TW201823376A - Colored photosensitive resin composition and color filter and image display device produced using the same having near-infrared transmittance and excellent optical density - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition which is a colored photosensitive resin composition containing a colorant, which contains 5 to 70% by weight of a blue pigment and 30 to 95% by weight of a brown pigment based on the total weight of the above colorant.

Description

   Colored photosensitive resin composition, color filter and image display device manufactured by same   

The present invention relates to a colored photosensitive resin composition, and a color filter and an image display device manufactured by the same.

Since color filters can be widely used in various display devices such as image pickup elements and liquid crystal display devices (LCD), their application range is rapidly expanding. The color filter may include three color coloring patterns of red, green, and blue, or three color coloring patterns of yellow, magenta, and cyan. A black matrix layer that prevents light leakage between pixels before each colored pattern, an over coat (OC) that corrects step changes between pixels to improve flatness, and maintains a cell gap between two substrates (Cell -gap) column spacers (CS; column spacers) to form a color filter.

The color filter widely used in the above-mentioned display device is generally manufactured by spin-coating a photosensitive photosensitive resin composition containing a pigment dispersion composition corresponding to the color of each pattern on a substrate on which a black matrix pattern is formed. Or slit coating for uniform coating, heating and drying, exposing and developing the formed coating film, and further repeating the heating and curing operation for each color as needed to form pixels of each color. A color filter is also produced by a coloring photosensitive resin composition using the pigment dispersion composition as a coloring material in processes that do not require a development process such as the above-mentioned coating method but an inkjet method and a printing method.

In the case of a black matrix layer or a columnar spacer, a colored photosensitive resin composition containing carbon black as a colorant is generally used, but carbon black has a disadvantage of having low electrical resistance. Therefore, it has been applied as a high-resistance material by the surface treatment of carbon, but in the case of carbon black, it is difficult to suppress the increase of the dielectric constant due to the characteristics of the carbon material when it is manufactured using a colored photosensitive resin composition, and particularly The near-infrared (Near-IR) has very poor transmittance characteristics.

For a color filter using a colored photosensitive resin composition, physical properties such as high brightness and high contrast are required. In particular, as the color filter using a colored photosensitive resin composition is recently applied to various fields of various image display devices To increase the demand for high reliability.

Korean Registered Patent No. 0,860,432 relates to a black photosensitive composition, which includes a photopolymerizable compound, a photopolymerization initiator, and an organic pigment and a black pigment as a shape stabilizer at a specific quality ratio.

However, in the case of the above-mentioned document, near-IR transmittance characteristics are poor, and most importantly, the following point has not been understood: in order to improve reliability, the residual film rate must be increased.

Therefore, it is necessary to develop a coloring photosensitive resin composition that can produce a color filter with improved near-infrared transmittance or optical density or excellent residual film rate.

Prior art literature

Patent literature

Patent Document 1: Korean Registered Patent No. 0,860,432 (September 19, 2008)

An object of the present invention is to provide a colored photosensitive resin composition capable of producing a color filter having a high residual film rate and excellent reliability.

Another object of the present invention is to provide a colored photosensitive resin composition capable of producing a color filter having excellent near-infrared transmittance or optical density.

Another object of the present invention is to provide a color filter and an image display device manufactured using the above-mentioned colored photosensitive resin composition.

The colored photosensitive resin composition according to the present invention for achieving the above object is a colored photosensitive resin composition containing a colorant, wherein the colorant contains a blue pigment 5 to 70 based on the total weight of the colorant. % By weight and brown pigments from 30 to 95% by weight.

The present invention also provides a color filter including the cured product of the colored photosensitive resin composition described above, and an image display device including the color filter.

The coloring photosensitive resin composition according to the present invention contains a coloring agent containing a blue pigment and a brown pigment in a specific content, and thus has a color filter capable of producing a high residual film rate, near-infrared transmittance characteristics, or excellent optical density. The advantages.

In addition, a color filter manufactured using the colored photosensitive resin composition of the present invention and an image display device including the color filter have advantages of excellent near-infrared transmittance, optical density, and residual film rate.

The present invention is described in further detail below.

In the present invention, when a component is "on" another component, it is not only the case where a component is in contact with another component, but also the case where there are other components between the two components.

In the present invention, when a certain part “contains” a certain constituent element, as long as there is no particular contrary description, other constituent elements are not excluded, which means that other constituent elements may be further included.

<Colored photosensitive resin composition>

One aspect of the present invention relates to a colored photosensitive resin composition, which is a colored photosensitive resin composition containing a colorant. The colorant contains 5 to 70% by weight of a blue pigment and brown based on the total weight of the colorant. Pigments are 30 to 95% by weight.

Colorant

The colorant according to the present invention is characterized in that it contains 5 to 70% by weight of a blue pigment and 30 to 95% by weight of a brown pigment based on the total weight of the colorant.

The colored photosensitive resin composition according to the present invention contains a blue pigment and a brown pigment contained in the above range based on 100% by weight of the total solid content of the colorant. Therefore, the near-infrared transmittance can be improved, and therefore, the optical density can be manufactured. Advantages of excellent color filters. In addition, since the residual film ratio is excellent, a color filter having high reliability can be manufactured.

The residual film rate is a value obtained by dividing the film thickness after the post-heat treatment by the film thickness before the subsequent heat treatment and multiplying by 100. A high residual film rate means that the change rate of the film thickness is small, and therefore it means excellent reliability.

In one aspect of the present invention, the blue pigment can include one or more blue pigments selected from the group consisting of: CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 21, CI Pigment Blue 28, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Blue 76.

The blue pigment may contain 5 to 70% by weight, specifically 8 to 65% by weight, and more specifically 10 to 60% by weight based on the total solid content of the colorant.

When the blue pigment is contained within the above range, there is an advantage that a color filter having excellent residual film rate or excellent near-infrared transmittance and optical density can be manufactured. When the content of the blue pigment is less than the above range, the near-infrared transmittance may be slightly reduced. When it exceeds the above range, the optical density may be slightly reduced and the residual film rate may be slightly reduced. Therefore, it is preferably within the above range. Contains the aforementioned blue pigment.

The brown pigment can include, for example, one or more brown pigments selected from the group consisting of C.I. Pigment Brown 26, C.I. Pigment Brown 28, C.I. Pigment Brown 83, and C.I. Pigment Brown 93. The above-mentioned brown pigment may contain 30 to 95% by weight, specifically 32 to 93% by weight, and more specifically 35 to 90% by weight with respect to 100% by weight of the entire solid content of the colorant.

When the brown pigment is contained within the above range, a colored photosensitive resin composition capable of producing a color filter having excellent residual film ratio, near infrared transmittance, or optical density can be obtained. When the content of the brown pigment is less than the above range, the near-infrared transmittance and optical density may be slightly reduced. When the content exceeds the above range, there may be a problem that the optical density or the residual film rate may be slightly reduced. Therefore, it is preferable. The said brown pigment is contained in the said range.

The colored photosensitive resin composition according to the present invention has the advantages that the near-infrared transmittance and optical density can be improved by including both the blue pigment and the brown pigment in the above range. In particular, by maximizing the improvement of the residual film rate, there is an advantage that a color filter having excellent reliability can be manufactured.

In another aspect of the present invention, the colorant can further include a purple pigment.

In another aspect of the present invention, the above-mentioned purple pigment can include one or more purple pigments selected from the group consisting of: CI Pigment Violet 14, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, and CI Pigment Violet 32, CI Pigment Violet 33, CI Pigment Violet 36, CI Pigment Violet 37, and CI Pigment Violet 38.

In the case where the coloring photosensitive resin composition according to the present invention further contains the above-mentioned purple pigment, this is desirable because it can exhibit a low color change rate, a high residual film rate, or an excellent optical density.

The purple pigment may contain 1 to 15% by weight, specifically 3 to 9% by weight, and more specifically 4 to 8% by weight, based on 100% by weight of the solid content of the colorant as a whole. But it is not limited to this.

In another aspect of the present invention, the colorant may contain 3 to 50% by weight, specifically 5 to 20% by weight, more specifically, based on the total weight of the colored photosensitive resin composition. Ground may contain 6 to 10% by weight.

When the content of the colorant is less than the above range, the tinting strength may be slightly reduced. When it exceeds the above range, the solvent resistance or adhesion may be reduced, which is disadvantageous from the viewpoint of the process. The above-mentioned colorant is contained in the range.

When the colored photosensitive resin composition according to the present invention is used as a black matrix layer, the above-mentioned colorant can provide light-shielding properties, and thus can prevent light leakage of the black matrix layer. The colored photosensitive resin according to the present invention When the composition is used as a columnar spacer, it can play a role of maintaining a cell gap while maintaining a constant elastic modulus.

The black matrix layer and the columnar spacer may be integrally formed. In short, the colored photosensitive resin composition according to the present invention can be used for producing a columnar spacer in which a black matrix layer is integrally formed. The above-mentioned black matrix layer integrally formed spacers do not form the black matrix layer and the columnar spacers separately, but can perform all the functions of the black matrix layer and the columnar spacers with one pattern, and can use the colored photosensitive resin according to the present invention. combination.

The colorant may contain other pigments in addition to the brown pigment, the blue pigment, and the purple pigment.

As the pigment, an organic pigment or an inorganic pigment generally used in this field can be used.

In addition, the above-mentioned pigments can also be subjected to resin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc., grafting treatment on the surface of the pigment using a polymer compound, etc., if necessary. A micronization process such as a sulfuric acid micronization method, a cleaning process using an organic solvent, water, or the like for removing impurities, or a ionic impurity removal process using an ion exchange method, or the like.

As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used. Specifically, for example, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, and isoindolinone pigments can be used. , Isoindoline pigment, osmium pigment, fluorenone pigment, dioxazine pigment, anthraquinone pigment, bi-anthraquinone pigment, anthracene pigment, anthrone pigment, indanthrone pigment, xanthones pigment, dermatanthone Pigments, diketopyrrolopyrrole pigments, and the like.

In addition, as the inorganic pigment, metal compounds such as metal oxides and metal complexes can be used. Specifically, for example, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black can be used. , Organic black pigments, titanium black, and oxides of metals such as red, green, and cyan which are mixed to form black, or composite metal oxides.

As the pigment, a pigment dispersion liquid in which the particle diameter of the pigment is uniformly dispersed is preferably used. As an example of a method for uniformly dispersing the particle diameter of the pigment described above, for example, a method of performing a dispersion treatment containing a pigment dispersant, this method is suitable because a pigment in which a pigment is uniformly dispersed in a solution can be obtained. Dispersions.

The pigment dispersant may include, for example, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, etc., which can be used individually or in combination of two or more, but Not limited to this.

The pigment dispersant is added in order to maintain the detackiness and stability of the pigment, and a pigment dispersant generally used in this field may be used without limitation.

The pigment dispersant can be, for example, Lubrizol's trade name: SOLSPERS 5000, but is not limited to this. In addition, it can also contain BMA (butyl methacrylate) or DMAEMA (N, N methacrylate). -Dimethylaminoethyl)). At this time, as the acrylate dispersant, an acrylate dispersant manufactured by the activity control method disclosed in Korean Laid-Open Patent No. 2004-0014311 is preferably used as the acrylate dispersant manufactured by the activity control method. Commercially available products, such as: DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc.

The acrylic dispersants exemplified above can be used individually or in combination of two or more.

As the pigment dispersant, in addition to the acrylic dispersant described above, other resin-based pigment dispersants can be used. As the other resin-based pigment dispersant, for example, a conventional resin-based pigment dispersant may be included, in particular, polyurethane, polycarboxylate represented by polyacrylate, unsaturated polyamine, polycarboxylic acid, polycarboxylic acid Carboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminophosphonium phosphates, polyhydroxycarboxylic acid esters, and modified products thereof Or an oily dispersant of amidine or their salts formed by the reaction of a polyester having a free carboxyl group and a poly (lower alkyleneimine); a water-soluble resin or a water-soluble polymer compound such as: ( (Meth) acrylic-styrene copolymer, (meth) acrylic- (meth) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylic acid Esters; ethylene oxide / propylene oxide addition products and phosphate esters.

As a commercial product of the above-mentioned resin-based dispersant, for example, as a cationic resin dispersant, trade names of BYK: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, and DISPER BYK can be included. -163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; Trade names of BASF (BASF): EFKA-44, EFKA-46, EFKA-47, EFKA -48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800 ; Trade names of Lubrizol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Trade names of Chuanyan Fine Chemical Co., Ltd .: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000 ; Trade names of Ajinomoto Co., Ltd .: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Co., Ltd .: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 and so on. In addition to the acrylic dispersant described above, other resin-based pigment dispersants may be used individually or in combination of two or more, and may be used in combination with the acrylic dispersant.

The content of the dispersant may be 5 to 70% by weight, and more preferably 15 to 68% by weight based on the solid content weight of the pigment, but is not limited thereto. However, in the case where the above-mentioned dispersant is contained in the above-mentioned content standard, this is desirable because the phenomenon of gelation after dispersion can be prevented. When the content of the dispersant is less than 5% by weight, micronization of the pigment may be slightly difficult, or gelation may occur after dispersion. When the content of the dispersant exceeds 70% by weight, viscosity may occur. Slightly raised issue.

In yet another aspect of the present invention, the colored photosensitive resin composition may further include one or more selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and additive.

Alkali soluble resin

The coloring photosensitive resin composition concerning this invention may contain alkali-soluble resin.

The alkali-soluble resin has reactivity and alkali-solubility based on the action of light or heat, functions as a solid content dispersion medium for a colorant, and can function as a binder resin.

As the alkali-soluble resin according to the present invention, an alkali-soluble resin having an acid value of 50 to 200 (KOH mg / g) is selected and used. The acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is related to solubility. If the acid value of the alkali-soluble resin is less than the above range, it is difficult to ensure a sufficient development speed. On the other hand, if it exceeds the above range, the adhesion to the substrate is reduced, short circuits of patterns are likely to occur, and the storage stability of the overall composition is high. Decrease and increase viscosity.

In addition, in the above-mentioned alkali-soluble resin, in order to increase the surface hardness for use as a color filter, it may be considered to limit the molecular weight and molecular weight distribution (Mw / Mn). The weight-average molecular weight is preferably 3,000 to 30,000, more preferably 5,000 to 20,000, and the molecular weight distribution has a range of 1.5 to 6.0, and preferably a range of 1.8 to 4.0. In this way, it is directly used for polymerization or purchase. The alkali-soluble resin having a molecular weight and a molecular weight distribution in the above range can not only increase the hardness as described above, but also have a high residual film ratio. In addition, the solubility of the unexposed portion in the developer is excellent, and the resolution can be improved.

The alkali-soluble resin includes one or more members selected from the group consisting of a carboxyl group-containing unsaturated monomer polymer, a copolymer with a monomer having an unsaturated bond copolymerizable therewith, and a combination thereof.

In this case, the unsaturated monomer containing a carboxyl group may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, or the like. Specifically, as the unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, and the like can be included. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. The unsaturated polycarboxylic acid may be an acid anhydride, specifically, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. In addition, the unsaturated polycarboxylic acid may be a mono (2-methacryloxyalkyl) ester thereof, and may include, for example, a mono (2-propenyloxyethyl) succinate, a mono (2-methyl succinate) Acrylic acid ethoxyethyl) ester, phthalic acid mono (2-acrylic acid oxyethyl) ester, phthalic acid mono (2-methacrylic acid oxyethyl) ester, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate having a dicarboxyl polymer at both ends, and examples thereof may include, for example, ω-carboxy polycaprolactone monoacrylate, ω-carboxy polycaprolactone mono Methacrylate, etc. These carboxyl group-containing monomers may be used alone or as a mixture of two or more.

In addition, the monomer copolymerizable with the carboxyl group-containing unsaturated monomer may include, for example, one or more selected from the group consisting of an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, and an unsaturated carboxylic acid aminoalkyl group. Ester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl carboxylic acid ester compounds, unsaturated ether compounds, vinyl cyanide compounds, unsaturated sulfonimine compounds, aliphatic conjugated diene compounds, A macromonomer having a monoacrylfluorene group or a monomethacrylfluorene group at the terminal, a bulky monomer, and a combination thereof.

More specifically, as the above copolymerizable monomer, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-styrene Methoxystyrene, p-methoxystyrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, M-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene and other aromatic vinyl compounds; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-acrylate Propyl ester, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate Ester, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy acrylate Propyl ester, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, acrylic acid 4-hydroxybutyl, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , Phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-benzene methacrylate Ethoxyethyl ester, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylic acid Ester, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene acrylate, methyl Dicyclopentadienyl acrylate, adamantane (meth) acrylate, (meth) acrylic acid Bornyl ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and unsaturated carboxylic acid esters such as glycerol monomethacrylate ; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, acrylic-2 -Aminopropyl, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate Unsaturated carboxylic acid amino alkyl ester compounds such as esters, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, and the like; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylate compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate; vinyl methyl Unsaturated ether compounds such as ether, vinyl ethyl ether, allyl glycidyl ether; ethyl acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene chloride, etc. Alkenyl cyanide compounds: Unsaturated fluorene amines such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamine Class; maleimide, benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and other unsaturated ammonium compounds; 1,3-butadiene , Aliphatic conjugated diene such as isoprene, chloroprene, etc .; and in polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate Polysiloxanes are huge monomers with monoacrylfluorene or monomethacrylfluorene at the end of the polymer molecular chain; monomers with a norbornyl main chain that can reduce the relative dielectric constant value, and diamonds Large-volume monomers such as monomers having an alkane main chain and monomers having a rosin main chain.

The alkali-soluble resin may contain 10 to 80% by weight, specifically 10 to 70% by weight, and more specifically 30 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. weight%.

In the case where the above-mentioned alkali-soluble resin is contained in the above range, this is desirable because it has sufficient solubility in the developing solution, so that the formation of a pattern becomes easy, and the film in the pixel area of the exposed portion is prevented from being reduced during development. The missing portion of the pixel area is reduced.

In the case where the alkali-soluble resin is not included in the above range, the non-pixel region may be slightly formed as a missing portion. When the content of the alkali-soluble resin exceeds the above range, the solubility in the developer is slightly reduced, and the pattern is slightly reduced. Formation becomes slightly more difficult.

Photopolymerizable compound

The photopolymerizable compound contained in the colored photosensitive resin composition of the present invention is a compound capable of polymerizing under the action of light and a photopolymerization initiator described later, and may include, for example, a monofunctional monomer, a difunctional monomer, and others Polyfunctional monomers, etc.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. , 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like.

The type of the difunctional monomer is not particularly limited, and may be, for example, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (methyl) ) Acrylate, triethylene glycol di (meth) acrylate, bis (propenyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

The kind of the polyfunctional monomer is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylation. Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate , Ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable compound include, but are not limited to, Miramer M600 by Miura Industries, Ltd. and the like.

The photopolymerizable compound may contain 1 to 20% by weight, preferably 1 to 15% by weight, and more preferably 2 to 10% by weight based on the total weight of the colored photosensitive resin composition, within the above range. When contained, there is an advantage that it is advantageous in terms of the strength and smoothness of the pixel region.

When the content of the photopolymerizable compound is less than the above range, the intensity of the pixel region may be slightly reduced, and when the content of the photopolymerizable compound exceeds the range, the smoothness may be slightly decreased. Within range.

Photopolymerization initiator

The coloring photosensitive resin composition concerning this invention can contain a photoinitiator. The photopolymerization initiator includes an oxime-based compound. The oxime-based compound may include, for example, 0-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, ethyl ketone-1- [9-ethyl-6- (2-methyl- 4-tetrahydropyranyloxybenzyl) -9H-carbazol-3-yl] -1- (O-ethylamidoxime) (trade name: Irgacure OXE-02, Ciba) Etc., but not limited to this.

In the case where the photopolymerization initiator of the present invention contains an oxime-based compound, due to the structural characteristics of the oxime-based compound, it is easier to form a pattern than an initiator containing a compound of another structure, and has the advantages of excellent pattern maintenance. .

The photopolymerization initiator may include 0.1 to 5% by weight, specifically 0.3 to 3% by weight, and more specifically, 0.4 to 1 based on the entire weight of the colored photosensitive resin composition. In this case, this is suitable because the sensitivity of the colored photosensitive resin composition can be increased and the exposure time can be shortened. Therefore, productivity is improved, and high resolution can be maintained. In addition, there is an advantage that the strength of a pixel region formed using the colored photosensitive resin composition and the smoothness at the surface of the pixel region become good.

Solvent

The solvent contained in the colored photosensitive resin composition of the present invention is not particularly limited, and various organic solvents used in the field of colored photosensitive resin compositions can be used.

The above solvents may specifically include ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and the like Diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc .; ethylene glycol alkyl ether ethyl Acid esters, such as methylcellulose acetate, ethylcellulose acetate, etc .; alkyl glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, etc .; alkoxyalkyl acetates, such as methoxybutyl acetate, methoxypentyl acetate, etc .; aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene Methylbenzene, etc .; ketones, such as methyl ethyl ketone, acetone, methylpentyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanone Alcohols, glycols, glycerol, etc .; esters, such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc .; cyclic esters, such as γ-butyrolactone, etc.

As for the above-mentioned solvents, in terms of coatability and drying properties, it may be preferable to include an organic solvent having a boiling point of 100 ° C to 200 ° C in the above-mentioned solvent, and more preferably, for example, an alkylene glycol alkyl ether acetic acid Esters, ketones, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and more preferably may include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acid esters, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the coloring photosensitive resin composition of the present invention may be 20 to 85% by weight, preferably 25 to 85% by weight, based on the total weight of the coloring photosensitive resin composition including the same. It preferably contains 30 to 80% by weight.

In the case where the content of the above-mentioned solvent is within the above-mentioned range, this is desirable because a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes also referred to as die coating) Machine), inkjet and other coating devices, the coating properties can be improved. When the content of the solvent is less than the above range, the coating properties may be slightly reduced, so the manufacturing process may be slightly difficult. When the content of the solvent is outside the above range, the formation of the colored photosensitive resin composition may occur. The problem that the performance of the color filter may be slightly reduced.

Additives

In order to improve coating properties or adhesion, the coloring photosensitive resin composition according to the present invention may further include additives such as adhesion promoters and surfactants.

In order to improve the adhesion to the substrate, the above-mentioned adhesion promoter may be added, and it may contain a silane coupling having a reactive substituent selected from a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and a combination thereof. Agent, but not limited to this. For example, the above-mentioned silane coupling agent may include, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc., which can be used alone Or use two or more of them in combination.

When the coloring photosensitive resin composition concerning this invention contains the said surfactant, there exists an advantage that coating property can be improved. For example, as the surfactant, BM-1000, BM-1100 (BM Chemie), FLUORAD FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), SH-28PA / -190 can be used. / SZ-6032 (Toray Silicone Co., Ltd.) and other fluorine-based surfactants, but not limited to this.

In addition, the colored photosensitive resin composition according to the present invention may further include additives such as an antioxidant, an ultraviolet absorber, and an anti-agglomerating agent within a range that does not hinder the effects of the present invention. The above-mentioned additives also do not hinder the effects of the present invention. Those within the range may be appropriately used by those skilled in the art. For example, the additive can be used in an amount of 0.05 to 10% by weight, specifically, 0.1 to 10% by weight, and more specifically, 0.1 to 5% by weight based on the entire weight of the colored photosensitive resin composition, but it is not Limited to this.

<Color filter>

Another aspect of the present invention relates to a color filter manufactured using the above-mentioned colored photosensitive resin composition.

In another aspect of the present invention, the color filter includes a pattern layer, a black matrix layer, and a columnar spacer. One or more of the black matrix layer and the columnar spacer may be the coloring sensitivity. A cured product of a resin composition.

In another aspect of the present invention, the black matrix layer and the columnar spacer may be integrally formed.

The pattern layer can be manufactured by a common method used by those skilled in the art, and the present invention is not limited to the above-mentioned manufacturing method.

With regard to the substrate, the color filter itself may be a substrate, or may be a portion where the color filter is located in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES), polycarbonate (PC), or the like.

Specifically, the black matrix layer and the columnar spacer may be a layer containing the colored photosensitive resin composition of the present invention, and may be a coating of the colored photosensitive resin composition, exposure, development, and thermal curing with a predetermined pattern. And formed layers. The manufacturing method of the color filter including the said pattern layer, the black matrix layer, the columnar spacer, or the black matrix layer integrally forming the columnar spacer can be formed by the method conventionally well-known in the art.

<Image display device>

In addition, another aspect of the present invention relates to an image display device including the color filter described above.

The color filter of the present invention can be applied not only to general liquid crystal display devices, but also to various image display devices such as electroluminescence display devices, plasma display devices, and field emission display devices.

Since the image display device of the present invention contains a coloring agent containing 5 to 70% by weight of a blue pigment and 30 to 95% by weight of a brown pigment, the image display device has excellent near-infrared transmittance, and thus has the advantage of excellent optical density. The rate is excellent, so it has the advantage of high reliability.

Hereinafter, in order to specifically explain this specification, examples will be described in detail. However, the embodiments described in this specification can be modified into various other forms, and the scope of this specification is not limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the specification to those skilled in the art. In addition, "%" and "part" which show content below are a weight basis unless there is particular notice.

Synthesis example: alkali soluble resin

Prepare a flask with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. Add 3,4-epoxytricyclodecane-8-yl (meth) acrylate and 3,4-epoxytricyclodecane-9-yl (meth) acrylate in a molar ratio of 50:50 40 parts by weight of the mixture, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of third butyl peroxy-2-ethylhexanoate, propylene glycol monomethyl ether 40 parts by weight of acetate (PGMEA) was mixed while stirring to prepare a mixture for a monomer dropping funnel. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added and mixed while stirring to prepare a mixture for a chain transfer agent dropping funnel. Then, 395 parts by weight of PGMEA was added to the flask, and the atmosphere in the flask was replaced with nitrogen from air. Then, the temperature of the flask was raised to 90 ° C. while stirring the mixture. Then, the monomer and the chain transfer agent were dripped from the dropping funnel. Dropwise addition was performed for 2 hours while maintaining 90 ° C. After 1 hour, the temperature was raised to 110 ° C and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH / g.

The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the alkali-soluble resin were measured using a GPC method under the following conditions.

An HLC-8120GPC (manufactured by Tosoh Co.) was used. The TSK-GELG4000HXL and TSK-GELG2000HXL column were used in series to connect the column temperature to 40 ° C. Tetrahydrofuran was used as a mobile phase solvent, and the measurement was performed while flowing at a flow rate of 1.00 ml / minute. The concentration of the measurement sample was 0.6% by weight, and the injection amount was 50 microliters, which was analyzed using an RI detector. The TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, and A-500 (manufactured by Tosoh Co.) were used as standard calibration materials, and the obtained alkali was measured under the above conditions. The weight average molecular weight and number average molecular weight of the soluble resin.

The polystyrene equivalent weight average molecular weight measured by GPC was 17,000, and the molecular weight distribution (Mw / Mn) was 2.3.

Production of colored photosensitive resin composition

The coloring photosensitive resin composition concerning an Example and a comparative example was manufactured with the composition shown in Table 1 mentioned below.

Colored substrate (glass substrate) manufacturing example

A glass substrate (Corning) of 5 cm x 5 cm was washed with a neutral detergent and water, and then dried. Then, the colored photosensitive resin compositions produced in Examples and Comparative Examples were each spin-coated on a glass substrate so that the final film thickness became 3.0 micrometers, pre-baked at 120 ° C, dried for 2 minutes, and the solvent was removed.

Then, exposure was performed at an exposure amount of 100 millijoules / cm ² (mJ / cm ² ) to form a pattern, and a non-exposed portion was removed using an alkaline aqueous solution. Then, it baked at 250 degreeC for 30 minutes, and produced the colored substrate.

Determination of residual film rate

The colored substrates manufactured in the examples and comparative examples were further subjected to a 2 hour post-baking process, and then the difference between the before and after 2 hours was compared using a film thickness measuring machine (Dektak 6M (Veeco)). It is shown in Table 2 below. The judgment criteria are as follows.

◎ (Excellent): The residual film rate is above 90%

○ (Good): The residual film rate is 80% or more and less than 90%

△ (Bad): Residual film rate is less than 80%

Measurement of near-infrared (Near-IR) transmission characteristics

The UV-2550 equipment (Shimadzu) was used to measure the transmission characteristics of near 900 nm wavelength near-infrared (Near-IR) on the colored substrates manufactured in the examples and comparative examples. The results are shown in Table 2 below. The near-infrared (Near-IR) measurement wavelength range is 900 nanometers. At this time, the transmittance must be 20% or more.

◎ (Excellent): Near-infrared transmittance is above 25%

○ (Good): Near-infrared transmittance is 20% or more and less than 25%

△ (Bad): Near-infrared transmittance is less than 20%

Optical density (O.D.) determination

The optical density of the colored substrates produced in the examples and comparative examples was measured using X-rite 361T (X-rite), and the optical density was evaluated in accordance with the following standards and shown in Table 2 below. The optical density in the present invention is based on 1.2 / micron.

◎ (Excellent): Optical density is 1.2 / micron or more

○ (Good): The optical density is 1.16 / micron or more and less than 1.20 / micron

△ (Bad): Optical density is less than 1.16 / micron

As can be seen from Table 2 above, the colored substrate produced using the colored photosensitive resin composition of the present invention has excellent near-infrared transmission characteristics and optical density, and the colored substrate produced according to the comparative example has near-infrared transmission characteristics and optical density. Neither is excellent.

In addition, it can be seen that the change rate of the film thickness of the colored substrate produced by the colored photosensitive resin composition of Examples 1 to 5 using the oxime-based compound as a photopolymerization initiator is remarkably small (high residual film rate). .

Claims (12)

    A coloring photosensitive resin composition, which is a coloring photosensitive resin composition containing a colorant. The colorant contains 5 to 70% by weight of a blue pigment and 30 to 95% by weight of a brown pigment based on the total weight of the colorant. %.         The colored photosensitive resin composition according to claim 1, wherein the blue pigment comprises one or more blue pigments selected from the group consisting of: CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 16, CI Pigment Blue 21, CI Pigment Blue 28, CI Pigment Blue 60, CI Pigment Blue 64, and CI Pigment Blue 76.         The colored photosensitive resin composition according to claim 1, wherein the brown pigment comprises one or more brown pigments selected from the group consisting of CI Pigment Brown 26, CI Pigment Brown 28, CI Pigment Brown 83, and CI Pigment Brown 93.         The colored photosensitive resin composition according to claim 1, wherein the colorant further comprises a purple pigment.         The colored photosensitive resin composition according to claim 4, wherein the purple pigment comprises one or more purple pigments selected from the group consisting of: CI Pigment Violet 14, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 33, CI Pigment Violet 36, CI Pigment Violet 37, and CI Pigment Violet 38.         The colored photosensitive resin composition according to claim 1, wherein the colorant is contained in an amount of 3 to 50% by weight based on the entire weight of the colored photosensitive resin composition.         The colored photosensitive resin composition according to claim 1, further comprising one or more selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and an additive.         The colored photosensitive resin composition according to claim 7, wherein the photopolymerization initiator includes an oxime-based compound.         A color filter comprising the cured product of the colored photosensitive resin composition according to any one of claims 1 to 8.         The color filter according to claim 9, wherein the color filter includes a pattern layer, a black matrix layer, and a columnar spacer, and one or more of the black matrix layer and the columnar spacer are A cured product of the colored photosensitive resin composition.         The color filter according to claim 10, wherein the black matrix layer and the columnar spacer are integrally formed.         An image display device includes the color filter according to claim 9.