KR20110054709A - A colored photosensitive resin composition, color filter and liquid crystal display device comprising thereof - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition, a color filter including the same, a liquid crystal display device are provided to overcome problems of a liquid crystal panel by improving the contrast and the brightness of a green colored layer. CONSTITUTION: A colored photosensitive resin composition includes a coloring agent and a binder resin. The coloring agent includes C.I. pigment green 58 and C.I. pigment green 36 in the ration of 99:1 to 81:19. The coloring agent further includes one or more pigments selected from a group including C.I. pigment green 7, C.I. pigment yellow 138, C.I pigment yellow 139, and C.I pigment yellow 150.

Description

A colored photosensitive resin composition, a color filter and a liquid crystal display including the same {A COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE COMPRISING THEREOF}

The present invention relates to a colored photosensitive resin composition, a color filter and a liquid crystal display including the same, and specifically, for a green colored layer having excellent contrast and brightness as well as an afterimage phenomenon due to liquid crystal contamination by ion dissolution of a pigment. It relates to a colored photosensitive resin composition, a color filter including the same, and a liquid crystal display device.

In general, a color filter having a plurality of colored layers arranged to correspond to a plurality of pixels is used in a liquid crystal display device to realize color image display.

Although the colored layer of the said color filter is formed with the coloring photosensitive resin composition, the conventional coloring material used for the photosensitive resin composition for forming a green colored layer has the limitation in pigment atomization and high contrast improvement. Accordingly, in order to realize high contrast and high brightness color characteristics, C.I. Techniques using pigment green 58 as the main pigment have been developed. Generally the above C.I. The coloring photosensitive resin composition for the green colored layer which uses pigment green 58 as a main pigment uses a small amount of pigments in order to match | process various characteristics in a process. However, when the conventional photopolymerization initiator is applied as it is under the condition of low pigment content as described above, storage stability is very poor, and foreign matter occurs during the process, resulting in a decrease in yield. CI when driven There is a problem that an afterimage occurs due to liquid crystal contamination due to utilization of Pigment Green 58.

An object of the present invention to solve the above problems is not only excellent contrast and brightness, but also a coloring photosensitive resin composition capable of forming a green colored layer having an improved afterimage phenomenon due to liquid crystal contamination by ion dissolution of the pigment, comprising the same It is to provide a color filter and a liquid crystal display device.

The present invention to achieve the above object,

C.I. Pigment Green 58 and C.I. Coloring agent (A) comprising a green pigment containing pigment green 36 in a mass ratio of 99: 1 to 81:19; And it provides the coloring photosensitive resin composition containing binder resin (B).

The colorant is C.I. Pigment Green 7, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139 and C.I. Pigment Yellow 150 may further include a pigment for color adjustment, which is selected from the group consisting of single or a mixture thereof.

The colored photosensitive resin composition may further include at least one selected from a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E).

The green pigment and the pigment for color adjustment may be included in a mass ratio of 30:70 to 90:10.

The colorant may be included in an amount of 5 to 60 parts by weight based on the solids of the colored photosensitive resin composition.

The binder resin (B) may be alkali soluble.

The binder resin (B) may be obtained by sequentially reacting a copolymer of a first monomer having an unsaturated bond and an epoxy group and a second monomer having an unsaturated bond with a third monomer having a unsaturated double bond and a carboxyl group and a polybasic acid anhydride. .

The binder resin may have a weight average molecular weight of 3,000 to 100,000.

The binder resin may be included in an amount of 5 to 90 parts by weight based on the solids of the colored photosensitive resin composition.

In order to achieve the other object of the present invention,

It provides a color filter comprising a colored layer formed of the colored photosensitive resin composition.

In order to achieve another object of the present invention,

A liquid crystal display device having the color filter is provided.

The coloring photosensitive resin composition of this invention can provide the green coloring layer excellent in contrast and brightness | luminance.

The coloring photosensitive resin composition of this invention can improve the afterimage phenomenon of a liquid crystal panel.

Therefore, the coloring photosensitive resin composition of this invention can be usefully used for manufacture of a color filter and the liquid crystal display device containing the same.

Hereinafter, the present invention will be described in detail so that those skilled in the art can easily practice.

The coloring photosensitive resin composition of this invention contains a coloring agent (A) and binder resin (B). The coloring photosensitive resin composition of this invention can provide the green colored layer which was excellent in contrast and brightness, and the afterimage phenomenon of the liquid crystal panel was improved.

The coloring agent (A) is C.I. Pigment Green 58 and C.I. Green pigments containing Pigment Green 36; C.I. Pigment green 58 can be used to form green colored layers with high contrast and brightness, as well as C.I. Including the pigment green 36, the afterimage phenomenon of the liquid crystal panel may be improved.

Pigment Green 58 and C.I. Pigment Green 36 may be included in a mass ratio of 99: 1 to 81:19. When included in the mass ratio, it is possible to manufacture a liquid crystal display device having a high resolution by improving the afterimage phenomenon of the liquid crystal panel while having high contrast and luminance.

In addition to the green pigment, the colorant may further include a pigment for adjusting the color tone. The color adjusting pigment may be an inorganic or organic pigment known in the art, but preferably C.I. Pigment Green 7, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139 and C.I. Pigment yellow 150, or a mixture thereof or more preferably selected from the group consisting of C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 or mixtures thereof can be used. C.I. Pigment Yellow 139 and C.I. This is because Pigment Yellow 150 is the most excellent in terms of improving luminance and contrast characteristics.

The green pigment and the pigment for controlling color tone may be included in a mass ratio of 30:70 to 90:10, and preferably may be included in a mass ratio of 40:60 to 80:20. Within this range, it is possible to form a green colored layer having a desired hue while improving luminance and contrast, and when exceeding the limited mass ratio, the color of the green colored layer is too yellowish or greenish when pannelized. The color balance of G, B may be mismatched, which may lead to a defect of the final liquid crystal display.

The colorant may be included in an amount of 5 to 60 parts by weight, and preferably 10 to 50 parts by weight, based on the solids of the colored photosensitive resin composition. Here, solid content means the remaining component except a solvent in a coloring photosensitive resin composition. When the colorant is included in an amount of 5 to 60 parts by weight, the color density of the pixel is sufficient when the thin film is formed, and no residue occurs because the omission of the non-pixel portion during development is not reduced.

The binder resin (B) functions as a binder and a dispersion medium of the colorant.

It is preferable to use the binder resin which has reactivity with light or heat, and alkali solubility. This is because it must be soluble in the alkaline developer used in the developing step for producing the color filter.

The binder resin is a copolymer of a first monomer (B1) having an unsaturated bond with an epoxy group and a second monomer (B2) having an unsaturated bond in a molecule thereof, and a third monomer (B3) having a unsaturated double bond and a carboxyl group and a polybasic acid anhydride ( It may be an unsaturated group-containing resin formed by sequentially reacting with B4).

Looking more specifically, the binder resin is a polymerization step; Unsaturated group addition step; And a reaction with polybasic acid anhydride.

The polymerization step is a step of polymerizing the first monomer (B1) and the second monomer (B2) to form a copolymer. Specifically, a solvent is introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask is replaced with nitrogen by air. Then, after heating up the solvent to 40 to 140 degreeC, the solution which added the 1st monomer, the 2nd monomer, and a polymerization initiator, and stirred and melt | dissolved at room temperature or heating was added to the said flask over 0.1 hour to 8 hours from the dropping lot. It is dripped and stirred at 40 degreeC-140 degreeC for further 1 hour to 10 hours, and a copolymer is obtained.

The first monomer (B1) may be used without limitation as long as it has a compound having an unsaturated bond and an epoxy group in one molecule, and specifically, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3 Single or mixtures thereof selected from the group consisting of, 4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclodecane-8-yl (meth) acrylate and methylglycidyl (meth) acrylate Can be used. Preferably, glycidyl (meth) acrylate can be used.

The second monomer (B2) may be used without limitation so long as it is a compound having an unsaturated bond polymerizable with the first monomer, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as 2-hydroxyethyl (meth) acrylate and aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl Cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cyclo Heptenyl (meth) acrylate, cyclooctenyl

(Meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, Monosaturated carboxylic acid ester compound and benzyl (meth) acryl of glycols, such as unsaturated carboxylic ester compound containing alicyclic substituents, such as pinene (meth) acrylate, and oligoethylene glycol monoalkyl (meth) acrylate Unsaturated carboxylic acid ester compound containing substituents which have aromatic rings, such as a latex, phenoxy (meth) acrylate, and rosin (meth) acrylate, aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, and vinyltoluene, and vinyl acetate Vinyl cyanide compounds such as carboxylic acid vinyl esters such as vinyl propionate, (meth) acrylonitrile and α-chloroacrylonitrile and N-cyclohexyl Mid-ray, may be used alone or as a mixture thereof selected from the group consisting of maleimide compounds, such as N- phenyl maleimide.

The solvent may be added in an amount of 0.5 to 20 parts by weight based on the content of the first monomer and the second monomer, and specifically, tetrahydrofuran, dioxane, ethylene glycol dimethylethyl, diethylene glycol dimethylethyl, acetone, methyl ethyl ketone , Methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl It is possible to use alone or a mixture thereof selected from the group consisting of ether, toluene, xylene, ethylbenzene, chloroform and dimethyl sulfoxide, but is not limited thereto.

The polymerization initiator may be diisopropylbenzenehydroperoxide, di-t-butylperoxide, benzoyl peroxide, t-butylperoxyisopropylcarbonate, t-amylperoxy-2-ethyl hexanoate, t- Organic peroxides such as butyl peroxy-2-ethylhexanoate, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbareronitoryl), dimethyl One or a mixture thereof may be used selected from the group consisting of nitrogen compounds such as -2,2'-azobis (2-methylpropionate), but is not limited thereto.

A chain transfer agent may be further included in order to control the molecular weight or the molecular weight distribution in the polymerization step, and as the chain transfer agent, α-methylstyrene dimer or a mercapto compound may be used, but is not limited thereto. The chain transfer agent may be included in an amount of 0.005 to 5 parts by weight based on the first monomer and the second monomer.

In the above polymerization conditions, a person skilled in the art can arbitrarily adjust the dosing method and the reaction temperature appropriately in consideration of the amount of heat generated by the production facility or polymerization.

The unsaturated group addition step is a step of adding an unsaturated double bond to the copolymer by reacting the copolymer of the first monomer and the second monomer with the third monomer (B3).

The third monomer (B3) which adds an unsaturated double bond may preferably be acrylic acid or methacrylic acid. The third monomer can be used in combination with a monomer containing an unsaturated carboxylic acid or a hydroxyl group and a carboxyl group. Specifically, a monomer containing an unsaturated carboxylic acid or a hydroxyl group and a carboxyl group can be used while using acrylic acid or methacrylic acid as the third monomer. The unsaturated carboxylic acid may be a single or a mixture thereof selected from the group consisting of crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. Specific examples of the monomer containing the hydroxy group and the carboxyl group include α- (hydroxymethyl) acrylic acid. Etc.

The reaction with the polybasic acid anhydride is a step of reacting the copolymer with the third monomer and then with the polybasic acid anhydride (B4). Specifically, after the copolymer obtained in the polymerization step is reacted with the third monomer, the polybasic acid anhydride is added thereto, followed by heating to 50 ° C to 150 ° C, preferably 80 ° C to 130 ° C. There is no need to add a catalyst in particular in the reaction step.

Specific examples of the polybasic acid anhydride include coharic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride and Phenol anhydride and the like or a mixture thereof may be used. Preferably, tetrahydrophthalic anhydride and coharic anhydride may be used.

The binder resin (B) may be 2 to 80 mol%, preferably 5 to 80 mol%, of repeating units derived from the first monomer with respect to the entire resin, and 2 to 90 mol of repeating units obtained from the second monomer. %, Preferably 5 to 90 mol%. In addition, the third monomer may be reacted at 2 to 100 mol%, preferably 5 to 100 mol% with respect to the epoxy equivalent of the first monomer, and the polybasic acid anhydride may react with the reaction of the first monomer and the third monomer. It can react with 2-100 mol% with respect to the hydroxyl group equivalent produced | generated, Preferably it is 5-100 mol%. The binder resin which has a repeating unit within the said range improves developability, solubility, heat resistance, etc.

The binder resin (B) may have a polystyrene reduced weight average molecular weight (hereinafter referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; using tetrahydrofuran as an eluting solvent), and may be 3,000 to 100,000. Preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed part in the developer is excellent and the resolution can be improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin may be 1.5 to 6.0, preferably 1.8 to 4.0. If molecular weight distribution is 1.5-6.0, developability is excellent.

The binder resin may have an acid value of 30 to 180 (mgKOH / g). If the acid value is less than 30 (mgKOH / g), the developability of the developer may be low and residues may remain on the substrate. If the acid value is more than 180 (mgKOH / g), the possibility of desorption of the pattern may increase. have. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution.

The binder resin may be included in an amount of 5 to 90 parts by weight, preferably 10 to 70 parts by weight, based on the solid content of the colored photosensitive resin composition. In the case where the binder resin is included in the above range, the solubility in the developing solution is sufficient, so that development residues are less likely to occur on the substrate of the non-pixel portion, and it is difficult to reduce the film portion of the pixel portion of the exposed portion at the time of development. Good.

The coloring photosensitive resin composition of this invention is a photopolymerizable compound (C); Photopolymerization initiator (D); And at least one selected from a solvent (E).

The photopolymerizable compound (C) is a compound that can be polymerized by the action of a photopolymerization initiator, and may be a monofunctional monomer, a bifunctional monomer or a polyfunctional monomer, but is preferably a bifunctional or higher monomer, more preferably. A polyfunctional monomer more than five functional can be used.

Specifically, the monofunctional monomer may be nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrroli Money, etc., but is not limited thereto. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol Bis (acryloyloxyethyl) ether of A, 3-methylpentanedioldi (meth) acrylate, and the like, but are not limited thereto. Specific examples of the polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and pentaerythritol tree. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, tipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol Hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.

The photopolymerizable compound may be included in an amount of 1 to 60 parts by weight, preferably 5 to 50 parts by weight, based on the solids content of the colored photosensitive resin composition. When included in the above range, the intensity and smoothness of the pixel portion are good.

The photopolymerization initiator (D) may be an acetophenone compound, a biimidazole compound, or an oxime compound, but is not limited thereto.

Specific examples of the acetophenone-based compound include diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- Oligomers, such as 1-one, or the compound represented by following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₄ are each independently substituted or unsubstituted by a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms. It is selected from a naphthyl group which is unsubstituted or substituted by a benzyl group or an alkyl group having 1 to 12 carbon atoms.

Specifically, the compound represented by Formula 1 is 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1- On, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2- Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholinophenyl ) Propan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propane-1-one, and the like, but are not limited thereto. It doesn't happen.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole or phenyl group at 4,4', 5,5 'position Although there exist an imidazole compound etc. which are substituted by the group, it is not limited to now. Preferably, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole or 2,2'-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole, etc. can be used.

Specific examples of the oxime-based compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one or a compound represented by one of the following Chemical Formulas 2 to 4:

[Formula 2]

(3)

[Formula 4]

The photopolymerization initiator may be included in an amount of 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, based on the solids content of the colored photosensitive resin composition. When included in the above range, the sensitivity of the colored photosensitive resin composition is increased to increase the strength and smoothness of the colored layer formed therefrom.

A photoinitiator can be used together with the said photoinitiator. When the photopolymerization initiator and the photopolymerization initiator are used in combination, the colored photosensitive resin composition may be highly sensitive, thereby improving productivity of the color filter.

The photopolymerization initiator may be specifically used an amine compound or a carboxylic acid compound, but is not limited thereto.

The photopolymerization initiator may be included in an amount of 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, based on the solids content of the colored photosensitive resin composition. When included in the above range, the sensitivity of the coloring photosensitive resin composition may be increased and the productivity of the color filter formed using the same may be improved.

The solvent (E) may be used without limitation, those known in the art, specifically, ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc. Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxy butyl acetate and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as γ-butyrolactone and the like, or a mixture thereof.

The solvent may be a boiling point of 100 ℃ to 200 ℃ considering the applicability and dryness, preferably alkylene glycol alkyl ether acetates, ketones, and 3-ethoxy propionate ethyl, 3-methoxy Single or a mixture thereof may be used selected from the group consisting of esters such as methyl propionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, And 3-methoxypropionate, and the like, or a mixture thereof.

The solvent may be included in an amount of 60 to 90 parts by weight, preferably 70 to 85 parts by weight based on the colored photosensitive resin composition. Applicability | paintability is favorable when a solvent is contained in the said range.

The coloring photosensitive resin composition of this invention can contain the additive known in the art within the range which does not impair the objective of this invention other than the said component. For example, additives such as fillers, polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and dispersants may be further included according to the needs of those skilled in the art.

Specific examples of the filler include glass, silica, alumina, and the like, and the other high molecular compound may specifically include a curable resin such as an epoxy resin and a maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl. Thermoplastic resins such as acrylate, polyester, and polyurethane. Specifically, the adhesion promoter is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethicone. Methoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane and the like. Specifically, the antioxidant may include 2,2′-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the ultraviolet absorber may specifically 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxy benzophenone, etc. are mentioned. Specific examples of the anti-aggregation agent include sodium polyacrylate, but are not limited thereto.

The dispersant serves to uniformly disperse the green pigment and the pigment for color tone adjustment. Specifically, the dispersant may be a surfactant such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, or polyacrylic, and the like, and these may be used alone or in combination of two or more thereof. It doesn't happen. Specifically, there are polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines, and the like. , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (Tochem Products), Mega Pack (MEGAFAC) Fukurad High School Co., Ltd., Florad (Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, Asahi Glass Co., Ltd.), SOLSPERSE (Geneva), EFKA ( EFKA Chemicals Co., Ltd., PB 821 (Ajino Motor Co., Ltd.), etc. are mentioned. The dispersant may be included in an amount of 1 part by weight or less, preferably 0.05 to 0.5 parts by weight, based on the colorant. When the dispersant is included in the above range, the pigment may be uniformly dispersed and a colored layer having a uniform color tone may be formed.

The present invention also provides a color filter including a green colored layer formed of the colored photosensitive resin composition of the present invention and a liquid crystal display device having the same.

The liquid crystal display device having the color filter including the green colored layer formed of the colored photosensitive resin composition of the present invention may reduce the afterimage phenomenon due to ion dissolution of the liquid crystal, thereby realizing high resolution.

The color filter according to the present invention includes a configuration well known to those skilled in the art, except that the colored photosensitive resin composition according to the present invention is used to form a green colored layer in the colored layer, and is well known. It can be easily manufactured through the manufacturing method. In addition, the liquid crystal display according to the present invention includes a configuration known to those skilled in the art, except that the color filter according to the present invention described above.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. This is for the purpose of illustrating the invention only, and thus the scope of the invention is not limited.

< Synthetic example  1> Preparation of Binder Resin

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube. A solution containing 3.6 g of azobisisobutyronitrile was added dropwise to the mixture containing 82.5 g (0.6 mole) of acrylate, 35.40 g (0.4 mole) of vinyltoluene and 136 g of propylene glycol monomethyl ether acetate. It was dripped at the flask over, and stirring was continued for 5 hours at 80 degreeC. The atmosphere in the flask was then air from nitrogen to 43.2 g of acrylic acid [0.6 mol (100 mol% of the epoxy group of glycidyl methacrylate used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone. Was added to the flask to continue the reaction at 110 DEG C for 4 hours, and then 45.6 g [0.3 mol (100 mol% of the hydroxy group generated in the previous reaction)] of THPA (tetrahydrophthalic anhydride) was added thereto. The reaction is continued for 2 hours at 110 ℃ Resin A having a solid acid value of 100 mgKOH / g was obtained. The weight average molecular weight of polystyrene conversion measured by GPC was 17,000, and molecular weight distribution (Mw / Mn) was 2.3.

< Synthetic example  2> Preparation of Binder Resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen introduction tube was prepared, and as the monomer dropping lot, 176 g (1.00 mole) of benzyl methacrylate, 35.4 g (0.30 mole) of methacrylic acid, vinyl 82.6 g (0.70 mol) of toluene, 4 g of t-butylperoxy-2-ethylhexanoate, and 40 g of propylene glycol monomethyl ether acetate were added thereto, followed by stirring and mixing to prepare n-dodecane as a chain transfer agent dropping tank. 6 g of thiols and 24 g of PGMEA were added thereto, followed by stirring and preparing. Thereafter, 395 g of propylene glycol monomethyl ether acetate was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, followed by stirring. The temperature of the flask was raised to 90 ° C. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 hours while maintaining 90 ° C, and after 1 h, the temperature was raised to 110 ° C to proceed for 8 hours to obtain a resin having a solid acid value of 70 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 21,000, and molecular weight distribution (Mw / Mn) was 2.2.

< Example  1 to 7>

The colored photosensitive resin composition was manufactured by the conventional method known in the art by the structure of following Table 1 including the binder resin manufactured by the said synthesis example. The unit in Table 1 is parts by weight.

< Comparative example  1 to 8

In the same manner as in Example, a colored photosensitive resin composition was prepared in the composition shown in Table 2 below. The unit in Table 2 is parts by weight.

C: dipentaerythritol hexaacrylate (KAYARAD DPHA; Nippon Kayaku)

D1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; Ciba Specialty Chemical)

D2: 4,4'-di (N, N'-dimethylamino) -benzophenone (EAB-F; Hodogaya Kagaku)

E: Propylene Glycol Monomethyl Ether Acetate

F1: pigment dispersant (acrylic)

F2: 3-methacryloxypropyltrimethoxysilane

< Experimental Example  1> VHR  Characteristic evaluation (afterimage evaluation)

Using the colored photosensitive resin composition prepared in the above Examples and Comparative Examples was measured specimens were prepared in the following manner. A 25 cm 2 glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol, followed by drying. On the said board | substrate, the coloring photosensitive resin composition prepared in the Example and the comparative example was spin-coated so that the film thickness after baking might be 3.0 +/- 0.5 micrometer, and then it pre-dried at 100 degreeC in the clean oven for 3 minutes. After cooling, the substrate was coated with the colored photosensitive resin composition and the interval between the quartz glass photomask (exposure section 30 mm x 30 mm) was set to 100 µm, and the atmosphere was made by using an ultra-high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd. In the atmosphere, light irradiation was performed at an exposure dose (365 nm) of 100 mJ / cm 2. 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 ° C. for a predetermined time, and then washed with water in a heating oven at 200 ° C. for 60 minutes after washing with a colored layer. Formed. The coating film of the colored substrate produced by the above method was immersed in VA liquid crystal at a concentration of 0.5%, and then left at 110 ° C. for 24 hours in a clean oven. The left sample was filtered through a 0.05 μm syringe filter to prepare a liquid crystal sample from which impurities were removed. The prepared liquid crystal sample was injected into the VHR Cell (E.H.C Co., Ltd., product name: KSRT-05 / B111N / NTS05X) which was cleaned through a Kepler injection method. After the injection, the VHR Cell was sealed with a UV sealant, and the indium electrode was deposited and left for 24 hours.

The VHR specimens obtained through the above method were left in a 60 ° C clean oven for 30 minutes, and then measured at an applied voltage of 1 V using a VHR measuring instrument (TOYO Coroporation Model 6254). The results measured through the above measurement method are shown in Table 3 below.

As an evaluation criterion, the initial applied voltage of 1 V passes through the liquid crystal contaminated by the green colored layer and is measured at the initial applied voltage of 1 V to 100%. If only 0.9V is measured, display 90%. VHR evaluation criteria are as follows.

◎: ≥90%, ○: 80% ≤VHR measurement <90%, X: VHR measurement <80

< Experimental Example  2> brightness and Color coordinates  Measure

The colored layer was formed by the following method using the coloring photosensitive resin composition manufactured by the said Example and the comparative example. That is, the colored photosensitive resin composition prepared in Examples and Comparative Examples by spin coating was applied on a glass substrate, then placed on a heating plate and maintained at 100 ° C. for 3 minutes to form a thin film. Subsequently, it was irradiated with luminous intensity of 100 mJ / cm 2 using a 1 kw high pressure mercury lamp containing all g, h and i lines. No special optical filter was used at this time. The thin film irradiated with ultraviolet rays was developed by immersing in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200 ° C. for 30 minutes. The thickness of the colored layer obtained through this was about 2-4 micrometers. Luminance and color coordinates of the colored layer was measured using a microscopic spectrometer OSP-SP2000 and the luminance results are shown in Table 3 below. Evaluation criteria of luminance are shown in Table 4 below. The color coordinate results are shown in Table 5 below.

< Experimental Example  3> Contrast  Measure

A colored layer was formed in the same manner as in Experimental Example 2, and the contrast was measured by using a top-contrast contrast meter BM-5A model, and the measurement standard was based on the contrast 1/30000 of the glass substrate (before forming the colored layer). The results are shown in Table 3 below. Evaluation criteria of the cons last (CR) is as follows.

◎: CR≥24000, ○: 22000≤CR <24000, △: 18000≤CR <22000, X: CR <18000

As shown in Table 3, when the colored layer is formed using the colored photosensitive resin composition of the present invention, it can be seen that the afterimage phenomenon is improved due to the excellent VHR evaluation result, and the brightness and contrast are also improved compared to the comparative example.

Accordingly, the colored photosensitive resin composition of the present invention can provide a green colored layer having improved afterimage phenomenon, excellent brightness and contrast, and can be usefully used for the production of color filters and liquid crystal display devices having improved physical properties and performance. .

Claims (11)

C.I. Pigment Green 58 and C.I. Coloring agent (A) comprising a green pigment containing pigment green 36 in a mass ratio of 99: 1 to 81:19; And Binder resin (B) is included, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, The colorant is C.I. Pigment Green 7, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139 and C.I. Pigment Yellow 150 The coloring photosensitive resin composition further comprises a pigment for color adjustment, which is selected from the group consisting of single or a mixture thereof. The method according to claim 2, Coloring photosensitive resin composition, characterized in that the green pigment and the pigment for color adjustment is contained in a mass ratio of 30:70 to 90:10. The method according to claim 1, The colored photosensitive resin composition is a photopolymerizable compound (C); Photopolymerization initiator (D); And at least 1 sort (s) chosen from a solvent (E) The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, The coloring photosensitive resin composition characterized by the above-mentioned coloring agent contained 5 to 60 weight part with respect to solid content of a coloring photosensitive resin composition. The method according to claim 1, The said binder resin (B) is alkali-soluble, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, The binder resin (B) is obtained by sequentially reacting a copolymer of a first monomer having an unsaturated bond and an epoxy group and a second monomer having an unsaturated bond with a third monomer having a unsaturated double bond and a carboxyl group and a polybasic acid anhydride. The coloring photosensitive resin composition which makes it. The method according to claim 1, The said binder resin (B) has a weight average molecular weight of 3,000-100,000, The coloring photosensitive resin composition characterized by the above-mentioned. The method according to claim 1, The said binder resin (B) is contained in 5 to 90 weight part with respect to solid content of a coloring photosensitive resin composition, The coloring photosensitive resin composition characterized by the above-mentioned. The color filter formed from the coloring photosensitive resin composition of any one of Claims 1-9. The color filter of Claim 10 is provided, The liquid crystal display device characterized by the above-mentioned.