KR101860580B1 - A black photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition comprising a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound is a black photosensitive resin composition comprising a polyfunctional acrylic compound.
The present invention also relates to a color filter including the black photosensitive resin, a bezel for a touch sensor panel, and a display device.

Description

Technical Field [0001] The present invention relates to a black photosensitive resin composition, a color filter including the black photosensitive resin composition,

The present invention relates to a black photosensitive resin composition, a color filter including the same, and a display device.

A color filter may be embedded in a color imaging device of an image sensor such as a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), etc., and may be used to actually obtain a color image . In addition, the color filter is widely used for a photographing element, a plasma display panel (PDP), a liquid crystal display (LCD), a field emission display (FEL), a light emitting display (LED) and the like. Particularly, in recent years, the use of LCDs has been further expanded, and accordingly, color filters have been recognized as one of the most important components in reproducing color tones of LCDs.

The color filter is obtained by uniformly applying a black photosensitive resin composition containing a black colorant corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed by spin coating, (Hereinafter also referred to as "firing") is performed for each color, thereby forming a pixel of each color . In recent years, a large-sized display has progressed at a high speed and a high contrast ratio is continuously required. Accordingly, a method of using a dye instead of the pigment dispersion method which has been conventionally used as a black method of a black photosensitive resin composition or using a dye and a pigment simultaneously . However, a black photosensitive resin composition for a color filter using a dye and a black color photosensitive resin composition for a hybrid type color filter using both a dye and a pigment simultaneously can provide a color filter excellent in transmittance. However, The sensitivity may be lowered depending on the kind of the ink. Therefore, studies have been actively made to solve the above problems and to prevent the sensitivity of the color filter from deteriorating.

On the other hand, Korean Patent Registration No. 10-0529638 discloses a photopolymerizable resin composition containing an N-phenylglycine and a triazine-based compound excellent in adhesion, resolution, surface margin and internal curability as an initiator, It seems to be insufficient for improving the sensitivity of the filter pattern formation.

Korean Patent Publication No. 10-2012-0083187

An object of the present invention is to improve the transmittance of the black photosensitive resin composition and to provide a fine pattern by producing a black photosensitive resin composition containing a polyfunctional acrylic compound.

In order to achieve the above object,

The present invention provides a black photosensitive resin composition comprising a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound comprises a compound represented by the following general formula (1).

[Chemical Formula 1]

Wherein R &_lt; 1 > is an alkyl group having 1 to 10 carbon atoms,

And m is an integer of 0 to 4.

The present invention also provides a color filter which is manufactured from the black photosensitive resin composition.

The present invention also provides a bezel for a touch sensor panel, which is manufactured from the black photosensitive resin composition.

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

The black photosensitive resin composition of the present invention has an advantage of being able to form an excellent transmittance and a fine pattern, and a color filter, a bezel for a touch sensor panel and a display device can be manufactured using the black photosensitive resin composition.

Fig. 1 is a photograph of the minimum patterns of Examples 1 to 4 and Comparative Examples 1 and 2. Fig.

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

The present invention relates to a black photosensitive resin composition comprising a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound comprises a compound represented by the following general formula (1).

[Chemical Formula 1]

Wherein R &_lt; 1 > is an alkyl group having 1 to 10 carbon atoms,

And m is an integer of 0 to 4.

The compound of Formula 1 is characterized by containing a fluorene group as a polyfunctional acrylic compound.

In addition, the black photosensitive resin composition of the present invention may further contain additives as required.

Hereinafter, the black photosensitive resin composition of the present invention will be described in detail for each component.

(A) Black pigment

Examples of the black pigment include carbon black, organic black pigment, titanium black, and a pigment in which red, blue, and green are mixed.

More specifically, the black pigment may be prepared by mixing a carbon black and two or more colored pigments to prepare a milled colored dispersion. Examples of usable carbon black include Sysho 5HIISAF-HS, Sisato KH, Sisato 3HHAF-HS, Sisato NH, Sisato 3M, Sisso 300HAF-LS, Sisso 116HMMAF-HS, 116MAF, Cysto FMFEF-HS, Cysto SOFEF, Cysto VGPF, Cysto SVHSRF-HS, and Cysto SSRF; Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram LR, # 2700, # 2600, # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 900, MCF88, # 52, # 50, # 47, # 45, # 45L, CF9, # 95, # 3030, # 3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; PRINTEX-55, PRINTEX-55, PRINTEX-45, PRINTEX-35, PRINTEX-55, PRINTEX-85, PRINTEX-75, PRINTEX- SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A; SPECIAL BLACK-550; RAVEN-1080 ULTRA, RAVEN-1060ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN- 420, RAVEN-410, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN- RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 can be used.

Examples of color pigments usable in combination with the carbon black include carmine 6B (CI12490), phthalocyanine green (CI 74260), phthalocyanine blue (CI 74160), Mitsubishi carbon black MA100, perylene black (BASF K0084. K0086) , Linol Yellow (CI 21090), Linol Yellow GRO (CI 21090), Benzidine Yellow 4T-564D, Mitsubishi Carbon Black MA-40, Victoria Pure Blue (CI42595) PIGMENT RED 97, 122, 149, 168, 177, 180, 192, 215, C.I. PIGMENT GREEN 7, 36, C.I. PIGMENT 15: 1, 15: 4, 15: 6, 22, 60, 64, C.I. PIGMENT 83, 139 C.I. PIGMENT VIOLET 23, etc. In addition, white pigments, fluorescent pigments, etc. may be used.

The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. Specific examples of the carbon black that is the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

The carbon black, which is the black pigment, may be a resin-coated carbon black. Since the carbon black coated with the resin has a lower conductivity than that of the carbon black not coated with the resin, excellent electrical insulation can be imparted to the black matrix or black column spacer when the spacer is formed.

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

( a1 ) Pigment Dispersant

Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. These surfactants may be used singly or in combination of two or more.

It is also preferable to include an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

As the pigment dispersant (a1), other resin type pigment dispersants other than the acrylic dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters. DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-160, BYK (trade name) 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co., In addition to the acrylic dispersant, other resin type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylic dispersant.

The content of the pigment dispersant (a1) is 5 to 60 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the solid content of the black pigment (A). If the content of the pigment dispersant (a1) exceeds 60 parts by weight, the viscosity may be increased. If the content of the pigment dispersant (a1) is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

The content of the black pigment (A) in the composition of the pigment dispersion is 20 to 90% by weight, preferably 30 to 75% by weight based on the total weight of the solid content. When the content of the pigment is in the range of 20 to 90% by weight, the viscosity is low, the storage stability is excellent, and the dispersion efficiency is high, which is effective in increasing the contrast ratio.

Therefore, the black pigment (A) is preferably contained in an amount of 3 to 20% by weight based on the total weight of the black photosensitive resin composition.

(B) an alkali-soluble resin

And is copolymerized with an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to obtain solubility in an alkali developing solution used in a development process for forming a pattern.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

As a method for imparting hydroxyl groups to the alkali-soluble resin, there may be mentioned a method of copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, a method of copolymerizing an ethylenically unsaturated monomer having a carboxyl group with a glycidyl group A method in which the compound is further reacted with a compound having a glycidyl group in addition to a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, and the like.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, And methacrylic acid glycidyl ester, and examples thereof include butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester. These may be used in combination of two or more kinds.

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble resin are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;

3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

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

In order to ensure the compatibility of the alkali-soluble resin and the storage stability of the black photosensitive resin composition, the acid value is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the developing speed of the black photosensitive resin composition is slow. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, And the viscosity tends to rise.

The content of the alkali-soluble resin is 0.5 to 50% by weight, preferably 1 to 35% by weight based on the total weight of the black photosensitive resin composition. When the content of the alkali-soluble resin is 0.5 to 50 wt%, the solubility of the developer is excellent and pattern formation is easy. In the development, the reduction of the film thickness of the pixel portion of the exposed portion is prevented,

(C) Photopolymerization  compound

The photopolymerizable compound is a compound capable of polymerizing under the action of the photopolymerization initiator (D) described below, and includes the polyfunctional acrylic compound of the above formula (1). In the present invention, a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer may be used in addition to the polyfunctional acrylic compound of the above formula (1), and preferably a bifunctional or higher polyfunctional monomer may be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N- But are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.

Preferred multifunctional monomers that may be used in combination with the compound of Formula 1 include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Erythritol hexa (meth) acrylate.

The photopolymerizable compound is preferably contained in an amount of 1 to 10% by weight, and more preferably 3 to 8% by weight based on the total weight of the black photosensitive resin composition. When the photopolymerizable compound is contained in an amount of 1 to 10% by weight, the strength of the pixel portion is excellent and the smoothness is improved.

(D) Light curing Initiator

The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). Particularly, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and cost, the photopolymerization initiator is preferably used in combination with an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, It is preferable to use at least one compound selected from the group consisting of compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, Is used.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include OXE01 and OXE02 of BASF.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- have.

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the black photosensitive resin composition of the present invention. Since the black photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiator auxiliary (D-1), at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

The photopolymerization initiator may be included in an amount of 0.01 to 15% by weight, preferably 0.1 to 7% by weight based on the total weight of the black photosensitive resin composition of the present invention. When the photopolymerization initiator is in the range of 0.01 to 15% by weight, the sensitivity of the photosensitive resin composition becomes high and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the photosensitive resin composition under the above-described conditions and the smoothness on the surface of the pixel portion can be improved. When the photopolymerization initiator includes the photopolymerization initiator, the photopolymerization initiator comprises 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator. If the content of the photopolymerization initiator is less than 10% by weight, the decrease in sensitivity due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process. When the photopolymerization initiator is further used, the photopolymerization initiator may include 0.01 to 15% by weight, preferably 0.1 to 7% by weight based on the total weight of the black photosensitive resin composition of the present invention. When the amount of the photopolymerization initiator is within the range of 0.01 to 15% by weight, the sensitivity of the black photosensitive resin composition becomes higher and the productivity of the color filter formed using the photosensitive resin composition is improved.

(E) Solvent

The solvent used in the conventional black photosensitive resin composition is not particularly limited so long as it is effective in dissolving the other components contained in the black photosensitive resin composition. The solvent may be selected from ethers, aromatic hydrocarbons, ketones, alcohols, esters And amides are preferred.

Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as? -Butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably an organic solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The above-mentioned solvents may be used alone or in combination of two or more. The solvent may be contained in an amount of 10 to 90% by weight, preferably 60 to 85% by weight based on the total weight of the black photosensitive resin composition of the present invention. When the above-mentioned solvent is in the range of 10 to 90% by weight, the coating property is good when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Provides a resolution effect.

(F) Additive

The additive may be optionally added, for example, other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti-aggregation agent.

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

The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than glycidyl ester resins, glycidyl amine resins or brominated derivatives of the above epoxy resins, epoxy resins and their brominated derivatives ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

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

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the epoxy resin curing agent include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), MH-700 have. The curing agents exemplified above may be used alone or in combination of two or more.

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

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of solid components in the black photosensitive resin composition.

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

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

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

A method of producing the black photosensitive resin composition of the present invention will be described below.

First, the black pigment (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or the whole of the pigment dispersant (a1) and the alkali-soluble resin (B) may be mixed and dissolved or dispersed with the solvent (E).

(B), a photopolymerizable compound (C), a photopolymerization initiator (D) and, if necessary, an additive (F) and a solvent (E) are further added to the mixed dispersion to a predetermined concentration, To prepare a black photosensitive resin composition.

The present invention also provides a color filter made of a black photosensitive resin composition and a display device having the same.

The above black photosensitive resin composition is coated on a substrate as described below, and photo-cured and developed to form a pattern.

First, a black photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of solid components of a black photosensitive resin composition formed in advance, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coating film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

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

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

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.

Using the black photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through each of the steps as described above.

In addition, a bezel for a touch sensor panel can be formed using the black photosensitive resin composition of the present invention.

When the black photosensitive resin composition of the present invention is used at the bezel portion of a touch sensor panel, light shielding can be prevented due to high light shielding ratio, and resistance change rate is low even after heat treatment at a high temperature. .

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

Manufacturing example  1. Carbon Preparation of dispersion (M1)

, 12.0 parts by weight of Carbon Black (MA-8, manufactured by Mitsubishi Corp.) as a black pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 44 parts by weight of propylene glycol monomethyl ether acetate as a solvent, Were mixed and dispersed by a bead mill for 12 hours to prepare a carbon dispersion M1.

< Multifunctional  Preparation of acrylic compound (Formula 1)

Synthetic example  One.

(1-ethyl- (3- (3-dimethylamino) propyl) -carbodiimide hydrochloride) with one equivalent of di-acid type fluorene derivative known to synthesize 2 equivalents of PETA (pentaerithritol triacrylate) And the coupling reaction was carried out at room temperature for 20 hours. Then, work-up was carried out using water and methylene chloride, and the compound of formula (2) in the form of a highly viscous liquid was obtained in a yield of about 80% by using silica gel column chromatography. The results of the reaction and structural analysis are as follows.

¹ H NMR

_{(400MHz, CDCl 3): δ} 7.86 (d, 4H), 7.80 (d, 2H), 7.55 (d, 2H), 7.40 (d, 2H), 7.30 (d, 2H), 7.18 (d, 2H), (S, 4H), 4.05 (s, 12H), 2.35 (s, 6H)

[Reaction Scheme 1]

Synthetic example  2.

(1-ethyl- (3- (3-dimethylamino) propyl) -carbodiimide hydrochloride) with one equivalent of di-acid type fluorene derivative known to synthesize 2 equivalents of PETA (pentaerithritol triacrylate) And the coupling reaction was carried out at room temperature for 20 hours. After work-up with water and methylene chloride, the compound of formula 3 in the form of a highly viscous liquid was obtained in about 85% yield using silica gel column chromatography. The results of the reaction and structural analysis are as follows.

¹ H NMR

_{(400MHz, CDCl 3): δ} 7.85 (d, 2H), 7.70 (d, 2H), 7.55 (d, 2H), 7.38 (d, 2H), 7.30 (d, 2H), 7.03 (d, 2H), (S, 4H), 4.05 (s, 12H), 2.35 (s, 6H)

[Reaction Scheme 2]

&Lt; Preparation of Black Photosensitive Resin Composition &

The components and compositions shown in Table 1 were stirred for 5 hours according to a conventional method to prepare a black photosensitive resin composition.

(Unit: parts by weight) division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 (M1) Carbon dispersion 100 100 100 100 100 100 (B) an alkali-soluble resin 3.2 3.2 3.2 3.2 3.2 3.2 (C) Photopolymerizable compound C-1 2.1 0.3 0.3 - - - C-2 - - - 0.3 - - C-3 - 1.8 - 1.8 2.1 - C-4 - - 1.8 - - 2.1 (D) a photopolymerization initiator 1.5 1.5 1.5 1.5 1.5 1.5 (E) Solvent 49.6 49.6 49.6 49.6 49.6 49.6 (F) Additive 1.4 1.4 1.4 1.4 1.4 1.4

(M1) Carbon dispersion: The carbon dispersion prepared in Production Example 1

(B) Alkali-soluble resin: Cadocet resin (WR-101, manufactured by Adeka)

(C) Photopolymerizable compound:

(C-1) Compound (2) prepared in Synthesis Example 1

(C-2) Compound (3) prepared in Synthesis Example 2

(C-3) dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

(C-4) pentaerythritol tetra (meth) acrylate (PETA, manufactured by Nippon Kayaku Co., Ltd.)

(D) Photopolymerization initiator: Ethanone-1- [9-ethyl-6-2 (-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol- (Irgacure OXE02, manufactured by Shiba Ltd.)

(E) Solvent: Propylene glycol monomethyl ether acetate

(F) Additive (adhesion promoter): 3-methacryloxypropyltrimethoxysilane

Experimental Example  1. Manufacture of color filters

A color filter was prepared using the black photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2.

Each of the above black photosensitive resin composition solutions was spin-coated on glass, followed by vacuum drying (VCD) to 65 Pa, followed by heat treatment at about 100 占 폚 for 2 minutes to form a coating film having a thickness of about 1.2 占 퐉. In order to observe the developing property, a photomask was used to expose under a high-pressure mercury lamp at an energy of 50 mJ / cm 2. The exposed substrate was developed in a 0.04% aqueous solution of KOH at 25 ° C by spraying method, washed with pure water, and dried, post-baked in a convection oven at 230 ° C for 20 minutes. The film prepared by the above method had a film thickness of 1.15 mu m, excellent in developing adhesion, and high in optical density of 4.3 or more.

Experimental Example  2. Developing adhesion test

The minimum pattern of the black photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 was measured to evaluate the adhesion.

A mask having a pattern thickness of 1 to 20 mu m and engraved in a unit of 1 mu m was used, and the minimum pattern was evaluated based on the mask size at which the pattern remained.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Minimal pattern
(탆) 4 4 4 4 6 7

As shown in Table 2, Examples 1 to 4 including the photopolymerizable compound of the present invention have a small minimum pattern and a high resolution pattern as compared with the comparative example.

Claims (5)

1. A black photosensitive resin composition comprising a black pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound comprises a compound represented by the following formula (1).
[Chemical Formula 1]

Wherein R &_lt; 1 &gt; is an alkyl group having 1 to 10 carbon atoms,
And m is an integer of 0 to 4. The black photosensitive resin composition according to claim 1, which comprises 3 to 20% by weight of a black pigment, 0.5 to 50% by weight of an alkali soluble resin, 1 to 10% by weight of a photopolymerizable compound, 0.01 to 15% To 10% by weight and 90% by weight based on the total weight of the black photosensitive resin composition. A color filter produced by the black photosensitive resin composition of claim 1. A bezel for a touch sensor panel, which is manufactured from the black photosensitive resin composition of claim 1. A display device comprising the color filter of claim 3.

Images