KR101374056B1 - Ink composition for color filter printing, color filter and liquid crystal display device comprising the color filter - Google Patents

Abstract

The present invention relates to a liquid crystal display device including a color filter printing ink composition, a color filter, and a color filter, and more particularly, by including a polyfunctional thiol compound as a binder resin, a thermosetting monomer, a colorant, a solvent, and a curing rate adjusting agent. When manufacturing RGB (Red / Green / Blue) color filter using gravure offset or intaglio offset method, it prevents surface staining by adjusting the curing speed balance between each ink and improves physical properties such as strength, solvent resistance and heat resistance. The present invention relates to a color filter printing ink composition, a color filter to which the ink composition is applied, and a liquid crystal display device having the color filter.

Color filters, liquid crystal displays, printing inks, polyfunctional thiol compounds

Description

TECHNICAL COMPOSING FOR COLOR FILTER PRINTING, COLOR FILTER AND LIQUID CRYSTAL DISPLAY DEVICE COMPRISING THE COLOR FILTER}

The present invention is a color filter printing ink composition for adjusting the curing rate balance between each ink in the manufacture of a color filter using a gravure offset or intaglio offset method, by applying the ink composition to prevent surface staining, such as strength, solvent resistance, heat resistance The present invention relates to a color filter having improved physical properties and a liquid crystal display device having the color filter.

The transparent colored layer of the color filter provided in the conventional liquid crystal display device is mainly manufactured by photolithography. The photolithography method is complicated in the processing process, and the materials and manufacturing equipment required for pattern formation are expensive. Therefore, there is a problem that the manufacturing cost increases. In addition, the disposal cost of the waste liquid generated in the development process and the like during the pattern formation is high, and such waste liquid is harmful and is a problem in terms of preventing environmental pollution.

Therefore, research has been conducted on a pattern formation method that requires low cost instead of photolithography and does not generate harmful waste liquids. Among them, the printing method can produce a transparent colored layer by simply printing and curing the ink of each color on a transparent substrate, so that the manufacturing process is simple and excellent in mass production, and the cost reduction of color filter manufacturing can be realized. Promising in a way

However, unlike the photolithography method, the printing process uses the ink composition to form the red, green, and blue patterns, and then thermally cures the same. Therefore, the difference in curing speed between the inks is different from the solvent contained in the ink composition. Induces a difference in the volatilization rate of, which causes a problem that the surface stains remain in each thin film.

As a method for solving the above problems, there is a method for printing and curing each layer of RGB separately, which is not economical because the manufacturing time is increased in the process. As another method, there is a method of reducing the difference in volatilization rate of the solvent by lowering the curing temperature, but this method also has a disadvantage that the curing time is long due to the lower curing temperature.

Accordingly, there is a need for development of an ink composition for printing color filters that can adjust a curing rate balance between inks when manufacturing RGB color filters.

The present invention provides a color filter printing ink composition which prevents surface staining and improves physical properties such as strength, solvent resistance, heat resistance, etc. by adjusting the cure rate balance between inks when manufacturing a color filter using a gravure offset or intaglio offset method. The purpose is to.

Another object of the present invention is to provide a color filter having high reliability by applying physical properties such as surface stains, strength, solvent resistance, heat resistance, etc. by applying the ink composition for printing a color filter of the present invention.

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

As a result of repeated studies to solve the above problems, the inventors of the present invention, the ink composition comprising a polyfunctional thiol compound in a specific ratio as a curing rate control agent when the RGB color filter using the gravure offset or intaglio offset method The present invention has been completed by focusing on adjusting the curing rate balance between inks to reduce the difference in volatilization rates of the solvents contained in the ink composition, thereby preventing surface stains and improving physical properties.

Therefore, the present invention is 10 to 50% by weight binder resin, 10 to 55% by weight thermosetting monomer, 15 to 55% by weight colorant, 10 to 50% by weight solvent, and 0.01 to 10% by weight of polyfunctional thiol compound as a curing rate control agent It provides a color filter printing ink composition comprising.

The present invention is a color filter comprising a plurality of transparent colored layer formed on the transparent substrate, the transparent colored layer is 10 to 50% by weight binder resin, 10 to 55% by weight thermosetting monomer, 15 to 55% by weight colorant, solvent 10 It provides a color filter, characterized in that the layer formed on the pattern of the transparent substrate by the printing method using the ink composition for color filter printing comprising 50 to 50% by weight, and 0.01 to 10% by weight of the multifunctional thiol compound.

The present invention provides a liquid crystal display device comprising a substrate and a color filter comprising a plurality of transparent colored layers formed on the substrate, wherein the transparent colored layer comprises 10 to 50 wt% of binder resin, 10 to 55 wt% of thermosetting monomer, and colorant. It is a layer formed on the pattern of the transparent substrate by a printing method using the ink composition for color filter printing comprising 15 to 55% by weight, 10 to 50% by weight, and 0.01 to 10% by weight of the multifunctional thiol compound. A liquid crystal display device is provided.

The ink composition for printing a color filter according to the present invention includes a polyfunctional thiol compound as a curing rate adjusting agent at a specific ratio, thereby curing between inks when preparing RGB (red, green, blue) color filters using a gravure offset or intaglio offset method. By adjusting the speed balance, it is possible to prevent stains on the surface of the transparent colored layer and to improve physical properties such as strength, solvent resistance, and heat resistance caused by the lack of curing degree, thereby easily forming a highly reliable color filter. have. In addition, the color filter can be manufactured in a more economical process through this.

The present invention is a color filter printing ink composition for adjusting the curing rate balance between each ink when manufacturing a color filter using a gravure offset or intaglio offset method, the physical properties such as surface staining, strength, solvent resistance, heat resistance by applying the ink composition An improved color filter and a liquid crystal display device having the color filter are provided.

Hereinafter, the present invention will be described in detail.

The ink composition for printing a color filter of the present invention comprises 10 to 50% by weight of binder resin, 10 to 55% by weight of thermosetting monomer, 15 to 55% by weight of colorant, 10 to 50% by weight of solvent, and a polyfunctional thiol compound as a curing rate regulator. It comprises 10% by weight.

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

Binder resin

In the present invention, the binder resin may be used without limitation as long as it is commonly used in the art, and may be used alone or in combination of two or more kinds of acrylic binder resins or polyester binder resins.

The acrylic binder resin may be a polymer polymerized from an acrylic monomer or a copolymer thereof.

Specific examples of the acrylic monomers include 2 to 8 carbon atoms such as acrylic acid, methacrylic acid, ethyl glycidyl ether (meth) acrylate, propyl glycidyl ether (meth) acrylate, and butyl glycidyl ether methacrylate. Alkyl glycidyl ether acrylates; Benzimidazole, methyl methacrylate, methyl alcohol acrylate, glycidyl methacrylate, phenylglycidyl ether (meth) acrylate; Tricyclodecyl methacrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyphenyl (meth) acrylate, 4-methoxyphenyl (meth) acrylate, 2-methoxybenzyl (meth ) Acrylate, 4-methoxybenzyl (meth) acrylate, 2-ethoxyphenyl (meth) acrylate, 4-ethoxyphenyl (meth) acrylate, 2-ethoxybenzyl (meth) acrylate, 4- Ethoxybenzyl (meth) acrylate, 2-chlorophenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate, 2-chlorobenzyl (meth) acrylate, 4-chlorobenzyl (meth) acrylate, 2 -Bromophenyl (meth) acrylate, 4-bromophenyl (meth) acrylate, 2-bromobenzyl (meth) acrylate, 4-bromobenzyl (meth) acrylate, etc. are mentioned. An acrylic monomer can be used individually or in combination of 2 or more types, respectively.

Here, (meth) acrylate means acrylate or methacrylate.

The acrylic binder resin preferably has a weight average molecular weight (hereinafter referred to as "weight average molecular weight") converted from polystyrene as a standard material to 4,000 to 30,000. When the weight average molecular weight is 4,000 to 30,000, the viscosity of the ink composition may be easily controlled, and thixotropy may be excellent to smooth the transition of the ink composition during printing.

The polyester-based binder resin may be a resin obtained by polycondensing a polybasic acid and a polyhydric alcohol.

Specific examples of the polybasic acid include aromatic saturated dibasic acids such as phthalic anhydride, isophthalic acid and terephthalic acid; Unsaturated dibasic acids such as maleic anhydride, fumaric acid, itaconic acid, and cyclaconic acid; Tribasic acids, such as trimellitic anhydride, etc. are mentioned.

The polybasic acid may also be used in combination with aliphatic saturated dibasic acids such as adipic acid, azeline acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and tetrachlorophthalic anhydride.

The polyhydric alcohol may be used in combination with a diol having a side chain or a trivalent or higher polyol. Specific examples of the diol having a side chain include neopentyl glycol, 1,4-butanediol, propylene glycol, and the like, and specific examples of trivalent or higher polyols include trimetholpropane, pentaerythritol, and glycerin. .

The polyester binder resin preferably has a weight average molecular weight of 4,000 to 20,000. When the weight average molecular weight is 4,000 to 20,000, the viscosity of the ink composition may be easily controlled, and thixotropy may be excellent to smooth the transition of the ink composition during printing.

The binder resin may be included in an amount of 10 to 50% by weight, preferably 10 to 35% by weight, based on the total content of the color filter printing ink composition of the present invention. If the content is less than 10% by weight, the coating film is not well formed, and if the content is more than 50% by weight, the viscosity is high, so that poor printing or poor printing stability during continuous printing.

Thermosetting monomer

In the present invention, the thermosetting monomer is preferably a (meth) acrylate monomer having two or more functional groups.

Specific examples of the (meth) acrylate monomers include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and neopentyl glycol di (meth) acryl Rate, 1,6-hexanediol di (meth) acrylate, triethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexyl (meth) acrylate, etc. are mentioned. In particular, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate having five or more functional groups have a high crosslinking density after thermosetting, and thus form a thin film that is stable even under high temperature (high temperature) and various solvents. As it is possible, it is more preferable. A thermosetting (meth) acrylate monomer can be used individually or in combination of 2 or more types, respectively.

The thermosetting monomer may be included in 10 to 55% by weight, preferably 15 to 43% by weight based on the total content of the color filter printing ink composition of the present invention. If the content is less than 10% by weight, the hardness of the print coating film is weak and may be easily damaged by the external environment, when the content exceeds 55% by weight, the pigment is not well dispersed.

coloring agent

In the present invention, any colorant may be used without limitation as long as it is commonly used in the art, and may include an organic pigment or an inorganic pigment.

The organic pigment may be a compound classified as a pigment in the Color Index (published by The Society of Dyers and Colorists), and specific examples thereof include C.I. Pigment Yellow 1, C.I. Pigment Yellow 3, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 16, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 53, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C. I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 128, C. I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 173, C.I. Pigment Yellow 194, C.I. Yellow pigments such as Pigment Yellow 214; C.I. Pigment Orange 13, C.I. Pigment Orange 31, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 42, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 55, C.I. Pigment Orange 59, C.I. Pigment Orange 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Orange pigments such as Pigment Orange 73; C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C. I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Red pigments such as Pigment Red 265; C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Blue pigments such as Pigment Blue 60; C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, C.I. Pigment Violet 36, C.I. Violet pigments such as Pigment Violet 38; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Green pigments such as Pigment Green 58; C.I. Pigment Brown 23, C.I. Brown pigments such as Pigment Brown 25; C.I. Pigment Black 1, C.I. Pigment Black 7 and the like. An organic pigment can be used individually or in combination of 2 or more types, respectively.

In particular, C.I. Pigment Red 254, C.I. Pigment Red 209, C.I. It is preferable to contain at least one selected from Pigment Red 242 and Pigment Red 177. In order to form green pixels, C.I. Pigment Green 36, C.I. Pigment Green 7, C.I. Pigment Green 58, C.I. Pigment Yellow 150 and C.I. It is preferable to contain one or more selected from pigment yellow 138, and to form a blue pixel, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 6 and C.I. It is preferable to contain 1 or more types chosen from pigment violet 23.

Specific examples of the inorganic pigments include titanium oxide, titanium black and carbon black, and these may be used alone or in combination of two or more thereof.

Organic pigments or inorganic pigments may be subjected to resin treatment, surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, graft treatment on the pigment surface with a high molecular compound or the like, and an atomization treatment using a sulfate atomization method. Alternatively, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed.

It is preferable that the pigment used as a coloring agent has a uniform average particle diameter and small particle size, and for this purpose, it can also disperse | distribute using surfactant as a pigment dispersant.

The colorant is preferably contained in 15 to 55% by weight relative to the total content of the color filter printing ink composition of the present invention. More preferably, the red ink is 15 to 50% by weight, the green ink is 25 to 50% by weight, and the blue ink is 14 to 40% by weight. When the content is within the above range, it is advantageous to obtain a desired color coordinate value, and the dispersion of the pigment is efficient. On the other hand, if the content is less than 15% by weight, the thickness of the coating film is increased, and the color contrast ratio and brightness are lowered. If the content is more than 55% by weight, printability and drying property are deteriorated, thereby causing a problem of continuous printing. do.

solvent

In the present invention, any solvent can be used without limitation as long as it is commonly used in the technical field of the present invention, and various organic solvents can be used.

Specific examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, Alkyl, such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol n-butyl ether, and propylene glycol phenyl ether Lenglycol alkyl ethers; Acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, 1,3-butylene glycol diacetate, methoxybutyl acetate and methoxypentyl acetate; Alkylene glycols such as diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ethyl acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate Alkyl ether acetates; 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, 1,3-butylene glycol, glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; and cyclic esters such as? -butyrolactone. These solvents can be used individually or in combination of 2 or more types, respectively.

In particular, it is preferable to contain at least 1 type of thing whose boiling point is 200-300 degreeC in consideration of the applicability | paintability and drying property of an ink composition. Specific examples of the solvent having a boiling point of 200 to 300 ° C include tripropylene glycol methyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, dipropylene glycol methyl ethyl acetate, 1,3- Butylene glycol diacetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 1, 3- butylene glycol, etc. are mentioned.

The solvent may be included in 10 to 50% by weight, preferably 15 to 45% by weight relative to the total content of the color filter printing ink composition of the present invention. When the content is within the above range, it is easy to realize the viscosity of the ink composition suitable for printing. On the other hand, if the content is less than 10% by weight, the transfer to the printed material may not be performed smoothly, resulting in poor transferability, resulting in printability problems. If the content exceeds 50% by weight, the overall viscosity of the ink composition may be lowered to give a blanket. There is a problem in printability because the transition to a blanket is not made smoothly.

Multifunctional Thiol compound

In the present invention, any of the polyfunctional thiol compounds can be used without limitation as long as the compound contains two or more mercapto groups in one molecule as a curing rate regulator.

Specific examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythritol tetrakis-3-mer Captopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

The polyfunctional thiol compound may be included in an amount of 0.01 to 10% by weight, preferably 0.02 to 7% by weight, based on the total content of the color filter printing ink composition of the present invention. When the content is less than 0.01% by weight, the effect as a curing rate regulator is insignificant, and when the content exceeds 10% by weight, the storage stability of the ink composition is not good.

The ink composition for printing a color filter of the present invention comprising the above components may further include additives such as fillers, other polymer compounds, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents, as necessary. .

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

As a specific example of another high molecular compound, Curable resin, such as an epoxy resin and a maleimide resin; Thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyurethane, and the like.

Commercially available surfactants may be used as the pigment dispersant, and specific examples include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 or more types, respectively. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. Commercially available products include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW, Kyoeisha Chemical Co., Ltd.), F-Top (EFTOP, Tochem Products Co., Ltd.), Mega Pack. (MEGAFAC, manufactured by Dai Nippon Ink Chemical Co., Ltd.), Florad (Flourad, manufactured by Sumitomo 3M Corporation), Asahi guard (manufactured by Asahi Glass), Surflon (manufactured by Asahi Glass,) (SOLSPERSE, Genenca Co., Ltd.), EFKA (made by EFKA Chemicals Co., Ltd.), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl tree Methoxysilane, etc. are mentioned.

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

Specific examples of the ultraviolet absorbent include 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

As an aggregation inhibitor, sodium polyacrylate etc. are mentioned, for example.

The additive may be included in an amount of 0.01 to 10% by weight based on the total content of the color filter printing ink composition of the present invention.

Hereinafter, the color filter which applied the ink composition for color filter printing of this invention is demonstrated.

The color filter of the present invention comprises a substrate and a transparent colored layer formed on the substrate.

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

The transparent colored layer includes a binder resin, a thermosetting monomer, a colorant, a solvent, and a color filter printing ink composition including a polyfunctional thiol compound as a curing rate adjusting agent, and may be a layer formed by printing the composition on a substrate and then heating it. .

More specifically, the transparent colored layer is a layer formed by printing the ink composition on the transparent substrate by a gravure offset or intaglio offset method using intaglio and blanket, and then heating it to a temperature of 150 to 250 ° C.

The transparent colored layer may be a plurality of layers.

The color filter is usually a black matrix and a red, green, and blue primary color pixel disposed on a substrate, but by using the ink composition of the present invention containing a colorant corresponding to any of these colors, A black matrix and three primary color pixels can be arranged on a substrate by using the ink composition of the present invention, in which a pixel can be obtained, and the colorant corresponding to the desired color also for other colors. At this time, the ink composition of the present invention may be applied only to one color, two colors or three colors of the black matrix and three primary colors. In addition, a black matrix can also be formed using the ink composition containing the black coloring agent of this invention as a light shielding layer.

The color filter as described above has a small difference in film thickness in the transparent colored layer surface, for example, a difference in film thickness in the surface may be 1 to 3 µm, preferably 0.15 µm or less, and more preferably 0.05 µm or less. Therefore, such a color filter is excellent in smoothness, and by providing the same in a color liquid crystal display device, a liquid crystal display device of excellent quality can be manufactured with high yield.

Hereinafter, the liquid crystal display device provided with the color filter of the present invention will be described.

The liquid crystal display device of the present invention includes a configuration known to those skilled in the art, except that the color filter of the present invention is provided, and any kind of liquid crystal display device to which the color filter of the present invention is applicable may be used. It is not particularly limited.

According to an aspect of the present invention, a counter electrode substrate including a thin film transistor (TFT element), a pixel electrode, and an alignment layer is opposed to each other at predetermined intervals, and a liquid crystal material is injected into a portion between the electrode substrates. And a transmissive liquid crystal display device including the liquid crystal layer formed thereon. There is also a reflective liquid crystal display device further comprising a reflective layer between the substrate of the color filter and the transparent colored layer.

According to another aspect of the present invention, there is a liquid crystal display device including a TFT substrate joined on a transparent electrode of a color filter, and a backlight fixed at a position where the TFT substrate overlaps the color filter. The TFT substrate includes an outer frame made of a light-proof resin surrounding a peripheral surface of a color filter, a liquid crystal layer made of a nematic liquid crystal imposed in the outer frame, and a plurality of pixels provided for each region of the liquid crystal layer. An electrode, a transparent glass substrate on which pixel electrodes are formed, and a polarizing plate formed on an exposed surface of the transparent glass substrate may be provided.

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

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

<Production of Ink Composition for Color Filter Printing>

Example  1. Preparation of Blue Ink Composition

23.0 wt% of acrylic resin (A-1300, manufactured by Aekyung Chemical Co., Ltd.) as a binder resin,

17.5% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a thermosetting monomer,

As a colorant, C.I. Pigment Blue 15: 6 and C.I. 18.5 weight% of the mixed pigment which pigment violet 23 mixed in the weight ratio of 90:10,

40.0% by weight of a mixed solvent in which propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate were mixed at a weight ratio of 1: 8 as a solvent,

1.0 wt% of trimethylolpropanetris-3-mercaptopropionate (TMMP, manufactured by Sakai Chemical Co., Ltd.) was mixed as a curing rate adjusting agent to prepare an ink composition for color filter printing.

Example  2 and 3. Preparation of Blue Ink Compositions

Except that each component in Example 1 was used in the content as shown in Table 1 was carried out in the same manner as in Example 1.

Example  4. Preparation of Red Ink Composition

In Example 1, each component was used in an amount as shown in Table 1 below, but C.I. Pigment Red 254 and C.I. The same procedure was followed as in Example 1, except that Pigment Red 177 used a mixed pigment mixed at a weight ratio of 64:36.

Comparative Example  1 to 3

Except that each component in Example 1 was used in the content as shown in Table 1 was carried out in the same manner as in Example 1.

The components of the color filter printing ink compositions prepared in Examples and Comparative Examples and their compositions are shown in Table 1 below. At this time, the content of each component represents weight%.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Binder resin 23.0 22.0 21.0 23.0 17.5 15.5 24.0 Thermosetting
Monomer 17.5 16.5 15.5 17.5 12.0 10.0 17.495 coloring agent 18.5 18.5 18.5 18.5 18.5 18.5 18.5 solvent 40.0 40.0 40.0 40.0 40.0 40.0 40.0 Curing Speed
Regulator 1.0 3.0 5.0 1.0 12.0 16.0 0.005

&Lt; Production of color filter &

Example  5

The blue layer is printed on the transparent substrate by the intaglio offset printing method on the transparent substrate, and the ink composition prepared in Example 4 is printed on the transparent substrate by the intaglio offset printing method. To print a red layer. Subsequently, the transparent colored layer of 1.9 micrometer thickness was formed by heating and hardening simultaneously at the temperature of 200 degreeC, and the color filter was manufactured.

Example  6 and 7, Comparative Example  4

In Example 5, instead of the ink composition prepared in Example 1, the ink composition prepared in Example 2 (Example 6), the ink composition prepared in Example 3 (Example 7), prepared in Comparative Example 3 The same procedure as in Example 5 was carried out except that the prepared ink composition (Comparative Example 4) was used.

Test Example

The storage stability of the color filter printing ink compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 3 and the intaglio offset printing method using an offset blanket on the transparent substrate were printed on a transparent substrate at 220 ° C. By heating to a temperature to form a transparent colored layer of the liquid crystal display of 1.9㎛ thickness, the physical properties thereof were measured by the following method and the results are shown in Table 2 below.

(1) Storage stability: The viscosity immediately after preparing the ink composition for color filter printing was measured, and after leaving at 25 degreeC for 1 week, the viscosity was measured again. The change in viscosity (ΔcP) was calculated and evaluated according to the following criteria.

○ ○ △ cP <1,000

Δ: 1,000 <ΔcP ≤ 2,000

X: 2,000 <ΔCp

(2) Pencil hardness: Using a pencil hardness tester (Sukbo Science Co., Ltd.), while holding the core of the pencil specified in KS G 2630 (pencil) at an angle of 45 ° and pressing it on the surface of the transparent colored layer with a load of 1 kg After moving to scratch the surface, it was evaluated according to the following evaluation criteria.

◎: 3H <hardness

○: H <hardness ≤ 3H

Δ: B <hardness ≤ H

X: 3B <hardness <B

-XX: hardness ≤ 3B

(3) Solvent resistance: After keeping each solvent of isopropyl alcohol (IPA), n-methyl 2-pyrrolidone (NMP), and gamma butyrolactone (GBL) constant at 23 degreeC, a transparent colored layer here The formed substrate was immersed for 30 minutes to measure color change (ΔE * ab). At this time, the CIE color coordinate values before and after solvent resistance evaluation were respectively measured using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus, Inc.), and calculated using Equation 1 below to the following evaluation criteria. Evaluated accordingly.

ΔE * ab = [(△ L *) ² + (△ a *) ² + (△ b *) ² ] ^1/2

In Equation 1, ΔE * ab represents a color change, ΔL * represents a lightness difference, Δa * represents a color difference between red and green, and Δb * represents a color difference between yellow and blue.

◎: ΔE * ab <1.5

○: 1.5 <ΔE * ab ≤ 2.0

Δ: 2.0 <ΔE * ab ≤ 2.5

X: 2.5 <ΔE * ab ≤ 3.0

XX: 3.0 <ΔE * ab

(4) Heat resistance: After leaving the board | substrate with a transparent colored layer left for 2 hours in 230 degreeC oven, color change ((DELTA) E * ab) was measured. At this time, the CIE color coordinate values before and after solvent resistance evaluation were respectively measured using a microscopic spectrophotometer (Model No. OSP-SP2000, Olympus, Inc.), and calculated using Equation 1 above, and then to the following evaluation criteria. Evaluated accordingly.

◎: ΔE * ab <1.5

○: 1.5 <ΔE * ab ≤ 2.0

Δ: 2.0 <ΔE * ab ≤ 2.5

X: 2.5 <ΔE * ab ≤ 3.0

XX: 3.0 <ΔE * ab

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pencil hardness ○ ○ ◎ ◎ ○ ○ ○ Solvent resistance IPA ◎ ◎ ◎ ◎ ◎ ◎ ◎ NMP ○ ◎ ◎ ◎ ◎ ◎ △ GBL ◎ ◎ ◎ ◎ ◎ ◎ ◎ Heat resistance ○ ◎ ◎ ◎ ◎ ◎ X Storage stability ○ ○ ○ ○ X X X

The color filter surface stains prepared in Examples 5 to 7 and Comparative Example 4 were measured by the following method, and the results are shown in Table 3 below.

(5) Surface spotting: The presence of abnormality in the shape of the surface of the red and blue patterns using an ultra-depth 3D shape measurement microscope (VK-9500, Keyence) was evaluated according to the following evaluation criteria. That is, it is most ideal that there are no foreign matters or abnormalities on the surface.

○: no abnormality in shape

-X: there is a problem with the shape

Example 5 Example 6 Example 7 Comparative Example 1 Surface stain ○ ○ ○ X

As shown in Tables 2 and 3, the ink composition for printing the color filters of Examples 1 to 4 according to the present invention is excellent in pencil strength, solvent resistance, heat resistance and storage stability, and particularly of the multifunctional thiol compound which is a curing rate regulator. It was confirmed that the better as the content increases. Moreover, it was confirmed that the surface stain did not generate | occur | produce the transparent colored layer of the color filter manufactured using the two types of ink compositions of the said Examples 1-4.

On the other hand, the ink compositions of Comparative Examples 1 to 2 containing an excessive amount of a multifunctional thiol compound had excellent physical properties but poor storage stability, and the ink composition of Comparative Example 3 containing a small amount of the polyfunctional thiol compound had a general balance of physical properties. It did not come true. In addition, the transparent colored layer prepared by using the two ink compositions of the ink composition and the other ink composition of Comparative Example 3 was confirmed that the surface stain was generated because the curing rate between different inks is not controlled.

Claims (5)

10 to 50 wt% of binder resin, 10 to 55 wt% of thermosetting monomer, 15 to 55 wt% of colorant, 10 to 50 wt% of solvent, and 0.01 to 10 wt% of polyfunctional thiol compound, wherein the multifunctional thiol compound is Tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol The ink composition for printing a color filter selected from the group consisting of tetrakis-3-mercaptopropionate. The ink composition of claim 1, wherein the content of the multifunctional thiol compound is 0.02 to 7 wt%. delete A color filter comprising a plurality of transparent colored layers formed on a pattern of a transparent substrate by a printing method using the ink composition for printing a color filter of claim 1. A liquid crystal display device comprising the color filter of claim 4.