KR20110039674A - A black photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

PURPOSE: A black photosensitive resin composition, a color filter, a liquid crystal display apparatus are provided to obtain the uniform optical density in the wavelength of 400 to 750nm and obtain the superior electric insulation property. CONSTITUTION: A black photosensitive resin composition includes a coloring material, a binder resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent. The coloring material includes carbon black and organic pigment. 5 to 10 parts by weight of the carbon black is contained with respect to 100.0 parts by weight of the coloring material. 90 to 95 parts by weight of the organic pigment is contained with respect to 100.0 parts by weight of the coloring material.

Description

A black photosensitive resin composition, a color filter and a liquid crystal display device having the same {A BLACK PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE HAVING THE SAME}

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

Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, or the like is generally obtained by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned by spin coating. Then, the operation of exposing and developing the coating film formed by heat-drying (hereinafter sometimes referred to as "preliminary firing") and further heat curing (hereinafter sometimes referred to as "post-firing") for each color is performed. It is manufactured by forming the pixel of each color repeatedly. The black matrix patterned here is usually formed of a black photosensitive resin composition.

Recently, the introduction of a black column spacer, which can also serve as a column spacer capable of supporting the TFT-array layer and the color filter layer through the black matrix, in which case the even optical density required for the normal black matrix ( Optical density (OD) as well as good electrical insulation are required.

When only carbon black is used to form a black column spacer, such as a conventional black matrix, OD satisfies but has a disadvantage of poor electrical insulation. In order to overcome such disadvantages, in Korea Patent Publication 2007-0094460, 2009-0056735, etc. It has been proposed a technique for improving the electrical insulation by using a pigment in combination.

However, conventionally known technologies have excellent OD at wavelength 550nm due to the problem of organic pigment type and content ratio, but OD at 700nm or more is remarkably decreased, resulting in red light leakage phenomenon in actual black matrix or black column spacer pattern formation. There is a problem.

It is an object of the present invention to provide a black photosensitive resin composition which is excellent in electrical insulation and has even optical density characteristics in the region of 400 nm to 750 nm.

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

Still another object of the present invention is to provide a liquid crystal display device having the color filter.

The present invention for achieving the above object comprises a coloring material (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), the coloring material (A) ) Includes carbon black (A1), which is a black pigment, and an organic pigment (A2), wherein the carbon black (A1), which is a black pigment, is contained in an amount of 5 to 10 parts by mass based on 100 parts by mass of solids of the coloring material (A), The said organic pigment (A2) provides the black photosensitive resin composition characterized by containing 90-95 mass parts with respect to 100 mass parts of solid content of a coloring material (A).

The organic pigment (A2) preferably comprises Pigment Red 254 and Pigment Red 242. It is preferable that the said pigment red 242 contains 25-200 mass parts with respect to 100 mass parts of solid content of pigment red 254.

In addition, the organic pigment (A2) may include Pigment Red 254, Pigment Red 242, Pigment Blue 15: 6, and Pigment Yellow 139. The organic pigment (A2) is Pigment Blue 15: 6 is 40 to 60 parts by mass, Pigment Red 254 is 5 to 20 parts by mass, Pigment Red 242 is 5 to 5 parts by mass based on 100 parts by mass of the solid content of the coloring material (A) 20 parts by mass and the pigment yellow 139 may be 10 to 30 parts by mass.

The present invention also provides a color filter comprising a black matrix or black column spacer formed by applying a black photosensitive resin composition on a substrate and exposing and developing in a predetermined pattern.

The black matrix or black column spacer has an average optical density (OD below 400) of 400 nm to 750 nm, and preferably at least 3.0 for each wavelength.

The present invention also provides a liquid crystal display device comprising the color filter.

The present invention provides a black photosensitive resin composition not only excellent in electrical insulation but also having a uniform optical density in the wavelength range from 400 nm to 750 nm. When the black matrix or the black column spacer is formed using the black photosensitive resin composition, a color filter having excellent electrical insulation and excellent light shielding characteristics and a liquid crystal display device including the same may be obtained.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The black photosensitive resin composition which concerns on this invention contains a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). In addition, although not particularly limited, the black photosensitive resin composition may optionally further include an additive (F).

Hereinafter, each component contained in the black photosensitive resin composition of this invention is demonstrated in detail.

Coloring material (A)

The coloring material (A) contains carbon black (A1) and organic pigment (A2), which are black pigments.

Carbon black (A1), which is the black pigment, is not particularly limited as long as it is a pigment having light shielding properties, and known carbon black can be used. Specific examples of the carbon black A1 as the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

In addition, carbon black (A1) which is the black pigment may use carbon black coated with a resin. Since the carbon black coated with the resin has lower conductivity than the carbon black coated with the resin, it is possible to impart excellent electrical insulation when forming the black matrix or the black column spacer.

The organic pigment (A2) may be applied to those commonly used in the art. When the organic pigment (A2) is used alone or in combination of two or more thereof, it is preferable to use one having an optical density similar to that of carbon black and providing excellent electrical insulation.

As the organic pigment (A2), various pigments used in printing ink, inkjet ink, etc. may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinone pigments. , Isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthhraquinoneyl pigments, anthrapyrimidine pigments, ananthronerone pigments, indanthrone pigments, pravantrons Pigments, pyranthrone pigments, diketopyrrolopyrrole pigments and the like.

In particular, the organic pigment may specifically include a compound classified as a pigment in the color index (Published by The society of Dyers and Colourists), and more specifically, a pigment having a color index (CI) number as follows. However, it is not necessarily limited to these.

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

C.I pigment black 1 and 7, etc.

The said organic pigment (A2) can be used individually or in combination of 2 or more types, respectively.

Preferably, the organic pigment (A2) may include Pigment Red 254 and Pigment Red 242. When the organic pigment (A) includes Pigment Red 254 and Pigment Red 242, it is possible to give excellent electrical insulation and even optical density. At this time, it is preferable that the said pigment red 242 contains 25-200 mass parts with respect to 100 mass parts of solid content of pigment red 254. If the content of Pigment Red 242 is less than 25 parts by mass based on the above criteria, the OD at 500 nm wavelength may be less than 3.0, which may cause light leakage. When the content of pigment red 242 is greater than 200 parts by mass, the OD value at 550 nm wavelength may be increased. Less than 3.0, there is a problem that light leakage can occur.

In addition, the organic pigment (A2) preferably comprises Pigment Red 254, Pigment Red 242, Pigment Blue 15: 6, and Pigment Yellow 139 in order to ensure better electrical insulation and even optical density. The organic pigment (A2) is Pigment Blue 15: 6 is 40 to 60 parts by mass, Pigment Red 254 is 5 to 20 parts by mass, Pigment Red 242 is 5 to 5 parts by mass based on 100 parts by mass of the solid content of the coloring material (A) 20 mass parts and pigment yellow 139 are 10-30 mass parts. When each component in the organic pigment (A) is included in the above range it can give excellent electrical insulation and even optical density.

The coloring material (A) may contain 5 to 15 parts by mass with respect to 100 parts by mass of the black photosensitive resin composition. When the content of the coloring material is less than 5 parts by mass, the optical density is not sufficient, and when the content of the coloring material is more than 15 parts by mass, the optical density may be sufficient, but pattern formation may be difficult.

At this time, the carbon black (A1) is contained 5 to 10 parts by mass based on 100 parts by mass of the solid content of the coloring material (A), the organic pigment (A2) is 90 to 90 parts by mass based on 100 parts by mass of the solid content of the coloring material (A). It is preferable to contain 95 mass parts. If the content of the carbon black (A) is less than 5 parts by mass based on the above criteria there is a problem that can not obtain an OD value of more than 4.0, and if it exceeds 10 parts by mass, the OD value is sufficient but there is a problem of poor electrical insulation.

Binder Resin (B)

The binder resin (B) may be applied to those commonly used in the art, and in particular, the binder resin (B) is preferably a copolymer of a compound having an unsaturated carboxyl group and another monomer copolymerizable with the same.

The compound having an unsaturated carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and each compound can be used alone or in combination of two or more thereof.

Specific examples of the compound having an unsaturated 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; And anhydrides of the dicarboxylic acids; Mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2- Carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, or a mixture thereof. Among the compounds having an unsaturated carboxyl group exemplified above, acrylic acid and methacrylic acid are preferred because of excellent copolymerization reactivity and solubility in a developing solution.

Other monomers copolymerizable with the monomer having a carboxyl group are monomers having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated carboxylate compounds such as acrylates; 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; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3- methacryloxyethyl oxetane, etc. And unsaturated oxetane carboxylate compounds.

In addition, the binder resin may be a cardo-based resin generally used in the art.

The cardo-based resin is 3,3-bis (4-hydroxyphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-3-methylphenyl) -2-benzofuran -1 (3H) -one, 3,3-bis (4-hydroxy-2,5-dimethylphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy- 1-naphthyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-5-isopropyl-2-methylphenyl) -2-benzofuran-1 (3H) -one , 3,3-bis (3,5-dibromo-4-hydroxyphenyl) -2-benzofuran-1 (3H) -one, 3,3-bis (4-hydroxy-3,5-di Iodinephenyl) -2-benzofuran-1 (3H) -one, 9,9-bis (4-hydroxyphenyl) -10-anthrone, 1,2-bis (4-carboxyphenyl) carbonan, 1, 7-bis (4-carboxyphenyl) carbonan, 2-bis (4-carboxyphenyl) -N-phenylphthalimidine, 3,3-bis (4'-carboxyphenyl) phthalide, 9,10-bis- (4-aminophenyl) -anthracene, anthrone dianiline, aniline phthalein and the like. Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone and bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxy Phenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane and bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorofetyl) methane and bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3- Methylphenyl) propane and 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-di Methylphenyl) ether and bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl ) Fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4 -Hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl ) Fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene and 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene and the like It may be obtained by polymerizing a compound containing at least one monomer.

The binder resin (B) may be contained in an amount of 5 to 50 parts by mass, and preferably 10 to 40 parts by mass with respect to 100 parts by mass of the solid content in the black photosensitive resin composition. If the binder resin (B) is within the content range on the basis of the above standard, the pattern can be formed, and the resolution and the residual film ratio are improved.

Photopolymerizable Compound (C)

The said photopolymerizable compound (C) is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroly Money, etc.

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound (C) may be used in the range of 1 to 60 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass of the binder resin (B) and the photopolymerizable compound (C) based on solid content. have. Since the pattern characteristic becomes favorable if the said photopolymerizable compound (C) is the range of 1-60 mass parts on the said reference | standard, it is preferable.

Photopolymerization Initiator (D)

Although the said photoinitiator (D) is not restrict | limited, It is preferable to use at least 1 sort (s) of compound chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.

In addition, the acetophenone-based compound may be a compound represented by the following formula (1).

<Formula 1>

In Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms. 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) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-, for example) Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimi Dazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, and a phenyl group at the 4,4', 5,5 'position is carbo The imidazole compound substituted with the alkoxy group etc. are mentioned. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole can be preferably used.

As said oxime compound, the compound etc. which are represented by following General formula (2)-4 are mentioned, for example.

<Formula 2>

<Formula 3>

<Formula 4>

Moreover, in addition to the photoinitiator mentioned above, the other photoinitiator etc. which are normally used in this field can also be used together if it is a grade which does not impair the effect of this invention. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, a polyfunctional thiol compound, etc. are mentioned, for example. These can be used individually or in combination of 2 types or more, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, and pentaerythritol tetrakis-3. Mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

According to this invention, you may use combining the photoinitiator (D-1) with the said photoinitiator (D). When the photopolymerization initiation aid (D-1) is used in combination with the photopolymerization initiator (D), the black photosensitive resin composition containing them is more sensitive, so that the productivity when forming the black matrix or the black column spacer is improved by using it. Do.

As the photopolymerization initiation assistant (D-1), one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.

Specific examples of the amine compound in the photopolymerization initiation assistant (D-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino Isoamyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), Aromatic amine compounds, such as 4,4'-bis (diethylamino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used. Specific examples of the carboxylic acid compound in the photopolymerization initiation assistant (D-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenyl And aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the photopolymerization initiator (D) is 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 (B) and the photopolymerizable compound (C) based on the solid content. In addition, the content of the photopolymerization initiation assistant (D-1) is 0.1 to 50 parts by mass, preferably 1 to 40, based on 100 parts by mass of the binder resin (B) and the photopolymerizable compound (C) based on solid content. It is mass part. When the content of the photopolymerization initiator (D) is in the above range on the basis of the above criteria, the black photosensitive resin composition is highly sensitive, and thus the strength of the pixel portion formed using the composition and the smoothness on the surface of the pixel portion become good. desirable. Moreover, since the sensitivity of a black photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition improves, when the usage-amount of a photoinitiator auxiliary (D-1) exists in said range on the said reference | standard.

Solvent (E)

The solvent (E) is not particularly limited, and various organic solvents commonly used in the art may be used.

Specific 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, and diethylene. Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol Alkoxy alkyl acetates, such as alkylene glycol alkyl ether acetates, such as a monomethyl ether acetate, a propylene glycol monoethyl ether acetate, and a propylene glycol monopropyl ether acetate, a methoxy butyl acetate, and a methoxy pentyl acetate,

Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene Alcohols such as glycol and glycerin, esters such as 3-ethoxy propionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

Among the solvents described above, organic solvents having a boiling point of 100 to 200 ° C in the solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxypropionic acid. Ester, such as ethyl and 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy Methyl propionate etc. are mentioned.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent (E) is 60-90 mass parts with respect to 100 mass parts of black photosensitive resin compositions containing it, Preferably it is 70-85 mass parts. When content of the said solvent (E) is the range of 60-90 mass parts on the said reference | standard, it applied with the coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (it may be called a die coater), and inkjet. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (F)

In the black photosensitive resin composition of this invention, it is also possible to use additives (F), such as a filler, another high molecular compound, a hardening | curing agent, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

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

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be mentioned.

The said hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

Specific examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a noblock type epoxy resin, other aromatic epoxy resins, and an alicyclic epoxy resin. , Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said commercially available epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) are mentioned, for example. (Manufactured by Nippon Ewha Co., Ltd.).

The hardening | curing agent and hardening auxiliary compound which were illustrated above can be used individually or in mixture of 2 or more types, respectively.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively.

As said surfactant, polyoxyethylene alkyl ether, polyoxy ethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethylene Imine, etc .; KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink Chemical Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), Solsperth (SOLSPERSE) (made by Lubrisol), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), Disperbyk-series (made by BYK-chemi), etc. are mentioned.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

The said adhesion promoter can be used individually or in combination of 2 or more types, respectively, It is preferable to use 0.01-10 mass parts with respect to 100 mass parts of solid content of a black photosensitive resin composition, Preferably it is 0.05-2 mass parts.

As a specific example of the said antioxidant, hindered phenol type, such as 2,2'- thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t- butyl- 4-methylphenol, is mentioned.

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

As a specific example of the said aggregation inhibitor, sodium polyacrylate etc. are mentioned.

The black photosensitive resin composition of this invention can be manufactured by the following method, for example.

The coloring material (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. Under the present circumstances, a pigment dispersant is used as needed and one part or all part of binder resin (B) may be mix | blended. After adding the remainder of binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and the additive (F) as needed to the obtained dispersion liquid (Hereinafter, it may be called a mill base), Therefore, further solvent is further added so that it may become a predetermined | prescribed concentration, and a desired black photosensitive resin composition is obtained.

Hereinafter, a color filter according to the present invention will be described.

The color filter according to the present invention includes a black matrix or a black column spacer obtained by applying the black photosensitive resin composition according to the present invention on the substrate and exposing and developing in a predetermined pattern. 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, and the type thereof is not particularly limited.

More specifically, the method of forming a pattern of a black matrix or a black column spacer using the black photosensitive resin composition according to the present invention includes applying the aforementioned black photosensitive resin composition on a substrate, and a part of the black photosensitive resin composition. Selectively exposing and developing step of removing the exposed area or the non-exposed area of the black photosensitive resin composition.

. In the coating step, the black photosensitive composition of the present invention is applied onto a substrate and preliminarily dried to remove volatile components such as a solvent to obtain a smooth coating film. The thickness of the coating film at this time is about 0.5-5 micrometers normally.

The exposing step is to irradiate ultraviolet rays to a specific region through a mask to obtain a desired pattern on the coating film obtained above. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that a parallel light beam may be irradiated uniformly to the whole exposure part, and a mask and a board | substrate will be correctly aligned.

The developing step is to prepare a desired pattern by contacting the coating film after the curing is completed with an aqueous alkali solution which is a developing solution to dissolve and develop the non-exposed areas. After image development, it can carry out after about 10 to 60 minutes of drying at 150-230 degreeC as needed.

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

The alkaline compound in the developer may be any of inorganic and organic alkaline compounds. Specific examples of the inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 types or more, respectively.

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.

The surfactant in the developer may be used both of nonionic surfactants, anionic surfactants or cationic surfactants. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like. Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate and dode Alkyl aryl sulfonates, such as sodium cinnaphthalene sulfonate, etc. are mentioned. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. The said surfactant can be used individually or in combination of 2 types or more, respectively.

The content of the surfactant in the developer is usually 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 in 100 parts by mass of the alkaline developer.

Through the above process, a black matrix or a black column spacer is obtained. Since the configuration and manufacturing method of the color filter are well known in the art, detailed description thereof will be omitted.

The black matrix or black column spacer of the color filter according to the present invention prepared as described above has excellent optical density (OD of below 400) to 750 nm on average of 4.0 or less and at least 3.0 for each wavelength. . Therefore, since the OD value of each wavelength of the black matrix or black column spacer of the color filter according to the present invention is at least 3.0 or more, light leakage phenomenon occurring when the OD value is less than 3.0 is prevented.

The present invention also includes a liquid crystal display device provided with the color filter described above.

The liquid crystal display of the present invention includes a configuration known in the art, except that the above-described color filter is provided. That is, all of the liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is faced at predetermined intervals, and a liquid crystal material is injected into the gap to form a liquid crystal layer. Can be. There is also 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 liquid crystal display device including a TFT (Thin Film Transistor) substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of nematic liquid crystals imposed in the outer frame, and a plurality of pixel electrodes provided for each region of the liquid crystal layer. , A transparent glass substrate on which the pixel electrode is formed, and a polarizing plate formed on the exposed surface of the transparent glass substrate.

The polarizing plate has a polarizing direction that traverses vertically and is made of an organic material such as polyvinyl alcohol. A plurality of pixel electrodes are connected with a plurality of thin film transistors each 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. Therefore, 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.

As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover, contains all modifications within the meaning and range equivalent to the claims. In addition, "%" and "part" which show content in a following example and a comparative example are a mass reference | standard unless there is particular notice.

<Black pigment dispersion preparation examples 1-9>

High-speed stirrer after mixing 20 mass parts of a coloring material (A), a dispersing aid (F1), a dispersing agent (F2), a solvent (E1), and a solvent (E2) in a container beforehand in each component of Table 1 below. After mixing for 2 hours at a linear speed of 5 m / s through a 0.5 Hp high speed mixer, 40 parts by mass of the solvent (E2) were further mixed, and a horizontal bead mill (manufactured by Dyno, ECM-Lab) To 0.3 m zirconia beads at a linear speed of 8 m / s and a flow rate of 2 kg / min for 3 hours, and after completion of the dispersion, add 19.1 parts by mass of the remaining amount of solvent (E2) to add a black pigment dispersion. BK1-9 were prepared.

Black Pigment Dispersion (BK) Production Example
1 (BK1) Production Example
2 (BK2) Production Example
3 (BK3) Production Example
4 (BK4) Production Example
5 (BK5) Production Example
(6BK6) Production Example
7 (BK7) Production Example
8 (BK8) Production Example
9 (BK9) Coloring material
(A) PBK 0.68 0.68 1.36 1.36 1.36 1.36 0 2.04 0.34 PR254 1.22 2.45 1.09 2.18 3.26 0 1.21 1.03 1.22 PR242 2.45 1.22 2.18 1.09 0 3.26 2.42 2.06 2.44 PY139 2.86 2.86 2.85 2.85 2.86 2.86 3.17 2.69 3.01 PB15: 6 6.39 6.39 6.12 6.12 6.12 6.12 6.80 5.78 6.59 Pigment Dispersant (F1) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Pigment Dispersant (F2) 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Solvent (E1) 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Solvent (E2) 79.1 79.1 79.1 79.1 79.1 79.1 79.1 79.1 79.1

<Detailed description of the ingredients used in Table 1 above>

Coloring material (A)

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

  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 (F1): Solsperse 5000 (manufactured by Lubrisol)

Dispersant (F2): Disperbyk-163 (manufactured by BYK chemi)

Solvent (E1): n-butanol

Solvent (E2): propylene glycol monomethyl ether acetate

<Examples 1-6, Comparative Examples 1-3>

Each component of the following Table 2 was mixed and the black photosensitive resin composition was obtained.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Black Pigment
Dispersion (BK) BK1
68 BK2
68 BK3
68 BK4
68 BK5
68 BK6
68 BK7
68 BK8
68 BK9
68 Binder
Resin (B) Cardo resin (WR-101, product made by Adeka Corporation)
4.2 Photopolymerization
Compound (C) Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
4.2 Photopolymerization
Initiator (D) Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Cibasa Produce)
1.0 Solvent (E) Propylene Glycol Monomethyl Ether Acetate
22.08 Additive (F1) Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)
0.5 Additive (F2) 3-methacryloxypropyltrimethoxysilane
0.02

Experimental Example

A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the black photosensitive resin composition which concerns on the said Example and a comparative example was exposed by exposure amount (365 nm) of 100 mJ / cm <2>, and spin-coating so that the film thickness after baking may be 3.0 micrometers when the image development process is skipped. Then, it dried preliminarily at 100 degreeC in the clean oven for 3 minutes. After cooling, the board | substrate to which this black photosensitive resin composition was apply | coated was irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Then, it baked after 30 minutes at 220 degreeC.

<Optical density measurement>

The optical density in 400 nm-750 nm wavelength was measured for the colored board | substrate produced by the said method using OSP-200 (made by Olympus). The measured results are shown in Table 3. As evaluation criteria, the average optical density OD _ave at a wavelength of 400 nm to 750 nm is preferably 4.0 or more, and the minimum optical density OD _min is preferably 3.0 or more.

<Measurement of relative dielectric constant>

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

Capacitance when an alternating voltage of 1 to 100 kHz, 1 V was applied to the aluminum electrode on the coating layer of the deposited specimen and the aluminum electrode of the non-coating layer using a capacitance meter (trade name LCR meter 4284A, Agilnet). It measured, and the dielectric constant was computed from the value, and is shown in Table 3. It is preferable that the dielectric constant is less than 5.0 as the evaluation criteria.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 OD _ave 4.1 4.2 4.3 4.3 4.1 4.1 3.6 4.5 3.9 OD _min 3.1 3.0 3.4 3.3 2.3 2.4 2.1 3.5 2.6 Relative dielectric constant 4.2 4.2 4.6 4.6 4.6 4.7 3.7 5.4 4.0

As shown in Table 3 above, the black photosensitive resin composition of the embodiment, which includes carbon black and organic pigment as a black pigment and is included in the preferred range of the present invention, has a uniform optical density and excellent electric insulation. It can be seen that a matrix or black column spacer is obtained. However, in Example 5 and Example 6, in which Pigment Red 254 and Pigment Red 242 were not combined with organic pigments, it was confirmed that optical density characteristics were not as good as those of Examples 1 to 4 using the combination of both. .

Particularly, in Examples 1 to 4, carbon black, which is a black pigment, and an organic pigment are included as the coloring material, but they are excellent in uniform optical density and electrical insulation at 400 nm to 750 nm compared to Comparative Example 2, which is outside the preferred range of the present invention. You can see that. In particular, in the case of the embodiment according to the present invention, since the OD value indicates a result of at least 3.0 or more, it can be seen that there is an effect of preventing light leakage that occurs when the OD value is less than 3.0.

Claims (8)

It comprises a coloring material (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), The coloring material (A) comprises a black pigment carbon black (A1) and an organic pigment (A2), Carbon black (A1) which is the said black pigment contains 5-10 mass parts with respect to 100 mass parts of solid content of a coloring material (A), and the said organic pigment (A2) contains 90 mass parts of 100 mass parts of solid content of a coloring material (A). To 95 mass parts is contained, The black photosensitive resin composition characterized by the above-mentioned. The black photosensitive resin composition of claim 1, wherein the organic pigment (A2) comprises Pigment Red 254 and Pigment Red 242. The black photosensitive resin composition according to claim 2, 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 the pigment red 254. The black photosensitive resin composition of claim 1, wherein the organic pigment (A2) comprises Pigment Red 254, Pigment Red 242, Pigment Blue 15: 6, and Pigment Yellow 139. The organic pigment (A2) according to claim 4, wherein Pigment Blue 15: 6 is 40 to 60 parts by mass, Pigment Red 254 is 5 to 20 parts by mass based on 100 parts by mass of solids of the coloring material (A). Red 242 contains 5 to 20 parts by mass, and Pigment Yellow 139 contains 10 to 30 parts by mass, the black photosensitive resin composition. A color filter comprising a black matrix or a black column spacer obtained by applying the black photosensitive resin composition of any one of claims 1 to 5 on a substrate and exposing and developing in a predetermined pattern. The color filter of claim 6, wherein the black matrix or the black column spacer has an optical density (OD) of 400 nm to 750 nm or more, and an average of 4.0 or more, and an OD value of each wavelength is 3.0 or more. A liquid crystal display device comprising the color filter of claim 6.