays, an electron beam, etc. can also be used in some cases.

The exposure amount varies depending on the kind of each component of the composition, the compounding amount and the dry film thickness, but when using a high pressure mercury lamp, the exposure amount is 500 mJ / cm ² or less (by a 365 nm sensor).

(3) developing stage

In the developing method, following the exposure step, an alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions, thereby remaining only the exposed portions to form a pattern.

(4) post-processing steps

There is a post-heating step for obtaining an image pattern obtained by development in the above process in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

Yet another embodiment provides a color filter including the black column spacer.

Hereinafter, preferred embodiments of the present invention are described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

( Example )

(Photosensitive resin composition production)

Example  One

To the composition shown in Table 1, after dissolving the photopolymerization initiator in a solvent, it was stirred at room temperature for 2 hours. Binder resin and a photopolymerizable monomer were added here, and it stirred at room temperature for 2 hours. After adding the colorant, the mixture was stirred at room temperature for 1 hour, and the silane coupling agent was added with other additives, and the mixture was stirred at room temperature for 1 hour. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition according to Example 1.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 7.125 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 3.919 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.400 TEB (Pharmasynthese) 0.150 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 27.687 EDM 16.400 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.800

(In Table 1, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 1, the colorant has a maximum transmittance at 400 nm)

(In Table 1, the pigment solids is included in 15% by weight relative to the total amount of the pigment dispersion)

Example 2

A photosensitive resin composition according to Example 2 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 2.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 7.125 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 3.919 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.400 TEB (Pharmasynthese) 0.150 coloring agent Pigment Dispersion 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 15.531 dyes Violet CF-002 (Kyungin Yang) 3.139 menstruum PGMEA 66.84 EDM 15.5 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.74

(In Table 2, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 2, the colorant has a maximum transmittance at 400 nm)

(In Table 2, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Example  3

A photosensitive resin composition according to Example 3 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 3 below.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 7.125 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 3.919 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.1375 TEB (Pharmasynthese) 0.4125 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 66.84 EDM 15.5 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.74

(In Table 3, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 3, the colorant has a maximum transmittance at 400 nm)

(In Table 3, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Example  4

A photosensitive resin composition according to Example 4 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 4.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 9.96 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 4.27 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.4125 TEB (Pharmasynthese) 0.1375 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 66.84 EDM 15.5 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.74

(In Table 4, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 4, the colorant has a maximum transmittance at 400 nm)

(In Table 4, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Example  5

A photosensitive resin composition according to Example 5 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 5 below.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 9.96 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 4.27 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.110 TEB (Pharmasynthese) 0.440 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 66.84 EDM 15.5 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.74

(In Table 5, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 5, the colorant has a maximum transmittance at 400 nm)

(In Table 5, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Example  6

A photosensitive resin composition according to Example 6 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 6.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 9.96 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 4.27 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.440 TEB (Pharmasynthese) 0.110 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 66.84 EDM 15.5 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.74

(In Table 6, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 6, the colorant has a maximum transmittance at 400 nm)

(In Table 6, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Comparative example  One

A photosensitive resin composition according to Comparative Example 1 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 7.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 9.96 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 4.27 Photopolymerization Initiator TEB (Pharmasynthese) 0.550 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 27.687 EDM 16.400 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.800

(In Table 7, above, TEB has a maximum absorbance at 345 nm.

(In Table 7, the colorant has a maximum transmittance at 400 nm)

(In Table 7, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Comparative example  2

A photosensitive resin composition according to Comparative Example 2 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared using the components mentioned below in the composition shown in Table 8.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 7.125 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 3.919 Photopolymerization Initiator OXE01 (Basf) 0.400 TEB (Pharmasynthese) 0.150 Colorant (pigment dispersion) 849R (Red R179 Millbase, ENF Corporation) 18.647 100Y (Yellow Y139 Millbase, ENF) 6.212 614B (blue 15: 6 Millbase, ENF Corporation) 18.770 menstruum PGMEA 27.687 EDM 16.400 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.800

(In Table 8, OXE01 has a maximum absorbance at 260 nm and 345 nm, TEB has a maximum absorbance at 345 nm)

(In Table 8, the colorant has a maximum transmittance at 400 nm)

(In Table 8, the pigment solids are included in 10% by weight relative to the total amount of the pigment dispersion)

Comparative example  3

A photosensitive resin composition according to Comparative Example 3 was prepared in the same manner as in Example 1, except that the photosensitive resin composition was prepared by using the components mentioned below.

(Unit: g) ingredient content Binder resin Cardo binder resin (V259ME, NSSC) 7.125 Photopolymerizable monomer Dipentaerythritol hexaacrylate (Japan Catalyst) 3.919 Photopolymerization Initiator NCI831 (ADEKA Corporation) 0.400 TEB (Pharmasynthese) 0.150 Colorant (pigment dispersion) Carbon Black (BK6616, Tokushiki) 43.520 menstruum PGMEA 27.687 EDM 16.400 Other additives γ-glycidoxy propyl trimethoxysilane (S-510, Chisso) 0.800

(In Table 9, NCI831 has a maximum absorbance at 380 nm, TEB has a maximum absorbance at 345 nm)

(In Table 9, the pigment solids is included in 15% by weight relative to the total amount of the pigment dispersion)

(evaluation)

Evaluation: Development margin evaluation

Light-shielding of 10 micrometers pattern among the column spacer patterns of the patterned specimen which completed the photosensitive resin composition of Examples 1-6 and Comparative Examples 1-3 by the coating, exposure (using a halftone mask), image development, and post-baking. The layer step thickness was measured by a non-contact thickness meter (3-D profiler), and the results of the slope change of the light shielding layer step thickness varying per 10 seconds of development time are shown in Table 10 below.

Center exposure amount (mJ) BP (seconds) Shading margins (ÅA / 10s) Example 1 70 145 1013 Example 2 70 187 842 Example 3 100 138 1178 Example 4 65 142 1254 Example 5 110 134 1345 Example 6 60 142 1466 Comparative Example 1 70 158 1742 Comparative Example 2 70 133 2192 Comparative Example 3 70 108 5481

(In Table 10, the development margin of the light shielding part means the thickness of the halftone region that changes every 10 seconds.)

Through the above Table 10, even if the central exposure amount is the same, the light shielding part development margin is a photosensitive resin composition comprising a colorant having a maximum transmittance at 360 nm to 410 nm and a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm, otherwise It can be confirmed that it is superior to the photosensitive resin composition. In addition, it is also confirmed that the photosensitive resin composition when the colorant and the photopolymerization initiator are included in a weight ratio of 1: 4 to 4: 1, for example, 1: 3 to 3: 1, respectively, has better light shielding part development margin than the photosensitive resin composition. Can be.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (16)

(A) 5% to 50% by weight of a colorant having a maximum transmittance at 360 nm to 410 nm;
(B) 0.1 wt% to 5 wt% of a photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm and a photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm;
(C) 1% to 10% by weight of the photopolymerizable monomer; And
(D) Solvent Residue
Including,
The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm is an oxime compound, The photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm is a triazine compound,
The photopolymerization initiator having a maximum absorbance at 360 nm to 410 nm and the photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm are each included in a weight ratio of 1: 3 to 3: 1.
The method of claim 1,
The colorant is a photosensitive resin composition comprising a pigment, a dye or a combination thereof.
The method of claim 2,
The pigment is a photosensitive resin composition is an organic pigment.
The method of claim 3,
The organic pigment is a photosensitive resin composition which is a mixture of two or more selected from the group consisting of a red pigment, a green pigment, a blue pigment and a yellow pigment.
The method of claim 1,
The photopolymerization initiator has a maximum absorbance at 370 nm to 410 nm.
delete delete delete delete The method of claim 1,
The photopolymerization initiator having a maximum absorbance at 310 nm to 360 nm comprises from 0.01% to 5% by weight based on the total amount of the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition further comprises (E) binder resin.
The method of claim 11,
The binder resin is a photosensitive resin composition comprising an acrylic binder resin, a cardo binder resin or a combination thereof.
The method of claim 11,
The binder resin is 5% by weight to 20% by weight relative to the total amount of the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine-based surfactant, a radical polymerization initiator, or a combination thereof.
The black column spacer manufactured using the photosensitive resin composition of any one of Claims 1-5 and 10-14.
A color filter comprising the black column spacer of claim 15.

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