KR101541195B1 - A red colored photosensitive resin composition, color filter and liquid crystal display device having the same - Google Patents

Abstract

The present invention relates to (A) Pigment Red 242 and C.I. (B) a binder resin comprising a polymer of a bulky monomer and a polymer of a bulky monomer and other polymerizable monomer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) solvent, wherein the CI Pigment Red 242 and Pigment Red 177 are mixed in a mass ratio of 10:90 to 90:10. A colored photosensitive resin composition for a red coloring layer, a color filter, and a liquid crystal display device .

The above-mentioned colored photosensitive resin composition for a red coloring layer is excellent in contrast and brightness, and has a color filter formed on a TFT substrate which does not have a problem of display failure which is caused by a voltage applied portion not operating correctly, A display device can be provided.

Color filter, high aperture ratio, relative dielectric constant

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition for a red coloring layer, a color filter, and a liquid crystal display device having the same. BACKGROUND ART [0002]

The present invention relates to a colored photosensitive resin composition for a red coloring layer, a color filter, and a liquid crystal display device having the same.

Generally, in a liquid crystal display device, a color filter having a plurality of colored layers corresponding to a plurality of pixels of a liquid crystal display element is arranged to realize color image display. This color filter is formed on the side of the opposing substrate opposite to the TFT substrate not on the substrate on which the thin film transistor (hereinafter referred to as TFT) on which the switching element is formed (hereinafter referred to as the TFT substrate) have.

However, when the color filter is disposed on the side of the counter substrate, positioning with respect to each pixel electrode on the TFT substrate is not simple and the aperture ratio is low. In addition, since the distance between the color filter and the liquid crystal layer is relatively large, a problem of lowering the display quality caused by the light incident from the oblique direction occurs.

To solve such a problem, Japanese Laid-Open Patent Publication No. 09-73078 discloses a technique for forming a color filter on a TFT substrate. However, there is a problem that the portion to which the voltage is applied does not operate correctly and display failure occurs. In order to suppress such display failure, Japanese Patent Application Laid-Open No. 2001-324611 discloses that the relative dielectric constant of a colored layer formed of a colored photosensitive resin composition forming a color filter is 10 or less.

However, in a liquid crystal display device of a large size and a high resolution, there is still a problem that a voltage applied portion does not operate correctly and display failure occurs. Particularly, in the case of a red coloring layer, There is a problem that contrast and brightness can not be obtained.

The object of the present invention is to provide a colored photosensitive resin composition for a red coloring layer which is formed on a TFT substrate which is not only excellent in contrast and brightness, but also has no problem of display failure caused by a voltage applied portion not operating correctly.

Another object of the present invention is to provide a color filter with improved display defects.

Another object of the present invention is to provide a liquid crystal display device with improved display defects.

In order to achieve the above object, the present invention provides a colored photosensitive resin composition for a red coloring layer formed on a TFT substrate, wherein the colored photosensitive resin composition for a red coloring layer comprises (A) (B) a binder resin comprising a polymer of a polymer or a vulcanizable monomer of (B) a vulcanizable monomer and another monomer capable of polymerizing with the same, (C) a photopolymerizable compound, D) a photopolymerization initiator, and (E) a solvent, wherein the CI Pigment Red 242 and Pigment Red 177 are mixed in a mass ratio of 10:90 to 90:10.

The C.I. Pigment Red 242 and C.I. Pigment Red 177 is preferably mixed in a mass ratio of 70:30 to 30:70.

The coloring material is preferably contained in an amount of 3 to 60 mass% based on the solid content in the colored photosensitive resin composition for a red coloring layer.

It is preferable that the above-mentioned vulcanizable monomer is at least one selected from a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton or a monomer having a rosin skeleton.

The binder resin may include a copolymer of a bulky monomer and a monomer having a carboxyl group.

The above-mentioned vulcanizable monomer is preferably a macromonomer having at least two bulky skeletons therein.

According to another aspect of the present invention, there is provided a color filter comprising a coloring layer formed on a TFT substrate, wherein the coloring layer is a red coloring layer formed using the colored photosensitive resin composition for a red coloring layer according to the present invention, And a color filter.

According to another aspect of the present invention, there is provided a liquid crystal display device including the color filter.

The colored photosensitive resin composition for a red coloring layer according to the present invention is free from the problem of poor display caused by a voltage applied portion not being operated correctly when applied to forming a red coloring layer on a TFT substrate, It is possible to provide an excellent color filter. Accordingly, it is possible to provide a high-quality liquid crystal display device which is improved in display defects, which is a disadvantage, while maintaining high aperture ratio characteristics, which is an advantage of conventional color filter on array (COA) type liquid crystal display devices.

The present invention is described in more detail below.

The colored photosensitive resin composition for a red coloring layer according to the present invention comprises (A) Pigment Red 242 and C.I. (B) a binder resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent.

The coloring material (A)

In order to provide a red coloring layer having a low relative dielectric constant, the coloring material is preferably a mixture of C.I. Pigment Red 242 and C.I. Pigment Red 177 < / RTI >

Preferably, the C. I. red 242 and the red 177 are mixed in a mass ratio of 10:90 to 90:10, more preferably 70:30 to 30:70, in order to adjust the color tone.

When the mixing mass ratio of the CI red 242 and the red 177 is within the range of 10:90 to 90:10, the contrast and the luminance are excellent, and in particular, the problem of the display failure that occurs due to the non- .

The coloring material according to the present invention may further include other coloring materials generally used in the art in addition to CI Red 242 and Red 177 within the scope of the present invention.

The content of the coloring material (A) is usually in the range of 3 to 60% by mass, preferably 5 to 55% by mass with respect to the solid content in the colored photosensitive resin composition for a red coloring layer. When the content of the coloring material (A) is in the range of 3 to 60 mass% on the basis of the above criteria, even when a thin film is formed, the color density of the pixel is sufficient and the residue of the non- .

In the present invention, the solid content in the color photosensitive composition for a red coloring layer means the sum of the components from which the solvent has been removed.

When the coloring material includes a pigment, a pigment dispersion containing a pigment dispersant and performing a dispersion treatment can be obtained in a state in which the pigment is uniformly dispersed in a solution.

As the pigment dispersant, for example, a surfactant such as a cationic, anionic, nonionic, amphoteric, polyester, polyamine, polyacrylic, and the like may be used. These surfactants may be used alone or in combination of two or more Can be used.

When a pigment dispersant is used, its amount to be used is 1 part by mass or less, more preferably 0.05 part by mass to 0.5 part by mass, per 1 part by mass of the coloring material in the colored photosensitive resin composition for a red coloring layer. When the amount of the pigment dispersant is within the above range, a pigment in a uniformly dispersed state can be obtained, which is preferable.

The binder resin (B)

The binder resin (B) usually has reactivity and alkali solubility due to the action of light or heat, and acts as a dispersion medium of a coloring material. The binder resin (B) contained in the colored photosensitive resin composition for a red coloring layer of the present invention functions as a binder resin for the coloring material (A) and has a property soluble in the alkaline developer used in the developing step for the production of the color filter .

The binder resin (B) according to the present invention comprises a polymer of a bulky monomer or a polymer of a bulky monomer and another monomer capable of polymerization.

The bulky monomer in the binder resin (B) may be at least one selected from a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton. The above-mentioned bulky keying monomer can be preferably used because it lowers the value of the relative dielectric constant. These bulky monomer may be used alone or in combination of two or more. The above-mentioned vulcanizable monomer is preferably a macromonomer having at least two bulky skeletons therein. The above-mentioned macromonomer is preferable because it lowers the value of the dielectric constant more effectively.

Examples of other monomers capable of polymerization with the above-mentioned bulky monomer include, for example, carboxyl group-containing monomers.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated tricarboxylic acid and the like .

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like.

The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate . These carboxyl group-containing monomers may be used alone or in combination of two or more.

The binder resin (B) according to the present invention may contain, in addition to the carboxyl group-containing monomer, a copolymer of the carboxyl group-containing monomer and another monomer copolymerizable with the carboxyl group-containing monomer.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- P-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p Aromatic vinyl compounds such as vinylbenzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated carboxylic acid esters; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzyl maleimide, N-phenyl maleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monoacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, , And the like. These monomers may be used alone or in combination of two or more.

The acid value of the binder resin of the present invention is preferably in the range of 20 to 200 (KOH mg / g). When the acid value is in the above range, the solubility in the developer is improved, the non-exposed portion is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed portion remains during development, thereby improving the film remaining ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") of the polymer of 3,000 to 200,000, preferably 5,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC; tetrahydrofuran as an elution solvent) Binder resins are preferred. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent, and the resolution is improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the binder resin (B) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) is 1.5 to 6.0, development is preferable.

The content of the binder resin (B) of the present invention is usually in the range of 5 to 85% by mass, preferably 10 to 70% by mass with respect to the solid content in the colored photosensitive resin composition for a red coloring layer. When the content of the binder resin (B) is 5 to 85% by mass on the basis of the above criteria, solubility in a developing solution is sufficient, so that development residue is not easily generated on the substrate of the non-pixel portion, And it is preferable that the non-pixel portion is omitted.

The photopolymerizable compound (C)

The photopolymerizable compound (C) contained in the colored photosensitive resin composition for a red coloring layer of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and includes monofunctional monomers, bifunctional monomers, .

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

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.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And pentaerythritol hexa (meth) acrylate.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The photopolymerizable compound (C) is used in a mass fraction of usually 5 to 50% by mass, preferably 7 to 45% by mass, based on the solid content in the colored photosensitive resin composition for a red coloring layer. When the photopolymerizable compound (C) is in the range of 5 to 50 mass% based on the above-mentioned criteria, it is preferable because the strength and smoothness of the pixel portion are good.

Photopolymerization initiator (D)

The photopolymerization initiator (D) used in the present invention preferably contains an acetophenone-based compound. Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane -1-one, and preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one. The above-exemplified photopolymerization initiators (D) may be used alone or in combination of two or more.

The photopolymerization initiator may be used in combination with a photopolymerization initiator other than the acetophenone-based photopolymerization initiator. Photopolymerization initiators other than acetophenone-based photopolymerization initiators include active radical generators, sensitizers, and acid generators that generate active radicals upon irradiation with light.

Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like. Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5 -Triazine, and the like.

Examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- Benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, a titanocene compound, etc. may be used. Can be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluene sulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene sulfone 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium p-toluenesulfonate, Diphenyl iodonium hexafluoroantimonate and the like, and nitrobenzyl tosylates, benzoin tosylates and the like. Also, as the active radical generator, there are compounds which generate an acid at the same time as an active radical, and for example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator (D) used in the colored photosensitive resin composition for a red coloring layer according to the present invention is preferably from 0.1 to 40% by mass, based on the solid content, of the total amount of the binder resin (B) Mass%, preferably 1 to 30 mass%. Within the above range, it is preferable that the colored photosensitive resin composition for a red coloring layer is highly sensitized so that the strength of the pixel portion formed by using the composition and the smoothness on the surface of the pixel portion become favorable.

In the present invention, a photopolymerization initiator can be used. The photopolymerization initiator is sometimes used in combination with a photopolymerization initiator, and is a compound used for promoting polymerization of a photopolymerizable compound initiated by a photopolymerization initiator. Examples of the photopolymerization initiator include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylamino benzoate Ethyl (4-dimethylaminobenzoic acid), 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone Amino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene And the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like.

The above-mentioned photopolymerization initiators (D) may be used singly or in combination of two or more. Commercially available photopolymerization initiators may be used. Examples of commercially available photopolymerization initiators include trade names " EAB-F " (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

When a photopolymerization initiator is used, its amount to be used is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. Within the above range, the sensitivity of the colored photosensitive resin composition for a red coloring layer is higher, and the productivity of a color filter formed using the composition tends to be improved.

Solvent (E)

The solvent (E) contained in the colored photosensitive resin composition for a red coloring layer of the present invention is not particularly limited and various organic solvents used in the field of the colored photosensitive resin composition can be used.

Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol 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, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, Ke , Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, 3- Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.

Among the above solvents, organic solvents having a boiling point of 100 占 폚 to 200 占 폚 in the solvent are preferably used from the viewpoint of coatability and dryness, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Propylene glycol monomethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-ethoxypropionate, and 3-methoxypropionate are more preferable. Examples of the solvent include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Methyl methoxypropionate, and the like. These solvents (E) may be used alone or in combination of two or more.

The content of the solvent (E) in the colored photosensitive resin composition for a red coloring layer of the present invention is usually 60 to 90% by mass, preferably 70 to 85% by mass, based on the total amount of the colored photosensitive resin composition for a red coloring layer %to be. When the content of the solvent (E) is in the range of 60 to 90% by mass on the basis of the above criteria, it can be applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater It is preferable because the coating property becomes good.

Additive (F)

In the colored photosensitive resin composition for a red coloring layer of the present invention, fillers, other polymer compounds and pigment dispersing agents are optionally added. (F) such as an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent.

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

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

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, (Trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Mega (Manufactured by Asahi Glass Co., Ltd.), Surfon (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kagaku Kogyo Co., Ltd., MEGAFAC (manufactured by Dainippon Ink and Chemicals Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon SOLSPERSE (manufactured by Genene), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 (aminoethyl) - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Trimethoxysilane, and the like.

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

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

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

The colored photosensitive resin composition for a red coloring layer of the present invention can be produced, for example, by the following method. The coloring material (A) is mixed with the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the coloring material becomes about 0.2 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (B) may be blended. (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), other components to be used if necessary, and optionally further solvents Is further added to a predetermined concentration to obtain a desired colored photosensitive resin composition for a red coloring layer.

In the present invention, in a color filter comprising a coloring layer formed on a TFT substrate, the coloring layer comprises a color filter including a red coloring layer formed using the colored photosensitive resin composition for a red coloring layer according to the present invention, A display device is provided.

The process of forming a colored layer using the colored photosensitive resin composition for a red coloring layer of the present invention will be described below with reference to Fig.

In the case of manufacturing a color filter by a COA (Color Filter on Array) method, pixel patterns of red, green, and blue are formed directly on a SiNx (protective layer) coating film of a TFT layer substrate (FIG. In this case, the red pixel pattern is formed using the colored photosensitive resin composition for a red coloring layer according to the present invention.

A positive photosensitive resin film is patterned by using a mask to remove the SiNx (protective layer) coating film as a process for forming an electrical conduction path between the TFT layer and the electrode (IZO layer) (FIG. 1B).

SiNx (protective layer) located on the lower surface (electric conduction path) of the positive photosensitive resin film is subjected to dry etching (dry etching) to form an electrical conduction path (FIG.

In order to remove the positive photosensitive resin film remaining on the pixel pattern of Fig. 1C, the positive photosensitive resin film layer is removed using a stripper developer (Fig. 1D).

An IZO layer to be used as a common electrode (IZO layer) with the TFT layer is deposited (Fig. 1E).

A positive photosensitive resin film is patterned on the common electrode (IZO layer) layer to form a common electrode (IZO layer) layer (Fig. 1F).

The exposed portion (the portion where the IZO layer is exposed) of the formed positive photosensitive resin film is removed by wet etching (wet etching) (Fig. 1G).

The positive photosensitive resin film is removed using a stripper developer to remove the remaining positive photosensitive resin film on the common electrode (IZO layer) of FIG. 1G (FIG. 1H).

The color filter according to the present invention including the colored layer manufactured as described above is characterized in that there is no problem of display failure that occurs due to the incorrect operation of the portion to which the voltage is applied, and the contrast and brightness are excellent. Accordingly, the present invention can provide a high-quality liquid crystal display device which improves the defective display, which is a disadvantage of the conventional COA (Color Filter on Array) type liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these embodiments by way of example. It is intended that the scope of the invention be indicated by the appended claims and include all changes that come within the meaning and range of equivalency of the claims which follow. In the following, "%" and "part" representing the content are on a mass basis unless otherwise specified.

Synthesis Example 1: Binder resin (B-1)

(0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and 118.0 g of vinyltoluene were placed in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube. 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were charged and stirred to prepare a mixture. As a chain transfer agent, 6 g of n-dodecanethiol , And PGMEA (24 g) were mixed and stirred. Thereafter, 395 g of propylene glycol monomethyl ether acetate was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 캜 while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The mixture was allowed to proceed for 2 hours each while maintaining the temperature at 90 캜. After 1 hour, the temperature was elevated to 110 캜 and maintained for 3 hours. Then, a gas introduction tube was introduced to obtain an oxygen / nitrogen mixed gas of 5/95 (v / v) And started bubbling. Then, 22.0 g (0.10 mole) of tricyclodecane (meth) acrylate, 33 mole% of the carboxyl group of the acrylic acid used in the present reaction), 2,2'-methylenebis (4-methyl- Butylphenol) and 0.8 g of triethylamine were placed in a flask, and the reaction was continued at 110 ° C for 8 hours to obtain a resin B-1 having a solid acid value of 70 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 16,000 and the molecular weight distribution (Mw / Mn) was 2.3.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin were measured using a HLC-8120GPC (manufactured by TOSOH CORPORATION) apparatus. The columns were obtained by connecting TSK-GELG4000HXL and TSK-GELG2000HXL in series , The column temperature was 40 ° C, the mobile phase solvent was tetrahydrofuran, the flow rate was 1.0 ml / min, the injection amount was 50 μl and the detector RI was used. The concentration of the sample was 0.6% by mass (solvent = tetrahydrofuran) TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION) were used as standard materials.

Synthesis Example 2: Binder Resin (B-2)

46.2 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was changed to nitrogen in air, and then 11.1 g of dicyclopentanyl methacrylate (About 0.051 mole) of benzyl methacrylate, 1.9 g of thiol glycolic acid and 6.0 g of t-butylperoxy-2-ethylhexanoate was added to the flask from a dropping funnel over 2 hours in a flask And the mixture was stirred at 120 占 폚 for 0.5 hour. Subsequently, 2.9 g of glycidyl methacrylate, 0.3 g of triphenylphosphine, and 0.06 g of methylhydroquinone were charged into the flask, and the mixture was allowed to react at 120 ° C. for 3 hours. The reaction solvent was added dropwise to 2 liters of n-hexane and then reprecipitated to obtain 82 g of a macromonomer M-1 in the form of a white powder. A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 151.9 g of propylene glycol monomethyl ether acetate. The atmosphere in the flask was changed to nitrogen in air, and then the temperature was raised to 120 ° C. A solution containing 2.7 g of the macromonomer (M-1) prepared above, 72.5 (0.41 mol) of benzylmethacrylate, 25.2 g (0.28 mol) of methacrylic acid and 1.3 g of t-butylperoxy-2-ethylhexanoate The solution was dropped from the dropping funnel into the flask over a period of 2 hours, and then continued at 120 DEG C for 0.5 hour to obtain a binder resin B-2 having a solid acidity of 160 KOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 26,000 and the molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 3: Binder Resin (B-3)

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen-introducing tube, and the atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, benzyl methacrylate 70.5 (0.10 mole) of rosin acrylate (Bimaseet 101, Arakawa Chemical Industries, Ltd.) and 136 g of propylene glycol monomethyl ether acetate was added to a mixture of azobis (0.40 mole), methacrylic acid (45.0 g) And 3.6 g of isobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 캜 for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g (0.2 mol) of glycidyl methacrylate (40 mol% based on the carboxyl group of the methacrylic acid used in the present reaction)], 0.9 g of trisdimethylaminomethylphenol, , And the reaction was continued at 110 DEG C for 6 hours to obtain a resin B-3 having a solid acid value of 99 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 28,000 and the molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 4: Binder Resin (B-4)

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen-introducing tube, and the atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, benzyl methacrylate 70.5 (0.10 mol) of 2- (2-methyl) adamantyl methacrylate and 136 g of propylene glycol monomethyl ether acetate was added to a mixture of azobis And 3.6 g of isobutyronitrile was added dropwise to the flask over 2 hours from the dropping funnel, and stirring was further continued at 100 캜 for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g (0.2 mol) of glycidyl methacrylate (40 mol% based on the carboxyl group of the methacrylic acid used in the present reaction)], 0.9 g of trisdimethylaminomethylphenol, And the reaction was continued at 110 DEG C for 6 hours to obtain a resin B-4 having a solid acid value of 99 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 23,000 and the molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 5: Binder Resin (B-5)

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen-introducing tube, and the atmosphere in the flask was changed to nitrogen in air. After raising the temperature to 100 캜, benzyl methacrylate 70.5 A solution of 3.6 g of azobisisobutyronitrile added to a mixture containing 0.40 g (0.40 mol) of methacrylic acid, 45.0 g (0.50 mol) of methacrylic acid and 136 g of propylene glycol monomethyl ether acetate was added to the flask Followed by further stirring at 100 DEG C for 5 hours. Subsequently, the atmosphere in the flask was changed from nitrogen to air, and 30 g (0.2 mol) of glycidyl methacrylate (40 mol% based on the carboxyl group of the methacrylic acid used in the present reaction)], 0.9 g of trisdimethylaminomethylphenol, And the reaction was continued at 110 DEG C for 6 hours to obtain a resin B-5 having a solid acid value of 99 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 19,000 and the molecular weight distribution (Mw / Mn) was 2.1.

≪ Examples 1 to 7 and Comparative Examples 1 to 6 >

A colored photosensitive resin composition having a composition as shown in Table 1 below was prepared.

Example Comparative Example One 2 3 4 5 6 7 One 2 3 4 5 coloring
material A-1 3.86 7.74 1.94 4.83 4.83 4.83 4.83 3.86 1.93 A-2 5.78 1.91 7.65 4.79 4.79 4.79 4.79 5.78 5.74 5.06 7.65 6.22 A-3 3.44 1.93 A-4 1.84 A-5 1.05 3.36 Binder
Suzy B-1 4.42 4.41 4.47 4.44 4.48 B-2 4.44 B-3 4.44 B-4 4.44 B-5 4.42 4.55 4.51 4.48 Photopolymerization
The compound (C) 3.76 3.76 3.76 3.76 3.76 3.76 3.76 3.76 3.76 3.76 3.76 3.76 Photopolymerization initiator D-1 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 1.03 D-2 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 Solvent (E) 79.84 79.84 79.84 79.84 79.84 79.84 79.84 79.84 79.84 79.84 79.84 79.84 additive F-1 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.94 0.94 F-2 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18

Coloring material (A-1): C.I. Pigment Red 242

Coloring material (A-2): C.I. Pigment Red 177

Coloring material (A-3): C.I. Pigment Red 254

Coloring material (A-4): C.I. Pigment Yellow 138

Coloring material (A-5): C.I. Pigment Yellow 150

Binder resins (B-1) to (B-5): Refer to Synthesis Examples 1 to 5

Photopolymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (D-1): 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369;

Photopolymerization initiator (D-2): 4,4'-di (N, N'-dimethylamino) -benzophenone (EAB-F; manufactured by Hodogaya Chemical Co.,

Solvent (E): Propylene glycol monomethyl ether acetate

Additive (F-1): Pigment dispersant (acrylic)

Additive (F-2): 3-methacryloxypropyltrimethoxysilane

<Experimental Example 1> Measurement of relative dielectric constant

- Measurement specimen production

A color filter including a colored layer produced using the colored photosensitive resin composition prepared according to the above Examples and Comparative Examples was prepared.

A glass substrate (# 1737, manufactured by Corning Incorporated) of 25 cm 2 was sequentially washed with a neutral detergent, water and alcohol, and then dried. An ITO electrode was deposited to a thickness of 0.150 mu m on this glass substrate. The red photosensitive resin composition was spin-coated on the substrate so as to have a thickness of 3.0 ± 0.5 μm after baking, and then preliminarily dried in a clean oven at 100 ° C. for 3 minutes. After cooling, the space between the substrate coated with this colored photosensitive resin composition and a quartz glass photomask (exposed portion: 30 mm × 30 mm) was set to 100 μm, and an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI Co., (365 nm) at an exposure dose of 100 mJ / cm &lt; 2 &gt;. Thereafter, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.06% of potassium hydroxide at 26 캜 for a predetermined time, developed and then heated in a heating oven at 200 캜 for 30 minutes, . 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.

- Measurement of relative dielectric constant

When an AC voltage of 1 to 100 kHz and a voltage of 1 V was applied to the aluminum electrode on the coating layer of the specimen obtained by the above method and the aluminum electrode of the non-coating layer using a capacitance meter (trade name: LCR meter 4284A, Agilnet) The electrostatic capacity was measured, and the relative dielectric constant was calculated from the value, and it is shown in Table 2 below. It is preferable that the relative dielectric constant is less than 5.0 as an evaluation standard.

<Experimental Example 2> Measurement of luminance, color coordinate and contrast

- Measurement specimen production

A coloring layer was prepared using the colored photosensitive resin composition prepared according to the above Examples and Comparative Examples. That is, this was coated on a glass substrate by spin coating, then placed on a heating plate, and held at a temperature of 100 캜 for 3 minutes to form a thin film. Subsequently, irradiation was conducted at a light intensity of 100 mJ / cm 2 using a 1 kw high-pressure mercury lamp containing g, h and i lines. No special optical filter was used at this time. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass substrate coated with the thin film was washed with distilled water, blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 30 minutes. The thickness of the obtained colored layer was 3 ± 1 μm.

- Measurement of luminance and color coordinates

And measured using a microscopic spectrometer OSP-SP2000. The luminance is shown in Table 2 below, and the color coordinates are shown in Table 3.

The evaluation criteria of the luminance (Y) are as follows.

?: Y? 18.0,?: 16? Y <18, X: Y <16

- Constrast measurement

The measurement was performed using a Topcon CONS Contrast Meter BM-5A model, and the measurement standard was a standard of a contrast of 1/30000 on a glass substrate (before the formation of a colored layer). The results are shown in Table 2 below.

The evaluation criteria of the contrast (CR) are as follows.

?: CR? 22000,?: 19000? CR <22000,?: 16000? CR <1900, X: CR <16000

Relative dielectric constant Luminance Contrast Example 1 4.2 ○ ◎ Example 2 4.2 ○ ◎ Example 3 4.2 △ ◎ Example 4 4.2 ○ ◎ Example 5 3.9 ○ ◎ Example 6 4.0 ○ ◎ Example 7 4.0 ○ ◎ Comparative Example 1 4.6 ○ ◎ Comparative Example 2 4.6 ○ △ Comparative Example 3 4.9 △ ○ Comparative Example 4 4.5 △ △ Comparative Example 5 5.1 X ◎ Comparative Example 6 4.8 △ ◎

Color (color coordinate) Example 4 Gx = 0.655, Gy = 0.327 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6

As shown in Table 2 above, according to the present invention, C.I. Pigment Red 242 and C.I. In Examples 1 to 7 using a binder resin containing a bulky monomer, Pigment Red 177 was superior in the relative dielectric constant, brightness, and contrast characteristics to the comparative examples using different combinations of coloring materials.

In particular, in the case of Example 5 using a macropolymer resin having a macromonomer monomer having a functional group as a binder resin as a binder resin, if the specific dielectric constant characteristics are further excellent, a bulkiness agent such as a rosin-based binder resin and an adamantane- It is confirmed that the relative dielectric constant characteristics of Examples 6 and 7 including the binder resin are also excellent.

As a coloring material, C.I. Pigment Red, 242 and C.I. In the case of Examples 1 to 7 using a binder resin containing a vulcanizable monomer while using Pigment Red 177, the relative dielectric constant value of Comparative Examples 1 and 2 was lower than that of Comparative Example 1 in which the same coloring material was used and the binder resin did not contain a vulcanizable monomer. You can see this is excellent.

As can be seen from Tables 2 and 3, when comparing Example 4 and Comparative Examples 1 to 6 from the viewpoint of the same chromaticity coordinates, the relative dielectric constant characteristics, the luminance and the contrast value of the Examples are compared This indicates that the probability of occurrence of defective display in a liquid crystal display device of a COA system of a large size and a high definition which forms a colored layer on the thin film transistor element is low.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram for forming a colored layer including a red colored layer on a substrate for driving a thin film transistor (TFT) type color liquid crystal display device using the red colored layer colored photosensitive resin composition of the present invention.

Description of the Related Art

Ⓐ: pixel pattern of R / G / B ⓑ: SiNx (protective layer)

Ⓒ: TFT layer ⓓ: Glass substrate

Ⓔ: Positive PR ⓕ: IZO layer (common electrode)

Claims (8)

A colored photosensitive resin composition for a red coloring layer formed on a TFT substrate, Wherein the colored photosensitive resin composition for red coloring layer comprises (A) Pigment Red 242 and C.I. (B) a binder resin comprising a polymer of a bulky monomer and a polymer of a polymerizable carboxyl group-containing monomer, (C) a photopolymerizable compound, (D) a photopolymerization initiator , And (E) a solvent, The C.I. Pigment Red 242 and C.I. Pigment Red 177 is mixed in a mass ratio of 90:10 to 10:90, Wherein the vulcanizable monomer is a monomer containing a bulky skeleton, Wherein the bulky skeleton is a norbonyl skeleton, an adamantane skeleton or a rosin skeleton. The method according to claim 1, The C.I. Pigment Red 242 and C.I. Pigment Red 177 is mixed in a mass ratio of 70:30 to 30:70. The method according to claim 1, Wherein the coloring material is contained in an amount of 3 to 60 mass% based on the solid content in the colored photosensitive resin composition for a red coloring layer. delete delete The method according to claim 1, Wherein the bulky monomer is a macromonomer having at least two bulky skeletons in the inside thereof. A color filter comprising a colored layer formed on a TFT substrate, Wherein the coloring layer comprises a red coloring layer formed using the colored photosensitive resin composition for a red coloring layer according to any one of claims 1 to 3 and 6. A liquid crystal display device comprising the color filter of claim 7.

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