KR101825019B1 - Black Photosensitive Composition, Color Filter and Liquid Crystal Display Device using thereof - Google Patents

Abstract

The present invention relates to a process for photopolymerizing a monomer having a coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), an alkoxysilane having an unsaturated hydrocarbon group and an unsaturated hydrocarbon, (F). The present invention also relates to a black photosensitive resin composition comprising the silica (F).
The black photosensitive resin composition according to the present invention exhibits adhesiveness and uniform optical density and thus can provide a color filter having excellent light shielding characteristics and a liquid crystal display device including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a black photosensitive resin composition, a color filter using the same and a liquid crystal display device using the same,

The present invention relates to a black photosensitive resin composition and a color filter and a liquid crystal display using the same.

A liquid crystal display device is an electronic device that changes electrical information into visual information by using a change in transmittance of liquid crystal. Such a liquid crystal display device typically has a structure in which a liquid crystal is injected between a color filter substrate and a TFT substrate, and the color filter is used for controlling optical characteristics and transmission characteristics of a liquid crystal display device.

In order to improve more uniform optical characteristics and transmission characteristics, a structure in which a column space or a column matrix is coupled to a color filter has recently been proposed. More specifically, a column matrix is formed at a boundary portion between colored layers such as red, green and blue of the color filter. However, such a column matrix causes a reduction in light leakage and contrast, and disturbing the current flow when a voltage is applied, resulting in display failure.

In order to solve such a problem, a method in which the column matrix and the column space are produced using a black photosensitive resin composition is attracting attention.

However, the conventional black photosensitive resin composition was intended to lower the dielectric constant by incorporating organic pigments or blackened organic pigments having low dielectric constant and high resistance value as a shape stabilizer, but it was found that the light uniformity and adhesiveness to the substrate were low, There is a problem that OD (optical density less than OD) falls or red light leakage occurs when forming a pattern.

An object of the present invention is to provide a black photosensitive resin composition excellent in electrical insulation and excellent in adhesion to a lower substrate.

Another object of the present invention is to provide a color filter comprising a black matrix or a black column spacer manufactured using the black photosensitive resin composition.

It is still another object of the present invention to provide a liquid crystal display device including the color filter.

According to an aspect of the present invention,

A coloring material (A); Binder resin (B); Photopolymerizable compound (C); A photopolymerization initiator (D); Solvent (E); And silica (F) surface-modified with photopolymerization of a monomer having an unsaturated hydrocarbon and an alkoxysilane having an unsaturated hydrocarbon group.

The alkoxysilane having an unsaturated hydrocarbon group may be at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyloxyminosilane, vinyltriisopropoxysilane and vinyltri-tert-butoxysilane.

The unsaturated hydrocarbon-containing monomer may be selected from the group consisting of 2-hydroxy-ethyl methacrylate, methyl methacrylate, methacrylic acid, ethylene glycol methacrylic acid, propylene glycol methacrylic acid, nonylphenylcarbitol acrylate, (Meth) acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 1,6-hexanediol di (Meth) acrylates such as neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (Meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The modified silica (F) may be represented by the following formula (1).

[Chemical Formula 5]

(R is independently a C ₂ to C ₅ alkylene group and n is an integer of 2 to 100)

The modified silica (F) may be contained in an amount of 1 to 20 parts by mass based on 100 parts by mass of the photopolymerizable compound (C).

The modified silica comprises:

Introducing a functional group into the surface of the silica particles with an alkoxysilane having an unsaturated hydrocarbon group, and then polymerizing the functional group-containing silacar with a monomer having an unsaturated hydrocarbon, followed by photopolymerization.

Another aspect of the present invention relates to a color filter comprising a black matrix or black column spacer made using a black photosensitive resin composition.

The relative dielectric constant of the black matrix or the black column spacer is 4.0 or less and the optical density (OD) from 400 nm to 750 nm is 4.0 or more on average.

Another aspect of the present invention relates to a liquid crystal display including the color filter.

The black photosensitive resin composition of the present invention is excellent in electrical insulation and adhesion, and can provide a uniform optical density.

When a black matrix or a black column spacer is formed using the black photosensitive resin composition according to the present invention, it is possible to provide a color filter having excellent electrical insulation and adhesiveness and improved light leakage.

Hereinafter, the present invention will be described in more detail to facilitate those skilled in the art.

The present invention provides a black photosensitive resin composition.

The black photosensitive resin composition of the present invention is excellent in electrical insulation and adhesion, and can provide a uniform optical density.

According to one embodiment of the present invention, the black photosensitive resin composition comprises a coloring material (A); Binder resin (B); Photopolymerizable compound (C); A photopolymerization initiator (D); Solvent (E); (F) which is surface-modified by photopolymerization of an alkoxysilane having an unsaturated hydrocarbon group and a monomer having an unsaturated hydrocarbon.

(A) Coloring material: Carbon black (A1) and organic pigment (A2)

The coloring material may include carbon black (A1) and organic pigment (A2) which are black pigments. The carbon black and the organic pigment can provide a black matrix or black column spacer with light shielding while at the same time providing excellent electrical insulation and optical density.

The content of the coloring material may be 5 to 15 parts by mass based on 100 parts by mass of the black photosensitive resin composition. If the content of the coloring material is less than 5 parts by mass, the optical density may be lowered. If the content of the coloring material is more than 15 parts by mass, the optical density may be improved, but pattern formation may be difficult.

(A1) carbon black

The carbon black (A1) may be included in an amount of 5 to 10 parts by mass based on 100 parts by mass of the solid content of the coloring material. If the content of the carbon black is less than 5 parts by mass, it may be difficult to obtain an OD value of 3.0 or more when the black matrix or black column spacer is formed. If the content is more than 10 parts by mass, the OD value may be sufficient.

Carbon black, which is a black pigment, is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. More specifically, the carbon black A1 may be a channel black, a furnace black, a thermal black, a lamp black, or the like. Further, the carbon black 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.

(A2) Organic pigment

The content of the organic pigment (A2) may be 90 to 95 parts by mass based on 100 parts by mass of the solid content of the coloring material. If the content of the organic pigment is less than 90 parts by mass, the content of the carbon black may relatively increase and the electrical insulation may be deteriorated. If the content of the organic pigment exceeds 95 parts by mass, the OD value may decrease.

The organic pigment may be an organic pigment generally used in the art, but may preferably be an organic pigment having an optical density similar to that of carbon black and capable of imparting excellent electrical insulation. At least one of the organic pigments (A2) may be used to provide the above-mentioned optical density, electrical insulation, and the like.

The organic pigments may be various pigments used in printing ink, ink jet ink and the like. Specific examples of the organic pigments include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, An anthanthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, A pyranthrone pigment, a diketopyrrolopyrrole pigment, and the like.

More specifically, the organic pigment (A2) may be a compound classified as pigment in the color index (The Society of Dyers and Colourists), for example,

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

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

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

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

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

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

C.I. Pigment Brown 28 and

C.I. (C.I.) numbers such as Pigment Black 1 and 7, but are not limited thereto.

Preferably, the organic pigment (A2) is selected from the group consisting of Pigment Red 254, Pigment Red 242, Pigment Blue 15: 6, Pigment Yellow 139 and the like to provide excellent electrical insulation and uniform optical density. But is not limited thereto.

According to one embodiment of the present invention, the organic pigment (A2) may include Pigment Red 254 and Pigment Red 242. The content of Pigment Red 242 may be 25 to 200 parts by mass based on 100 parts by mass of the solid content of Pigment Red 254. When the content of Pigment Red 242 is less than 25 parts by mass, OD at a wavelength of 500 nm is less than 3.0, light leakage may occur, and when the amount is more than 200 parts by mass, OD value at a wavelength of 550 nm is less than 3.0 And light leakage phenomenon may occur.

According to one embodiment of the present invention, the organic pigment (A2) may include Pigment Red 254, Pigment Red 242, Pigment Blue 15: 6 and Pigment Yellow 139, 40 to 60 parts by mass of Pigment Blue 15: 6, 5 to 20 parts by mass of Pigment Red 254, 5 to 20 parts by mass of Pigment Red 242, and 5 to 20 parts by mass of Pigment Red 139 relative to 100 parts by mass of the organic pigment (A2) 10 to 30 parts by mass. When the content of the pigment is within the above range, the black photosensitive resin composition may exhibit excellent electrical insulation and uniform optical density.

(B) binder resin

The binder resin (B) makes it possible to form a pattern upon use of the black photosensitive resin composition, and can improve the resolution and the residual film ratio of the color filter.

The binder resin may be contained in an amount of 5 to 50 parts by mass, preferably 10 to 40 parts by mass, based on 100 parts by mass of the solid content in the black photosensitive resin composition. When the content of the binder resin is less than 5 parts by mass, it may be difficult to form a pattern with the resin composition. When the content of the binder resin is more than 50 parts by mass, a color filter having a low resolution and a residual film ratio due to an excessive binder resin can be provided.

The binder resin may include those conventionally used in the art. Specifically, the binder resin may include one selected from the group consisting of a compound having an unsaturated carboxyl group, a copolymer with another monomer copolymerizable with the unsaturated carboxyl group, It may be more than species, but it is not a limitation now.

The compound having an unsaturated carboxyl group may be a carboxylic acid compound having an unsaturated double bond capable of polymerization, and more specifically, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of the dicarboxylic acid; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends such as? -carboxypolycaprolactone mono (meth) acrylate, monomethyl (meth) acrylate, monomethyl maleic acid, (Meth) acryloyloxy) ethyl succinate, mono-2 - ((meth) acryloyloxy) ethyl phthalate and mono-2 - ((meth) acryloyloxy) ethyl succinate.

According to one embodiment of the present invention, the compound having an unsaturated carboxyl group may be acrylic acid or methacrylic acid in order to provide excellent copolymerization reactivity and solubility in a developing solution.

Other monomers copolymerizable with the carboxyl group-containing monomer are monomers having a carbon-carbon unsaturated bond, and more specifically, aromatic vinyl compounds such as styrene,? -Methylstyrene, and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinylcyanide compounds such as acrylonitrile, methacrylonitrile and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-ethyl- Unsaturated oxetanecarboxylate compounds, and the like, but the present invention is not limited thereto.

The cardade resin is a mixture of 3,3-bis (4-hydroxyphenyl) -2-benzofuran-1 (3H) (3H) -one, 3,3-bis (4-hydroxy-2,5-dimethylphenyl) (3H) -one, 3,3-bis (4-hydroxy-5-isopropyl-2-methylphenyl) -2-benzofuran- , 3,3-bis (3,5-dibromo-4-hydroxyphenyl) -2-benzofuran-l (3H) (4-hydroxyphenyl) -10-anthrone, 1,2-bis (4-carboxyphenyl) carboran, 1, Bis (4'-carboxyphenyl) phthalide, 9,10-bis- (4-carboxyphenyl) (4-aminophenyl) -anthracene, anthrone dianiline, and aniline phthalein. Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, (4-hydroxyphenyl) propane, bis (4-hydroxy-3-chlorophenyl) Methylphenyl) ether and bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis 3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9- ) Fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) But are not limited to, those prepared by polymerizing a compound containing at least one monomer selected from the group consisting of

(C) Photopolymerization  compound

The content of the photopolymerizable compound (C) may be 1 to 60 parts by mass, preferably 5 to 50 parts by mass based on 100 parts by mass of the total amount of the binder resin (B) and the photopolymerizable compound based on the solid content. When the photopolymerizable compound (C) is contained in the content range, good pattern characteristics can be provided at the time of pattern formation using the black photosensitive resin composition.

The photopolymerizable compound is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and may include at least one member selected from the group consisting of monofunctional monomers, bifunctional monomers and other polyfunctional monomers, May be a bifunctional or higher polyfunctional monomer.

Specific examples of the monofunctional monomer include polypropylene glycol methacrylate, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like, 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, 3-methylpentanediol di (meth) acrylate, and the like, 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 tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol But are not limited to, hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

(D) Light curing Initiator

The photopolymerization initiator (D) improves the sensitivity of the black photosensitive resin composition and can improve the strength and surface smoothness of the pixel portion when the pixel portion is formed using the same.

The content of the photopolymerization initiator may be 0.1 to 40 parts by mass, preferably 1 to 30 parts by mass based on 100 parts by mass of the total amount of the binder resin and the photopolymerizable compound based on the solid content. When the content of the photopolymerization initiator is within the above range, the sensitivity of the black photosensitive resin composition becomes high, and the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion can be improved.

The photopolymerization initiator may be at least one selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound, and an oxime compound, but is not limited thereto.

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, and the like.

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 -On oligomers, and the like.

The acetophenone compound may be a compound represented by the following general formula (1), but is not limited thereto.

[Chemical Formula 1]

Wherein R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted with an alkyl group having a carbon number of 1 to 12 Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 2-amino (4-morpholinophenyl) propan-1-one, 2-methyl- 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one 2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino It is not limited.

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-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, phenyl group in the 4,4' An imidazole compound substituted by a group, or the like. Preferred are 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) , 5,5'-tetraphenylbiimidazole, and the like, but the present invention is not limited thereto.

The oxime compound may be a compound represented by the following general formulas (2) to (4), but is not limited thereto.

(2)

(3)

[Chemical Formula 4]

The black photosensitive resin composition according to the present invention may further contain a photopolymerization initiator generally used in this field as long as it does not impair the effects of the present invention in addition to the photopolymerization initiator described above. For example, Phenanthone compounds, thioxanone compounds, anthracene compounds, and polyfunctional thiol compounds, but the present invention is not limited thereto.

Specific examples of the benzoin-based compound include, but are not limited to, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

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, but is not limited thereto.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- However, the present invention is not limited thereto.

Specific examples of the anthracene compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, , But is not limited thereto.

Specific examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis- Mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like, but are not limited thereto.

In addition, the photopolymerization initiator may optionally contain at least one selected from the group consisting of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10- , Camphorquinone, methyl phenylclyoxylate, titanocene compound, and the like.

(D-1) Light curing  Initiator

The black photosensitive resin composition may further include a photopolymerization initiator in addition to the photopolymerization initiator.

When the photopolymerization initiator is used in combination with the photopolymerization initiator, the black photosensitive resin composition containing the photopolymerization initiator can exhibit improved sensitivity, and productivity of the black matrix or black column spacer can be improved when the resin composition is used.

The content of the photopolymerization initiator may be 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass based on 100 parts by mass of the total amount of the binder resin and the photopolymerizable compound based on the solid content. When the content of the photopolymerization initiator is within the above range, the sensitivity of the black photosensitive resin composition becomes higher, and the productivity of the color filter can be improved by the black photosensitive resin composition.

The photopolymerization initiator may be at least one selected from the group consisting of an amine compound and a carboxylic acid compound.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4- 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis Diethylamino) benzophenone, and the like, but may preferably be an aromatic amine compound.

Specific examples of the carboxylic acid compound in the photopolymerization initiator auxiliary (D-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenyl Aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid, no.

(E) Solvent

The content of the solvent (E) is 60 to 90 parts by mass, preferably 70 to 85 parts by mass with respect to 100 parts by mass of the black photosensitive resin composition containing the solvent (E). When the content of the above-mentioned solvent (E) is within the above range, the resin composition is applied by using a roll coater, a spin coater, a slit and spin coater, a slit coater (or a die coater) When applied with a coating device, good coating properties can be provided.

The solvent is not particularly limited and various organic solvents conventionally used in the art can be used.

Examples of the solvent (E) 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 dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate , Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate, alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate, benzene, toluene, xylene, mesitylene and the like Aromatic hydrocarbons 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 propionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone, but are not limited thereto.

According to an embodiment of the present invention, an organic solvent having a boiling point of 100 ° C to 200 ° C may be used so that the applicability and dryness of the resin composition may be further improved. More specifically, alkylene glycol alkyl ether acetates , Ketones, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and the like, but the present invention is not limited thereto.

(F) modified silica

The modified silica (F) provides excellent adhesion and electrical insulation to the black photosensitive resin composition, and can also provide a black matrix or black column space with an OD of at least 3.0 using the composition.

The modified silica is dispersed and used in the above-mentioned photopolymerizable compound (C), and the amount of the modified silica is 1 to 20 parts by mass, preferably 5 to 15 parts by mass, per 100 parts by mass of the photopolymerizable compound (C) . If the amount of the modified silica is less than 1 part by mass, the adhesion of the black photosensitive resin composition to the modified silica composition and the electrical insulation improvement effect can not be obtained. If the amount of the modified silica exceeds 20 parts by mass, .

The modified silica is a surface modified by photopolymerization with an alkoxysilane having an unsaturated hydrocarbon group and a monomer having an unsaturated hydrocarbon.

The modified silica can be prepared by the following method.

(1) The primary silica particles are synthesized by using alkoxysilane as a precursor and adding water, ethanol and ammonia water to cause hydrolysis and condensation reaction (sol-gel method) of alkoxysilane.

(2) An alkoxysilane having a functional group, that is, an unsaturated hydrocarbon group is introduced onto the surface of the silica using an alkoxysilane having an unsaturated hydrocarbon group on the surface of the primary silica particles as a crosslinking agent.

(3) mixing the functional group-introduced silica particles with a monomer having an unsaturated hydrocarbon, and then carrying out a photopolymerization reaction to prepare a modified silica.

The alkoxysilane having the unsaturated hydrocarbon group may be at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane and vinyltet-butoxysilane. It may preferably be vinyltriethoxysilane.

The unsaturated hydrocarbon-containing monomer may be selected from the group consisting of 2-hydroxy-ethyl methacrylate, methyl methacrylate, methacrylic acid, ethylene glycol methacrylic acid, propylene glycol methacrylic acid, nonylphenylcarbitol acrylate, (Meth) acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 1,6-hexanediol di (Meth) acrylates such as neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (Meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but is not limited thereto.

According to one embodiment of the present invention, the unsaturated hydrocarbon-containing monomer may be at least one selected from the group consisting of 2-hydroxy-ethyl methacrylate, methyl methacrylate, methacrylic acid, ethylene glycol methacrylic acid and propylene glycol methacrylic acid have.

The alkoxysilane having the unsaturated hydrocarbon group may be mixed in an amount of 0.05 to 0.5 moles relative to the alkoxysilane.

The monomer having the unsaturated hydrocarbon may be contained in an amount of 1 to 2 times the number of moles of the alkoxysilane having the unsaturated hydrocarbon group, preferably 1.5 to 2 times the number of moles.

According to one embodiment of the present invention, the modified silica may be represented by the following formula (5), but is not limited thereto.

[Chemical Formula 5]

(Wherein R is independently an alkylene group of C ₂ to C ₅ and n is an integer of 2 to 100)

(G) Additive

The black photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, a curing agent, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-

Specific examples of the filler include glass, silica, alumina, and the like.

Specific examples of the other polymeric compound include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like. But it is not limited thereto.

The curing agent is used for enhancing deep curing and mechanical strength. The curing agent may be at least one thermoplastic resin selected from the group consisting of an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound, but is not limited thereto .

The epoxy compound in the curing agent may be at least one selected from the group consisting of a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a Novolak epoxy resin, other aromatic epoxy resin, an alicyclic epoxy resin, Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than brominated derivatives, epoxy resins and brominated derivatives of such epoxy resins, But is not limited to, at least one thermoplastic resin selected from the group consisting of an epoxy resin, an epoxy resin, a glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate.

In the curing agent, the oxetane compound may be at least one thermoplastic resin selected from the group consisting of carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, Resin, but is not limited thereto.

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. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, But the present invention is not limited thereto.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of commercially available epoxy resin curing agents include epoxy resin curing agents commercially available under the trade names (ADEKA HARDONE EH-700) (ADEKA INDUSTRY CO., LTD.), Trade names (RICACIDO HH) Manufactured by Ewha, Japan), and the like, but the present invention is not limited thereto.

As the pigment dispersant, a commercially available surfactant may be used, and it may be at least one selected from the group consisting of silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. It is not.

Specific examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimine (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Megapack (Manufactured by Asahi Glass Co., Ltd.), Sulfur (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.) But are not limited to, SOLSPERSE (manufactured by Lubrisol), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and Disperbyk-series (manufactured by BYK-chemi).

The adhesion promoter may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like, but is not limited thereto.

The content of the adhesion promoter may be 0.01 to 10 parts by mass, preferably 0.05 to 2 parts by mass based on 100 parts by mass of the solid content of the color photosensitive resin composition.

The antioxidant may be selected from the group consisting of hindered phenols such as 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6- Or more, but is not limited thereto.

The ultraviolet absorber may be at least one selected from the group consisting of 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, but is not limited thereto .

Specific examples of the anti-aggregation agent include, but are not limited to, sodium polyacrylate.

Another embodiment of the present invention relates to a method for producing the black photosensitive resin composition. The production method of the resin composition may include, but is not limited to, a dispersion step and a mixing step.

The dispersing step is a step of dispersing the coloring material in a solvent. More specifically, the coloring material (A) is mixed with the solvent (E) in advance and dispersed by using a bead mill or the like until the average particle diameter of the coloring material becomes about 0.2 탆 or less (a mill base The dispersing step may further include a part or all of the pigment dispersant or the binder resin (B).

The mixing step is a step of adding and mixing the dispersion and the additive. More specifically, the balance of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), the modified silica (F) and, if necessary, the additive (G) An additional solvent is further added so as to have a predetermined concentration to obtain a desired black photosensitive resin composition.

Another embodiment of the present invention relates to a color filter manufactured using the black photosensitive resin composition.

The color filter may include a black matrix or a black column spacer manufactured by using the black photosensitive resin composition.

The black matrix or the black column spacer of the color filter may exhibit an excellent optical density (optical density (OD) from 400 nm to 750 nm on average of 4.0 or less and a minimum value of 3.0 or more for each wavelength. Therefore, since the OD value of each wavelength of the black matrix or the black column spacer of the color filter according to the present invention is at least 3.0 or more, the light leakage phenomenon can be prevented when the OD value is less than 3.0. In addition, since the inorganic particles are made of silica modified with a polymer surface, excellent adhesion can be obtained and a dielectric constant of 4.0 or less can be exhibited.

According to an embodiment of the present invention, the method of manufacturing the black matrix or the black column spacer of the color filter may include a coating step and a pattern forming step, but the present invention is not limited thereto.

In the applying step, the black photosensitive resin composition is coated on a substrate and pre-dried to remove volatile components such as a solvent to obtain a smooth coated film. The thickness of the coating film at this time is usually about 0.5 to 5 mu m.

The method of applying the resin composition is not particularly limited, but may be spin coating, roll coating, dip coating, spray coating, and the like.

The substrate may be a glass plate, a silicon wafer, a plate of a plastic substrate such as polyethersulfone (PES), polycarbonate (PC), or the like, but is not limited thereto.

The pattern formation step may include an exposure step and a development step.

The step of exposing is a step of selectively exposing a part of the black photosensitive resin composition applied on the substrate.

The exposure step is a step of irradiating ultraviolet light to a specific region through a mask to cure the coated film obtained in the above to obtain a desired pattern. At this time, an apparatus such as a mask aligner or a stepper can be used so that the entire exposed portion is uniformly irradiated with parallel rays and the mask and the substrate are accurately positioned.

The developing step is a step of removing the exposed region or the non-exposed region of the black photosensitive resin composition after the exposing step.

In the developing step, the coated film after completion of the curing is contacted with an alkali aqueous solution, which is a developing solution, to dissolve and expose the non-exposed region, thereby producing a desired pattern. After development, drying can be carried out at about 150 to 230 DEG C for about 10 to about 60 minutes, if necessary.

The developing solution used in the developing step may be an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound in the developer may be either an inorganic or an organic alkaline compound. The inorganic alkaline compound is selected from the group consisting of sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Potassium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium hydrogen carbonate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, and the like, but is not limited thereto.

The concentration of the alkaline compound in the developer is in the range of 0.01 to 10% by mass, more preferably 0.03 to 5% by mass with respect to the developer.

The surfactant in the developer may be any of a nonionic surfactant, an anionic surfactant or a cationic surfactant. Examples of the nonionic surfactant 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 sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like, but the present invention is not limited thereto.

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 lauryl sulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate and dodecylnaphthalene And alkyl aryl sulfonic acid salts such as sodium sulfonate. However, the present invention is not limited thereto.

The cationic surfactant may be an amine salt such as stearylamine hydrochloride or lauryltrimethylammonium chloride, or a quaternary ammonium salt.

The content of the surfactant in the developing solution may be 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, and more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the alkali developing solution.

The constitution and the manufacturing method of the color filter including the black matrix or the black column spacer can use a conventionally known method and are not particularly limited in the present invention.

Another embodiment of the present invention relates to a liquid crystal display device manufactured using the black photosensitive resin composition.

The liquid crystal display device may include the color filter according to the present invention or may include the black space or the matrix alone. Although the structure of the liquid crystal display device is not particularly limited in the present invention, a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode and an orientation layer is faced at a predetermined interval, and a liquid crystal material To form a liquid crystal layer. It may also be a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer.

As another example, a TFT (thin film transistor) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed at a position where the TFT substrate overlaps the color filter may be used. The TFT substrate includes an outer frame made of a light-proof resin surrounding the peripheral surface of the color filter, a liquid crystal layer made of a nematic liquid crystal placed in the outer frame, a plurality of pixel electrodes , A transparent glass substrate on which pixel electrodes are formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarization direction transverse to the perpendicular direction, and is made of an organic material such as polyvinyl alcohol. Each of the plurality of pixel electrodes is connected to a plurality of thin film transistors formed on a glass substrate of a TFT substrate. If a predetermined potential difference is applied to a specific pixel electrode, a predetermined voltage is applied between the specific pixel electrode and the transparent electrode. Accordingly, the electric field formed according to the voltage changes the orientation of the region corresponding to the specific pixel electrode of the liquid crystal layer.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Manufacturing example

A: Preparation of modified silica

Mixture 1 in which the precursor (F1) and the solvent (E1) were mixed and the mixture 2 in which the solvent (E1) and the solvent (E2) were mixed was mixed in each of the components described in Table 1 below for 3 hours and 30 minutes Lt; / RTI > After mixing with the crosslinking agent (F2) after the stirring, the mixture was further stirred for 19 hours, and the photopolymerizable compound (F3) and the photopolymerization initiator (D1) were mixed and exposed with an exposure dose (365 nm) of 100 mJ / (F).

The modified silica (F) Production Example 1 (MF1,%)) The precursor (F1) Tetraethylorthosilicate
5.38 Solvent (E1) ethanol
76.76 Solvent (E2) water
13.10 Solvent (E3) ammonia
1.23 Crosslinking agent (F2) Vinyltriethoxysilane
0.97 Photopolymerization
Chemicals (F3) Polypropylene glycol methacrylate
2.43 Photopolymerization
Initiator (D1) -9- ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Irgacure OXE02; Produce)
0.13

The modified silica (F) is purified by centrifuging and redispersing using ethanol in a dispersed form in a solvent to obtain pure modified silica (F). The modified silica (F) thus obtained was dispersed in the photopolymerizable compound (C) and redispersed in an amount of 10 parts by mass based on 100 parts by mass of the total photopolymerizable compound (C).

B-1 to B-4: black pigment Dispersant

20 parts by mass of the coloring materials (A), the dispersant (G1), the dispersant (G2), the solvent (E4) and the solvent (E5) were mixed in a container in a vessel of a high speed stirrer The mixture was further stirred at a linear velocity of 5 m / s for 2 hours via a 0.5 Hp high speed mixer, and then 40 parts by mass of the solvent (E2) was further mixed and kneaded in a horizontal type bead mill (ECM-Lab, Dispersion was carried out for 3 hours at a linear velocity of 8 m / s and a flow rate of 2 kg / min using 0.3 mm zirconia beads. 19.1 parts by mass of the residual amount of the solvent (E5) after completion of dispersion was added to obtain a black pigment dispersion BK1 ~ 4 were prepared.

(Unit: parts by mass) The black pigment dispersion (BK) Manufacturing example B-1
(BK1) B-2
(BK2) B-3
(BK3) B-4
(BK4) Coloring material
(A) PBK 0.68 1.36 1.36 0 PR254 1.22 1.09 3.26 1.21 PR242 2.45 2.18 0 2.42 PY139 2.86 2.85 2.86 3.17 PB15: 6 6.39 6.12 6.12 6.80 The pigment dispersant (G1) 0.3 0.3 0.3 0.3 The pigment dispersant (G2) 4.0 4.0 4.0 4.0 Solvent (E4) 3.0 3.0 3.0 3.0 Solvent (E5) 79.1 79.1 79.1 79.1

≪ Detailed Description of Components Used in Table 2 &

The coloring material (A)

PBK: Carbon Black (MA-8, manufactured by Mitsubishi)

- PR254: Pigment Red 254 (BT-CF, manufactured by Ciba)

- PR242: Pigment Red 242 (Scarlet 4RF 01, manufactured by Clariant)

- PY139: Pigment Yellow 139 (2YK-CF, manufactured by Ciba)

- PY15: 6: Pigment Blue 15: 6 (EP-193, manufactured by DIC Corporation)

Dispersant (G1): Solsperse 5000 (manufactured by Lubrisol)

Dispersant (G2): Disperbyk-163 (BYK chemi)

Solvent (E4): n-butanol

Solvent (E5): Propylene glycol monomethyl ether acetate

≪ Examples 1 to 7, Comparative Examples 1 to 4 >

The components shown in Table 3 below were mixed to obtain a black photosensitive resin composition.

(Unit: parts by mass) division Example One 2 3 4 5 6 7 Black pigment
The dispersion (BK) BK1
67.70 BK2
67.70 BK3
67.70 BK4
67.70 BK1
67.84 BK1
67.42 BK1
67.14 Binder
Resin (B) 4.18 4.18 4.18 4.18 4.19 4.16 4.15 Photopolymerization
The compound (C) 4.18 4.18 4.18 4.18 4.19 4.16 4.15 Light curing
Initiator (D) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Solvent (E) 22.0 22.0 22.0 22.00 22.05 21.91 21.80 The modified silica (F) 0.42 0.42 0.42 0.42 0.21 0.83 1.24 Additive (G1) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Additive (G2) 0.02 0.02 0.02 0.02 0.02 0.02 0.02

(Unit: parts by mass) division Comparative Example One 2 3 4 Black pigment
The dispersion (BK) BK1
68.0 BK2
68.0 BK3
68.0 BK4
68.0 Binder
Resin (B) 4.2 4.2 4.2 4.2 Photopolymerization
The compound (C) 4.2 4.2 4.2 4.2 Light curing
Initiator (D) 1.0 1.0 1.0 1.0 Solvent (E) 22.08 22.08 22.08 22.08 The modified silica (F) 0 0 0 0 Additive (G1) 0.5 0.5 0.5 0.5 Additive (G2) 0.02 0.02 0.02 0.02

≪ Detailed Description of Components Used in Tables 3 and 4 &

Binder resin (B): Cadocase resin (WR-101, manufactured by Adecase)

Photopolymerizable compound (C): dipentaerythritol hexaacrylate

(KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (D):

-9- ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Irgacure OXE02; Produce)

Solvent (E): Propylene glycol monomethyl ether acetate

Additive (G1): Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd.)

Additive (G2): 3-methacryloxypropyltrimethoxysilane

<Experimental Example>

A 2-inch square glass substrate (# 1737, manufactured by Corning Incorporated) was sequentially washed with a neutral detergent, water and alcohol, and then dried. The black photosensitive resin composition according to the above Examples and Comparative Examples was exposed to an exposure amount (365 nm) of 100 mJ / cm 2 on this glass substrate and spin coating was carried out so that the film thickness after the post-firing was 3.0 μm when the development step was omitted , And then pre-dried in a clean oven at 100 DEG C for 3 minutes. After cooling, the substrate coated with the black photosensitive resin composition was irradiated with light (365 nm) at an exposure dose of 100 mJ / cm 2 using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI CO., LTD. Thereafter, it was baked at 220 캜 for 30 minutes.

&Lt; Optical density measurement &

Optical densities of the colored substrates produced by the above method were measured at wavelengths of 400 nm to 750 nm using OSP-200 (manufactured by Olympus Corporation). The measured results are shown in Table 3. As an evaluation standard, the average optical density ODave at a wavelength of 400 nm to 750 nm is 4.0 or more, and the minimum optical density ODmin is preferably 3.0 or more.

&Lt; Measurement of relative dielectric constant &

An aluminum electrode was formed on a colored substrate made by the above method using an aluminum vacuum deposition equipment and a mask. At this time, the aluminum electrode was deposited to a thickness of 0.075 ± 0.025 μm on the coloring layer and the non-coating layer (ITO electrode) in a circular shape with a diameter of 5 mm.

The electrostatic capacity when an AC voltage of 1 to 100 kHz and 1 V was applied to the aluminum electrode on the coating layer of the deposited sample and the aluminum electrode of the non-coating layer using a capacitance meter (trade name: LCR meter 4284A, Agilnet) And the relative dielectric constant was calculated from the value, and is shown in Table 5. It is preferable that the relative dielectric constant is less than 4.0 as an evaluation criterion.

<Adhesion Measurement>

When the color pattern substrate produced by the above method was evaluated by an optical microscope, the following pattern was evaluated as a degree of peeling phenomenon.

○: No pattern peeling

△: 1 to 3 pattern peeling

X: Pattern peeling 4 or more

division Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 OD _ave 4.0 4.3 4.1 3.5 4.1 4.0 4.1 4.1 4.3 4.1 3.6 OD _min 3.0 3.3 2.3 2.0 3.1 2.9 2.9 3.1 3.4 2.3 2.1 Relative dielectric constant 3.5 3.9 3.8 3.2 3.1 4.1 4.3 4.2 4.6 4.6 3.7 Adhesiveness ○ ○ ○ △ △ ○ ○ △ × △ △

Referring to Table 5, the black photosensitive resin composition according to the present invention contains carbon black, which is a black pigment, and modified silica, which is an organic pigment and inorganic particles, as a coloring material, and has a uniform optical density from 400 nm to 750 nm, I can confirm that it is excellent. In addition, since the OD value of the colored substrate formed according to the embodiment of the present invention shows a result of at least 3.0 or more, it can be confirmed that the light leakage phenomenon when the OD value is less than 3.0 when applied to the color filter can be prevented.

The black photosensitive resin composition of the present invention is excellent in electrical insulation and adhesion, and can provide a uniform optical density.

When a black matrix or a black column spacer is formed using the black photosensitive resin composition according to the present invention, a color filter having excellent electrical insulation and adhesiveness and excellent in light shielding property and a liquid crystal display device including the same can be provided.

Claims (12)

A coloring material (A); Binder resin (B); Photopolymerizable compound (C); A photopolymerization initiator (D); Solvent (E); And silica (F) surface-modified by photopolymerization of a monomer having an unsaturated hydrocarbon with an alkoxysilane having an unsaturated hydrocarbon group,
Wherein the coloring material (A) comprises Pigment Red 254 and Pigment Red 242 as the carbon black (A1) and the organic pigment (A2)
Wherein the modified silica (F) is contained in an amount of 1 to 20 parts by mass based on 100 parts by mass of the photopolymerizable compound (C)
Wherein the Pigment Red 242 is contained in an amount of 25 to 200 parts by mass based on 100 parts by mass of the solid content of Pigment Red 254. The method according to claim 1,
Wherein the alkoxysilane having an unsaturated hydrocarbon group is at least one member selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyloxyminosilane, vinyltriisopropoxysilane and vinyltri-tert-butoxysilane By weight based on the total weight of the black photosensitive resin composition. The method according to claim 1,
Wherein the monomer having an unsaturated hydrocarbon is selected from the group consisting of 2-hydroxy-ethyl methacrylate, methyl methacrylate, methacrylic acid, ethylene glycol methacrylic acid, propylene glycol methacrylic acid, nonylphenylcarbitol acrylate, (Meth) acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, 1,6-hexanediol di (Meth) acrylates such as neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (Meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. The method according to claim 1,
Wherein the modified silica (F) is represented by the following formula (5): &lt; EMI ID =
[Chemical Formula 5]

(R is independently a C ₂ to C ₅ alkylene group and n is an integer of 2 to 100) delete The method according to claim 1,
The modified silica (F) is:
Introducing a functional group into an alkoxysilane having an unsaturated hydrocarbon group on the surface of the silica particles and then polymerizing the functional group-introduced silica with a monomer having an unsaturated hydrocarbon, followed by photopolymerization. delete delete delete A color filter comprising a black matrix or a black column spacer manufactured using the black photosensitive resin composition of any one of claims 1 to 4. 11. The method of claim 10,
Wherein the optical density of the black matrix or black column spacer from 400 nm to 750 nm is 4.0 or more on average. A liquid crystal display device comprising the color filter of claim 10.