KR101840984B1 - A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter comprising a black matrix, a column spacer or a black column spacer prepared by using the colored photosensitive resin composition, and a display device comprising the color filter. The colored photosensitive resin composition comprises: a coloring agent including a blue pigment and an orange pigment; an alkali-soluble resin; a photopolymerizable compound; a photopolymerizable initiator; and a solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter including a black matrix, a column spacer or a black column spacer manufactured using the same, and a display device including the color filter column spacer or black column spacer prepared by using the composition, and a display device comprising the color filter}

The present invention relates to a colored photosensitive resin composition, a black matrix made using the same, a color filter including a column spacer or a black column spacer, and a display device including the color filter.

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter used in the image pickup device or the liquid crystal display device may be a color pattern of three colors of red, green and blue or a color pattern of three colors of yellow, magenta and cyan Cyan).

The coloring pattern of each of the color filters is generally formed using a colored photosensitive resin composition comprising a coloring agent such as pigment or dye, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

The colored photosensitive resin is an essential material such as a color filter, a liquid crystal display material, an organic light emitting element, and a display. For example, in the case of a color filter used in a liquid crystal display, the color filter includes pixels composed of red, green, and blue colors, A black matrix is formed at the boundary between the coloring layers of the respective colors. In addition, the black column spacer (BCS) is a portion directly contacting the liquid crystal and functions not only as a black matrix but also as a spacer for holding a cell gap. Thus, a black column spacer Characteristics are required.

In recent years, the proportion of LCDs in flat panel displays has been increasing, and the backlight has been adopted as the screen becomes larger. As the backlight brighter, the black matrix also requires higher shading characteristics than the conventional one. However, when the pigment content is increased to improve the light shielding property, it is difficult to realize the basic characteristics of the black matrix such as compression displacement and elastic recovery rate. When the content of carbon black is increased in order to lower the pigment content, the process characteristic is continuously deteriorated, , Thereby causing a problem that the yield of production is lowered.

Korean Patent Laid-Open No. 10-2011-0027079 discloses a black photosensitive composition and a light-shielding layer formed using the same, discloses a black photosensitive composition containing orange, blue and violet pigments in a specific mixing ratio. However, It is not sufficient to improve the elastic recovery rate and the like.

Korean Patent Laid-Open No. 10-2014-0121824 discloses a black photosensitive composition containing an orange, a blue and a violet pigment in a specific mixing ratio. However, improvement in optical density and the like is not sufficient .

Korean Patent Publication No. 10-2011-0027079 Korean Patent Publication No. 10-2014-0121824

Disclosure of the Invention The object of the present invention is to provide a colored photosensitive resin composition excellent in solvent resistance, optical density, transmittance, color coordinates and elastic recovery rate.

It is still another object of the present invention to provide a color filter including a pattern layer made of the colored photosensitive resin composition, and a display device including the color filter.

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the colorant comprises a blue pigment and an orange pigment,

The blue pigment is a mixture of C.I. Pigment Blue 16 is provided.

The present invention also provides a color filter comprising a column spacer, a black matrix, or a black column spacer made of the colored photosensitive resin composition of the present invention.

The present invention also provides a display device including the color filter of the present invention.

The colored photosensitive resin composition of the present invention is used in combination with an orange pigment. By including Pigment Blue 16, it is possible to improve basic optical properties such as optical density (OD / 占 퐉), 750 nm transmittance, 950 nm transmittance and color coordinates, and also improve physical properties such as reliability and elastic recovery rate .

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

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the colorant comprises a blue pigment and an orange pigment,

The blue pigment is a mixture of C.I. Pigment Blue < RTI ID = 0.0 > 16. < / RTI >

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

coloring agent

The colorant used in the present invention is one which is shielding against visible light, and the colorant of the present invention includes a blue pigment and an orange pigment.

In the present invention, the blue pigment is a mixture of C.I. Pigment Blue 16 ". The C.I. When Pigment Blue 16 is included, a better optical density (OD / 占 퐉) can be obtained and the influence in a specific wavelength region can be reduced.

More specifically, C.I. Pigment Blue 16 is a blue pigment that does not contain a center metal and contains C.I. Pigment Blue 15: 6, the electrical characteristics of the product can be improved, and C.I. It is possible to exhibit better characteristics in terms of color expression as compared with the case of containing Pigment Blue 60. [

The orange pigment serves to improve the optical density by reducing the transmittance in the region of 400 to 550 nm. The kind of the orange pigment is not particularly limited, but C.I. Pigment Orange 46, 62, 64, 68, 72 and 77, and it is preferable to use at least one selected from the group consisting of C.I. Pigment Orange 64 is most preferably used.

The blue pigment may be included in the colored photosensitive resin composition in an amount of 8 to 22% by weight, preferably 10 to 18% by weight based on the total weight of the solid content of the colored photosensitive resin composition. The orange pigment may be contained in an amount of 3 to 12% by weight, preferably 5 to 10% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the above-mentioned blue pigment and orange pigment are contained in the above-described range, a colored photosensitive resin composition having excellent reliability and optical characteristics such as optical density and transmittance can be obtained.

In addition, the colored photosensitive resin composition of the present invention may further comprise a violet pigment as an additional colorant. The violet pigment serves to improve the optical density (O.D.) by reducing the transmittance in the region of 400 to 600 nm. In addition, the content of the organic black pigment can be reduced through the use of the violet pigment, and the reliability of the colored photosensitive resin composition can be improved. The type of the violet pigment is not particularly limited, but C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36 and 37 is preferably used. It is most preferable to use Pigment Violet 23.

The violet pigment may be contained in an amount of 3 to 18% by weight, preferably 5 to 15% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the violet pigment is included in the above range, a colored photosensitive resin composition having excellent optical density and color coordinate can be obtained.

In addition, the colored photosensitive resin composition of the present invention may further comprise a black pigment as an additional colorant. The black pigment is not particularly limited as far as it is light-shielding at visible light, but it is preferably used in combination with at least one selected from the group consisting of lactam black, aniline black, perylene black, titanium black and carbon black . The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black can be used. Specific examples of the carbon black that is the black pigment include channel black, furnace black, thermal black, lamp black, and the like. The carbon black may be coated with a resin, and the carbon black coated with the resin may have a lower conductivity than that of the uncoated carbon black, so that it is possible to impart excellent electrical insulation when forming the black matrix or the column spacer.

The black pigment may be contained in an amount of 12% by weight or less, preferably 10% by weight or less, based on the total weight of the solid content of the colored photosensitive resin composition. When the above-mentioned black pigment is included in the above range, it can have better characteristics in terms of optical density (OD / 占 퐉) and color rendering property.

In the present invention, the colorant is contained in an amount of 18 to 55% by weight, preferably 20 to 50% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is contained in an amount of 18 to 55% by weight, the optical density and the reliability are excellent.

In the present invention, the solid content in the colored photosensitive resin composition means the sum of the components from which the solvent has been removed.

In addition, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment by adding a dispersant and the like, and a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by the above method.

Alkali-soluble resin

In the present invention, an alkali-soluble resin usually makes the non-exposed portion of the photosensitive resin layer formed using the photosensitive resin composition alkali-soluble and can also act as a dispersion medium for the pigment. The alkali-soluble resin may be selected from among various polymers used in the relevant application fields, but a binder resin containing an epoxy group may be more effective.

This is because the alkali-soluble resin containing the epoxy group may affect the reliability improvement. The molecular weight of the alkali-soluble resin used may be in the range of 3,000 to 40,000 and preferably in the range of 5,000 to 30,000. In addition, the acid value of the alkali-soluble resin is preferably in the range of 50 to 200 mgKOH / g based on the solid content. When the acid value of the alkali resin satisfies the above-described range, there is an advantage that the developability against alkali development is excellent, the occurrence of residue is suppressed, and the adhesion of the pattern is improved.

The alkali-soluble resin is contained in an amount of 5 to 60% by weight, preferably 20 to 50% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above-mentioned range, the dispersibility of the colorant is increased, pattern formation is easy, and the resolution and the residual film ratio are improved.

Photopolymerizable compound

The photopolymerizable compound of the present invention contains an unsaturated bond and undergoes a photoreaction with the photoinitiator to form a photosensitive resin layer. The polymerizable compound to be used in the present invention includes a commonly used (meth) acrylate in a functional group When the composition contains an unsaturated group and is photosensitive, there is no limitation in use.

Specific examples of the photopolymerizable compound include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, But are not limited to, glycol acrylate, glycol acrylate, glycol acrylate, glycol acrylate, lithol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Bisphenol A diacrylate, trimethylolpropane triacrylate, novolak epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. . The above-mentioned photopolymerizable compounds may be used alone or in combination of two or more thereof.

The photopolymerizable compound may be included in the total solid content of the colored photosensitive resin composition in an amount of 5 to 50% by weight, more preferably 10 to 40% by weight. When the content of the photopolymerizable compound is within the above range, it is preferable that the sensitivity is excellent and the pattern characteristic is well formed.

Photopolymerization initiator

The photopolymerization initiator of the present invention initiates a radical reaction of the photosensitive resin composition to cause curing and improve the sensitivity. The photopolymerization initiator is a photopolymerization initiator generally used in a photosensitive resin composition, and oxime, acetophenone, benzophenone, triazine, thioxanthone, benzoin, and imidazole compounds can be used.

Oximeimino-1-phenylpropan-1-one and the like, and more preferable examples of the oxime-based compounds include OXE01 and OXE02 of BASF Corporation, which are commercially available products.

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- Methyl [4- (1-methylvinyl) phenyl] propane-1-one, 2-benzyl-2-dimethylamino- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and the like. In addition, photopolymerization initiators other than the acetophenone-based photopolymerization initiator may be used in combination. 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, benzoisobutyl ether and the like.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylphenazine, 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.

The thioxanthone compound is specifically exemplified by 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Santon et al.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

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

These photopolymerization initiators may be used singly or in combination of two or more.

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the total weight of the solid content in the colored photosensitive resin. When the photopolymerization initiator is contained within the above range, the pattern formation becomes favorable, the colored photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed by using the composition and the smoothness on the surface of the pixel portion tend to be favorable, Do.

In the present invention, a photopolymerization initiator may be used in addition to the photopolymerization initiator.

The photopolymerization initiation assistant is a compound used for promoting polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiation assistant include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, Based compound and a sulfonic acid-based compound.

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.

These photopolymerization initiators (D) may be used singly or in combination of two or more thereof. Commercially available photopolymerization initiators may be used as the photopolymerization initiator. Commercially available photopolymerization initiators include, for example, trade names "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like.

 When these photopolymerization initiators are used, the amount of the photopolymerization initiator is usually 10 moles or less, preferably 0.01 to 5 moles per mole of the photopolymerization initiator. Within the above range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of the color filter formed using the composition tends to be improved, which is preferable.

solvent

The solvent used in the conventional colored photosensitive resin composition can be used without particular limitation so long as it is effective in dissolving other components contained in the colored photosensitive resin composition and does not react with the solvent. In particular, an ether, an acetate, an aromatic Hydrocarbons, ketones, alcohols or esters.

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

These solvents may be used alone or in combination of two or more.

It is preferable to use an organic solvent having a boiling point of 100 to 200 in terms of coating property and drying property, and a solvent having a different boiling point may be mixed with the solvent.

The content of the solvent in the colored photosensitive resin composition of the present invention may be 60 to 90% by weight, preferably 65 to 85% by weight, based on the total weight of the colored photosensitive resin composition containing the colored photosensitive resin composition. When the content of the solvent is within the above range, it is preferable that the leveling property and the coating property are good and curing is easy.

additive

The colored photosensitive resin composition of the present invention includes other additives in addition to the above-mentioned components according to the needs of the ordinary skilled artisan to the extent that the object of the present invention is not impaired.

The additive may specifically include, for example, at least one additive selected from the group consisting of a thermal initiator, a curing agent, a adhesion promoter, and a surfactant.

The thermal initiator causes a curing reaction by heat to maximize the initiation efficiency. The thermal initiator may be a peroxide-based compound.

Specific examples of the thermal initiator include, but are not limited to, tetramethyl butyl peroxyneodecanoate (eg Perocta ND, NOF), bis (4-butylcyclohexyl) peroxydicarbonate (eg Peroyl TCP Perfluoroalkane (ex. Perbutyl ND, manufactured by NOF), dipropyl peroxydicarbonate (ex. Peroyl NPP, manufactured by NOF Corporation), di (2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate , NOF Corp.), diisopropyl peroxy dicarbonate (e.g., Peroyl IPP, NOF), diethoxyethyl peroxydicarbonate (e.g., Peroyl EEP, NOF), diethoxy (Peroyl OEP, NOF), hexyl peroxydicarbonate (e.g., Perhexyl ND, NOF), dimethoxybutyl peroxydicarbonate (e.g. Peroyl MBP, NOF Peroyl SOP, NOF), dibutyl peroxydicarbonate, dicetyl peroxy dicyclohexylcarbodiimide, bis (3-methoxy-3-methoxybutyl) peroxydicarbonate Dicabo Peroxypivalate, hexyl peroxypivalate (ex. Perhexyl PV, NOF), and the like. Perbutyl (NOF), trimethyl hexanoyl peroxide (e.g., Peroyl 355, NOF), dimethylhydroxybutyl peroxyneodecanoate (ex Luperox 610M75) , Atofina (manufactured by Atofina), amyl peroxyneodecanoate (ex Luperox 546M75, Atofina), butyl peroxyneodecanoate (ex Luperox 10M75, Atofina), t-butyl peroxy Butyl peroxypivalate, neopentyl peroxypivalate, neoheptanoate, amyl peroxypivalate (ex Luperox 546M75, Alofina), t-butyl peroxypivalate, t-amylperoxy-2-ethylhexanoate, Oxy-2-ethylhexanoate, lauryl peroxide, dilauroyl peroxide, didecanoyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 2,2- Bis (tert-butylperoxy) -cyclohexane, 2,5-bis (butylperoxy) -2,5-dimethylhexane, 2,5- Butyl peroxide, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, tert-butyl peracetate, Peracetic acid, and potassium persulfate may be used.

With respect to the content of the thermal initiator, it is preferably contained in an amount of 1 to 10% by weight, and more preferably 1 to 5% by weight based on the total solid content of the colored photosensitive resin composition. When it is contained in the above-mentioned contents, it is more preferable for fairness and undercut.

The curing agent is used for increasing the curing depth and mechanical strength, and specific examples thereof include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

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

The curing agent may be used together with a curing assistant compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agents include commercial products such as ADEKA HARDONA EH-700 (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (manufactured by New Japan Chemical Co., Ltd.) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The adhesion promoter is an additive which is used for improving coatability and adhesiveness with a substrate, and is a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, . Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldimethoxysilane , 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, -Mercaptopropyltrimethoxysilane, trimethoxysilylbenzoic acid, vinyltriacetoxysilane,? -Isocyanate propyltriethoxysilane, and the like.

The surfactant can be used for further improving the film-forming property of the photosensitive resin composition, and for example, a surfactant such as silicon, fluorine, ester, cationic, anionic, nonionic or amphoteric surfactant can be used , A silicone surfactant or a fluorine surfactant can be preferably used.

TS-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4400 of GE Toshiba Silicones such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., 4460 and TSF-4452. F-472, F-482 and F-489 (Dainippon Ink and Chemicals, Inc.), BM-1000 and BM-1100 (trade names, (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), and the like.

Further 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, polyethylene (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoei Chemical Co., Ltd.), F-Top (Tochem Products Inc.), Megapack (Dainippon Ink Chemical Industry Co., Ltd.), Florad (Asahi Glass Co., Ltd.), Sorusparas (Zeneca Co., Ltd.), EFKA (EFKACHEMICALS Co., Ltd.), and PB821 (Ajinomoto Co., Ltd.).

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

The additive can be suitably added and used by those skilled in the art within a range not hindering the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the colored photosensitive resin composition.

The colored photosensitive resin composition according to the present invention can be produced, for example, by the following method. The colorant is mixed with a solvent and dispersed. If necessary, a dispersant may be further used, and some or all of the alkali-soluble resin may be blended. The remaining amount of the alkali-soluble resin, the photopolymerizable compound, the photopolymerization initiator, other components to be used if necessary, and, if necessary, the additional solvent are further added to the obtained dispersion (hereinafter, also referred to as mill base) To obtain a desired colored photosensitive resin composition.

A pattern layer including a column spacer, a black matrix and / or a black column spacer, a color filter, and a liquid crystal display

The present invention also relates to a color filter comprising a pattern layer produced using the colored photosensitive resin composition.

The color filter according to the present invention has an advantage of high reliability due to high optical density and excellent shielding property. The color filter includes a substrate and a pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where a color filter is placed on a display device or the like, and is not particularly limited. The substrate can be glass, silicon (Si), may be a silicon oxide (SiO _x) or a polymer substrate, the polymer substrate, such as polyether sulfone (polyethersulfone, PES), or polycarbonate (polycarbonate, PC).

The pattern layer may include a column spacer, a black matrix and / or a black column spacer as a layer containing a cured product of the colored photosensitive resin composition of the present invention.

The column spacer, the black matrix and / or the black column spacer according to the present invention has an advantage of high reliability and excellent shielding due to high optical density. In particular, the colored photosensitive resin composition of the present invention can be suitably used for producing a black column spacer (black matrix integrated spacer), and the black column spacer does not form a black matrix and a column spacer, Means that the matrix and the column spacer are integrally formed.

The pattern layer may be a layer formed by applying the above-mentioned colored photosensitive resin composition and exposing, developing, and thermosetting in a predetermined pattern, and the pattern layer may be formed by performing a method commonly known in the art.

The color filter including the substrate and the pattern layer as described above may further include a partition wall formed between the respective patterns, and may further include a black matrix, but is not limited thereto.

The present invention also relates to a display device including the color filter. In short, the liquid crystal display device according to the present invention may include a color filter including a pattern layer containing a cured product of the above-mentioned colored photosensitive resin composition.

The color filter of the present invention is applicable not only to a general liquid crystal display device but also to various image display devices such as an electroluminescence display device, a plasma display device, and a field emission display device. When the liquid crystal display device includes the color filter including the pattern layer according to the present invention, there is an advantage that the shielding property and the reliability are excellent.

A typical patterning process for forming a black matrix, column spacer or black column spacer according to the photolithography method

a) applying a colored photosensitive resin composition to a substrate;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking.

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, in particular, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

The coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The alkali development after exposure is performed for the purpose of removing the colored photosensitive resin composition in a portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 캜, preferably 20 to 40 캜, using a developing machine or an ultrasonic cleaner .

The post-baking is performed in order to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 DEG C for 10 to 120 minutes. Post-baking is performed by using an oven, a hot plate, or the like as in pre-baking.

In this case, the thickness of the black matrix is preferably 0.2 to 20 占 퐉, more preferably 0.5 to 10 占 퐉, and particularly preferably 0.8 to 5 占 퐉.

The film thickness of the column spacer and the black column spacer is preferably 0.1 탆 to 8 탆, more preferably 0.1 탆 to 6 탆, and particularly preferably 0.1 탆 to 4 탆.

The black matrix, the column spacer, or the black column spacer made of the colored photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesion, electrical insulation and light shielding property, and is excellent in heat resistance and solvent resistance, It is possible to improve the reliability.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following embodiments can be appropriately modified and changed by a person skilled in the art within the scope of the present invention.

Synthetic example. Alkali-soluble resin (B) Synthesis

277 g of methoxybutyl acetate was added to an internal 1-L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and heated to 80 ° C. Then, a mixture of 3,4-epoxytricyclo [5.2.1.0,2,6] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0,2,6] decan-8- And a molar ratio of 50:50, 49 g of methacrylic acid and 23 g of azobisdimethylvaleronitrile were dissolved in 350 g of methoxybutyl acetate to prepare a mixed solution. The mixed solution was dropped into the flask over 5 hours using a dropping funnel, and the reaction was carried out for 3 hours to prepare a dispersion resin (solid content (NV) 35.0% by weight). The prepared dispersion resin had an acid value of 69.8 KOH mg / g, a weight average molecular weight (Mw) of 12,300 and a dispersion degree (Mw / Mn) of 2.1.

Examples 1 to 12 and Comparative Examples 1 to 2

The colored photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 and 2 were prepared according to the composition shown in Table 1 below.

[Table 1]

(Unit: parts by weight)

O64: C.I. Pigment Orange 64

B16: C.I. Pigment Blue 16

V23: C.I. Pigment Violet 23

CB: carbon black

OBP: Organic Black Pigment

B15: 6: C.I. Pigment Blue 15: 6

B60: C.I. Pigment Blue 60

B (dispersion resin): An alkali-soluble resin

M (photopolymerizable compound): dipentaerythritol hexaacrylate (DPHA) (Nippon Kayaku Co., Ltd.)

PI (photopolymerization initiator): 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime) (Irgacure OXE-02: Ciba four)

D1 (additive 1): Sol Spurs 5000 (Lubrisol)

D2 (additive 2): F554 (DIC)

S (solvent): Propylene glycol monomethyl ether acetate (PGMEA)

Fabrication of Substrate

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the colored photosensitive resin compositions prepared in Example 1 and Comparative Example was spin-coated on the glass substrate to a final film thickness of 3.0 占 퐉, prebaked at 80 to 120 占 폚 and dried for 1 to 2 minutes to prepare a solvent Respectively. Then, exposure was performed at an exposure amount of 25 to 35 mJ / cm ² to form a pattern, and an unexposed area was removed using an aqueous alkaline solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

Experimental Example

1. Reliability Evaluation

A substrate is manufactured so that a black photosensitive resin is applied to the entire surface without a pattern, on the basis of the above substrate manufacturing standards. It is cut into a size of 3 x 3 cm, immersed in NMP solvent, and heated at 100 캜 for 60 minutes. After that, only the NMP solvent is extracted, and the degree of elution in the NMP solvent is measured by using a UV-vis spectrometer, and the absorbance is expressed as an integral value of 300 to 800 nm. Specific evaluation criteria are as follows, and the measurement results are shown in Table 2 below.

[Evaluation standard]

Reliability (NMP elution reliability): 300 to 800 nm Abs

Excellent ⊚: Not more than 0.5

Good ○: more than 0.5 and less than 1.0

Shortage △: more than 1.0 and less than 1.2

Worsening X: Above 1.2

2. Evaluation of optical characteristics

Based on the substrate manufacturing standards as described above, optical characteristics are evaluated with a substrate made to be coated with a black photosensitive resin on the entire surface without a pattern. UV-vis (UV-2550, manufactured by Shimadzu) is used. In the evaluation of optical characteristics, the optical density was measured at 400 to 650 nm, and the measured values at each wavelength were confirmed in the near-IR region at 700 to 750 nm and 950 nm. 361T, X-rite) was used to measure the transmittance at a center wavelength of 510 nm, and the optical density to a thickness of 1 mu m was determined. The specific evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.

[Evaluation standard]

(1) Optical density

Excellent ◎: 1.3 or more

Good ○: 1.1 or more to less than 1.3

Insufficient: at least 1.0 and less than 1.1

Worsening X: Less than 1.0

(2) Transmittance at 750 nm

Excellent?: 10T% or less

Good O: 10T% to 12T% or less

Insufficient: 12T% or more to 15T% or less

Worsening X: over 15T%

(3) Transmittance at 950 nm

Excellent ⊚: 15T% or more

Good ○: 12T% or more to less than 15T%

Insufficient: 10T% or more to less than 12T%

Worsening X: Less than 10T%

3. Evaluation of color coordinates

With reference to the substrate manufacturing standards as described above, a substrate was manufactured so that a black photosensitive resin was coated on the entire surface without a pattern, and color coordinates were measured. The x and y coordinate values were measured using a Contrast Tester (CT-1, Tsubosak Co.). The specific evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.

[Evaluation standard]

(1) x coordinate value

Excellent ⊚: not more than 0.1

Good: more than 0.1 to less than 0.2

Insufficient: more than 0.2 to less than 0.4

Worsening X: Greater than 0.4

(2) y coordinate value

Excellent ⊚: Not more than 0.05

Good ◯: more than 0.05 to less than 0.15

Shortage?: Over 0.15 to less than 0.25

Worsening X: Greater than 0.25

4. Evaluation of elastic recovery rate

A substrate having a column spacer pattern was produced on the basis of the above-described production standards. The fabricated substrate was measured for thickness and height of pattern in a reference state using SNU (SIS-2000, SNU). Thereafter, a hardness meter (Nano-indenter HM500, Fisher) was pressed at a rate of 2 mN / sec to a point where the pattern was deformed by 1 μm using a planar indenter, and holding time was held for 5 seconds at a point of 1 μm deformation. Then, the SNU was used to measure the thickness and height of the pattern, and the elastic recovery rate was measured by the thickness change of the pattern before and after the pattern. The specific evaluation criteria are as follows, and the evaluation results are shown in Table 2 below.

[Evaluation standard]

Excellent ◎: 98% or more

Good ○: 96% or more to less than 98%

△: Less than 96% ~ 94%

Worsening X: Less than 94%

[Table 2]

The colored photosensitive resin compositions of Examples 1 to 12 exhibited excellent results in terms of reliability, optical density, light transmittance, color coordinates, and elastic recovery rate as compared with Comparative Examples 1 and 2. In addition, Example 2 including a violet pigment exhibited superior reliability and optical density as compared with Example 1, and the reliability and optical density characteristics of Examples 3 to 12 further including a black pigment were excellent And other properties such as light transmittance, color coordinates and elastic recovery rate also showed excellent results.

Claims (12)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
Wherein the colorant comprises a blue pigment and an orange pigment,
Wherein the blue pigment is CI Pigment Blue 16. [2] The composition of claim 1, wherein the orange pigment is selected from the group consisting of C.I. Pigment Orange 46, 62, 64, 68, 72 and 77. The colored photosensitive resin composition according to claim 1, The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises a violet pigment as an additional colorant. 4. The composition of claim 3, wherein the violet pigment is selected from the group consisting of C.I. And at least one selected from the group consisting of Pigment Violet 14, 19, 23, 29, 32, 33, 36 and 37. The colored photosensitive resin composition of Claim 1, The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises a black pigment as an additional colorant. The colored photosensitive resin composition according to claim 5, wherein the black pigment comprises at least one selected from the group consisting of lactam black, aniline black, perylene black, titanium black and carbon black. The colored photosensitive resin composition according to claim 1, which comprises 18 to 55% by weight of a colorant, 5 to 60% by weight of an alkali-soluble resin, 5 to 50% by weight of a photopolymerizable compound and 0.1 to 40% by weight of a photopolymerization initiator based on the total solid content of the colored photosensitive resin composition By weight based on the total weight of the colored photosensitive resin composition, and 60 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises at least one additive selected from the group consisting of a thermal initiator, a curing agent, an adhesion promoter, and a surfactant. A pattern layer made of the colored photosensitive resin composition according to any one of claims 1 to 8. The pattern layer according to claim 9, wherein the pattern layer is at least one selected from the group consisting of a column spacer, a black matrix and a black column spacer. A color filter comprising the patterned layer of claim 9. A display device comprising the color filter of claim 11.