KR102335614B1 - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

The present invention comprises a non-reactive alkali-soluble resin and a photopolymerization initiator (A), wherein the photopolymerization initiator (A) contains a photopolymerization initiator (a1) containing two oxime groups in one molecule, a color filter process Colored photosensitive resin composition that can prevent problems in the manufacturing process and prevent the occurrence of holes in the formed pattern by enabling the shape of the pattern to be implemented in the form of a taper after the middle post-bake process , to a color filter and an image display device including the same.

Description

Colored photosensitive resin composition, color filter and image display device including the same

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

A method of forming a color filter using a colored photosensitive resin composition, wherein a coating film of the colored photosensitive resin composition is formed on a substrate or a substrate on which a light-shielding layer of a desired pattern is formed in advance, and light is transmitted through a photomask having a predetermined pattern. The method of obtaining the pixel of each color by irradiation (henceforth exposure), developing, dissolving and removing an unexposed part, and post-baking after that is mainly used.

In addition, in recent years, in the technical field of color filters, the content of the colorant occupied in the colored photosensitive resin composition is aimed at shortening the tact time by reducing the exposure amount and in order to respond to the recent demand for high color purity of image display devices. (ratio) is increasing, and due to this, as the content of components other than the colorant decreases, problems such as reduced adhesion and generation of residues may occur during the manufacture of color filters.

In this regard, Korean Patent Registration No. 10-0875269 includes an alkali-soluble resin, an acrylic photopolymerizable monomer, a photoinitiator, a pigment, and a solvent, wherein the alkali-soluble resin comprises a) at least one double bond represented by a specific formula ethylenically unsaturated monomers comprising; b) an ethylenically unsaturated monomer having at least one carboxyl group; and c) for a color filter capable of producing a high-resolution color filter composed of ultra-fine pixels, which has no residue, has excellent adhesion, and is characterized in that it is a copolymer of the ethylenically unsaturated monomer copolymerizable with the monomer of b). Although a photosensitive resin composition and a color filter using the same have been described, when a color filter is manufactured using such a composition, the shape of the pattern is formed in the form of a reverse taper before the post-heat treatment process (post-bake), which causes an error in the process there is

Republic of Korea Patent Registration No. 10-0875269 (2018.12.15.)

The present invention is to solve the above problems, and the color photosensitive resin composition that does not cause problems in the process because it is possible to form the shape of the pattern after the post-baking process belonging to the high heat treatment during the color filter manufacturing process in a forward tapered shape, An object of the present invention is to provide a color filter and an image display device comprising the.

The colored photosensitive resin composition of the present invention for achieving the above object includes a non-reactive alkali-soluble resin and a photopolymerization initiator (A), wherein the photopolymerization initiator (A) is a photopolymerization initiator (a1) comprising two oxime groups in one molecule It is characterized in that it includes.

In addition, the color filter of the present invention is characterized in that it contains a cured product of the above-described colored photosensitive resin composition.

In addition, the image display apparatus of the present invention is characterized in that it includes the above-described color filter.

The colored photosensitive resin composition of the present invention has an advantage in that a problem in the manufacturing process does not occur by enabling the shape of the pattern to be implemented in the form of a forward taper after the post-baking process during the manufacturing process of the color filter.

The color filter of the present invention has the same advantages as described above.

The image display apparatus of the present invention has the same advantages as described above.

1 to 3 schematically illustrate a process of manufacturing a color filter.

In the present invention, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

In the present invention, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

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

<Colored photosensitive resin composition>

The colored photosensitive resin composition according to an embodiment of the present invention includes a non-reactive alkali-soluble resin and a photopolymerization initiator (A), wherein the photoinitiator (A) contains a photopolymerization initiator (a1) containing two oxime groups in one molecule It has the advantage that there is no problem in the manufacturing process by enabling the shape of the pattern to be implemented in the form of a taper after the post-bake process during the color filter process, and there is a hole in the formed pattern. There is an advantage to prevent this from occurring.

non-reactive Alkali-soluble resin

Since the colored photosensitive resin composition according to an embodiment of the present invention includes a non-reactive alkali-soluble resin, it is possible to implement a shape of a color pattern formed during manufacturing of a color filter in a shape of a forward taper.

According to one embodiment of the present invention, the glass transition temperature of the non-reactive alkali-soluble resin may be 0 ℃ or less, the weight average molecular weight may be 3,000 to 12,000. In this case, the weight average molecular weight means the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent). The weight average molecular weight may be preferably 6,000 to 10,000, and when the weight average molecular weight is included within the range suggested in the present invention, the hardness of the pattern is improved, the film remaining ratio is improved, and the ratio of the developer -There is an advantage that the solubility and resolution of the exposed part are improved.

In addition, according to an embodiment of the present invention, the non-reactive alkali-soluble resin may specifically not include an epoxy group or an unsaturated double bond in a molecule.

According to one embodiment of the present invention, the non-reactive alkali-soluble resin having a glass transition temperature of 0° C. or less may include 10 to 50 wt% of a repeating unit derived from a compound having a glass transition temperature of a homopolymer of 0° C. or less, and Preferably, it may be included in an amount of 15 to 40% by weight, and the compound is specifically selected from the group consisting of ethyl acrylate, n-butyl acrylate, (meth)acrylate 2-ethylhexyl, n-hexyl acrylate, and lauryl (meth)acrylate. It may be one or more selected, but is not limited thereto.

Specifically, the non-reactive alkali-soluble resin may be a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.

Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated carboxylic acids such as unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule such as unsaturated tricarboxylic acids. can be heard Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, a crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methacryloyloxyalkyl)ester thereof, for example, mono(2-acryloyloxyethyl succinate), mono(2-methacryloyloxyethyl succinate) ), mono(2-acryloyloxyethyl phthalate), mono(2-methacryloyloxyethyl) phthalate, etc. are mentioned. In addition, the unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxy polymer at both terminals, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. can Each of the carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of the other monomer copolymerizable with the carboxyl group-containing monomer include an ethylenically unsaturated monomer containing a double bond, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, and p-chlorostyrene. , o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m -Aromatic vinyl compounds, such as vinylbenzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Oxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acryl Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclo Unsaturated carboxylic acids such as pentadiethyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate Esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, etc. unsaturated carboxylic acid aminoalkyl esters; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N- Unsaturated amides, such as 2-hydroxyethyl methacrylamide; Maleimide, N-phenyl maleimide. unsaturated imides such as N-cyclohexyl maleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; polymer molecules of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane and macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of the chain. These monomers can be used individually or in mixture of 2 or more types, respectively.

The non-reactive alkali-soluble resin is specifically, (meth) acrylic acid / methyl (meth) acrylate / (meth) acrylic acid 2-ethylhexyl copolymer, (meth) acrylic acid / benzyl (meth) acrylate / (meth) acrylic acid 2 -Ethylhexyl copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid 2-ethylhexyl copolymer, (meth)acrylic acid / benzyl (meth)acrylic Rate/N-phenylmaleimide/(meth)acrylic acid 2-ethylhexyl copolymer, (meth)acrylic acid/(meth)acrylic acid 2-ethylhexyl/styrene/benzyl (meth)acrylate copolymer, (meth)acrylic acid/succinic acid Mono (2-acryloyloxyethyl) / styrene / (meth) acrylic acid 2-ethylhexyl copolymer, (meth) acrylic acid / benzyl (meth) acrylate / (meth) acrylic acid 2-ethylhexyl / glycerol mono (meth) and acrylate copolymers, but is not limited thereto.

As used herein, (meth)acrylate means acrylate and/or methacrylate.

According to one embodiment of the present invention, the acid value of the non-reactive alkali-soluble resin may be 20 to 200 mgKOH / g. When the acid value satisfies the above range, the solubility in the developer is improved, so that the non-exposed portion is easily dissolved and the sensitivity is increased. As a result, there is an advantage in that the pattern of the exposed portion remains during development to improve the remaining film rate. In this case, the acid group is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be obtained by titration using an aqueous potassium hydroxide solution.

According to an embodiment of the present invention, the non-reactive alkali-soluble resin may be included in an amount of 10 to 80 parts by weight, preferably from 20 to 70 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition including the same. have. When the content of the alkali-soluble resin is included within the above range, it is possible to form a color pattern, there is an advantage that the resolution and the remaining film rate can be improved.

light curing initiator (A)

The colored photosensitive resin composition according to an aspect of the present invention includes the photopolymerization initiator (a1) including two oxime groups in one molecule, thereby implementing the shape of the pattern after the post-bake process in the form of a forward taper when manufacturing the color filter. There is this.

In addition, according to an embodiment of the present invention, the molecular weight of the photopolymerization initiator (a1) may be 400 to 750. When the molecular weight is satisfied, there is an advantage that a forward taper can be implemented more easily.

Specifically, the photopolymerization initiator (a1) may include at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 7.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

The photopolymerization initiator (a1) of the present invention described above may be synthesized and used by a person skilled in the art with organic chemistry knowledge by a conventional method, or may be purchased and used commercially.

According to an embodiment of the present invention, the colored photosensitive resin composition of the present invention may further include a photopolymerization initiator (a2) other than the above-described photopolymerization initiator (a1).

The photopolymerization initiator (a2) may be used without particular limitation as long as it can polymerize a photopolymerizable compound to be described later, for example, acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, triazine-based, oxime-based, onium A salt system, a nitrobenzyl tosylate system, or a benzoin tosylate system is mentioned. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 -hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one oligomer and the like, and 2-methyl-2-morpholino-1-(4-methylthiophenyl ) propan-1-one is more preferable. In addition, a plurality of acetophenone-based compounds and other photoinitiators may be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based compound include active radical generators, sensitizers, and acid generators that generate active radicals by irradiating light. Examples of the active radical generator include a benzoin-based compound, a benzophenone-based compound, a thioxanthone-based compound, a triazine-based compound, or an oxime-based compound. Examples of the benzoin-based compound include benzoin, benzoinmethyl ether. , benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4 -benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. Examples of the oxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -propoxythioxanthone and the like. As the triazine-based compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methyl Toxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4- dimethoxyphenyl)ethenyl]-1,3,5-triazine; and the like. As an oxime compound, 2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione,1-(4-methylsulfanyl-phenyl)-butane-1,2 -Butane-2-oxime-O-acetate, 1-(4-methylsulfanyl-phenyl)-butan-1-one oxime-O-acetate, hydroxyimino-(4-methylsulfanyl-phenyl)-ethyl acetate ester-O-acetate and hydroxyimino-(4-methylsulfanyl-phenyl)-acetic acid ethyl ester-O-benzoate. Examples of the sensitizer include 2,4,6-trimethylbenzoyl. Diphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacrylic acid Don, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo nate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned. Also, there are compounds that generate active radicals and acids at the same time among these compounds. For example, the triazine-based photopolymerization initiator may also be used as an acid generator.

The total content of the above-described photopolymerization initiator (A) may be included in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition including the same. When the content of the photopolymerization initiator (A) is included within the above range, the sensitivity is improved and the exposure time to light is shortened, thereby improving productivity and maintaining high resolution.

The coloring photosensitive resin composition of this invention may further contain a photoinitiation adjuvant as needed. The photopolymerization initiation adjuvant may be used in combination with the above-described photopolymerization initiator (A), and may be used to promote polymerization of the photopolymerizable compound whose polymerization is initiated by the photopolymerization initiator (A). As said photoinitiation adjuvant, an amine compound, an alkoxyanthracene type compound, a thioxanthone type compound, etc. are mentioned. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4 '-bis(ethylmethylamino)benzophenone etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone is preferable. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. and the like. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned. The above photopolymerization initiators may be used alone or in combination of two or more. In addition, as the photopolymerization initiation adjuvant, a commercially available product may be used, and the commercially available photopolymerization initiation adjuvant includes, for example, EAB-F (manufactured by Hodoga Yagaku Kogyo Co., Ltd.). As a combination of a photoinitiator and a photoinitiation adjuvant preferable for the coloring photosensitive resin composition of this invention, diethoxy acetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl-2- morpholino-1 -(4-methylthiophenyl)propan-1-one/4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-phenylpropan-1-one/4,4'-bis (diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one/4,4′-bis(diethylamino)benzo Phenone, 1-hydroxycyclohexylphenyl ketone/4,4'-bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one oligomer/4,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one/4,4'-bis A combination of (diethylamino)benzophenone, etc. are mentioned, More preferably, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one/4,4'-bis (diethylamino)benzophenones. As described above, when the photopolymerization initiator and the photopolymerization initiation adjuvant are used together, the photopolymerization initiation adjuvant is preferably used in an amount of 10 moles or less per 1 mole of the photopolymerization initiator, and more preferably in an amount of 0.01 to 5 moles.

The colored photosensitive resin composition according to an embodiment of the present invention may further include one or more selected from the group consisting of a colorant, a photopolymerizable compound, a solvent, and an additive.

coloring agent

The colorant is a composition that can be applied variously depending on the use of the color filter, and the type of the colorant is not particularly limited in the present invention.

The colorant may be any one of a pigment, a dye, or a natural colorant, and a compound classified as a pigment in the color index (published by The Society of Dyers and Colorists) may be used as the pigment. As the colorant of the present invention, an organic pigment may be preferable in terms of excellent heat resistance and color development.

Specific examples of preferred pigments that can be used in the present invention 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 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. red pigments such as Pigment Red 264 and C.I. 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 color 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. Black pigments, such as Pigment Black 7, etc. are mentioned.

Among them, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Violet 23, C.I. Pigment Blue 15:6 and C.I. It may be desirable to include one or more pigments selected from Pigment Green 36.

The above organic pigments and inorganic pigments may be used alone, or two or more types may be mixed and used. For example, to form a red pixel, C.I. Pigment Red 254 and C.I. For those containing Pigment Yellow 139, for forming the green pixel, C.I. Pigment Green 58, C.I. Pigment Yellow 150 or C.I. For those containing Pigment Yellow 138, C.I. Containing Pigment Blue 15:6 may each be preferable to improve color reproducibility, but is not limited thereto.

One or more of the dyes of the present invention may be used without limitation as long as they have solubility in organic solvents. Preferably, it is preferable to use a dye that has solubility in organic solvents and can secure reliability such as solubility in alkali developer, heat resistance, and solvent resistance. As the dye, an acid dye having an acid group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide compound of an acid dye, and derivatives thereof may be used. In addition, azo-based, xanthene-based, phthalocyanine Acid dyes and derivatives thereof can also be selected. The dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colorists), or a known dye described in a dyeing note (color dye).

As a specific example of the dye, C.I. As a solvent dye,

C.I. yellow dyes such as solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;

C.I. red dyes such as solvent red 8, 45, 49, 122, 125, 130;

C.I. orange dyes such as solvent orange 2, 7, 11, 15, 26, 45, 56, 62;

C.I. blue dyes such as solvent blue 35, 37, 45, 59, 67;

C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.

Also C.I. as an acid dye

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, etc. ;

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422, 426 and other red dyes;

orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324:1 blue dyes such as , 335 and 340;

Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19;

Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.

Also as a C.I. direct dye

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141 and other yellow dyes;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and other red dyes;

orange dyes such as C.I. direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 blue dye;

Violet dyes, such as C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.

Also, C.I. As modanto dye

yellow dyes such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

CI Modanto Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dyes;

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

Violet dyes such as C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

and green dyes such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

The colorant may be included in an amount of 10 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition including the colorant. When the content of the colorant is included within the above range, a pattern having sufficient color density and sufficient mechanical strength when made of a color filter may be formed.

In the present invention, the solid content of the colored photosensitive composition means the total of the components from which the solvent is removed.

Among the above pigments, organic pigments are, if necessary, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment of the surface of the pigment with a polymer compound, etc., atomization treatment by sulfuric acid refinement, etc., impurities A washing treatment with an organic solvent or water for removal, or a removal treatment with an ion exchange method for ionic impurities, etc. can be performed. The colorant preferably has a uniform particle size. When the colorant is a pigment, a pigment dispersion in a state in which the pigment is uniformly dispersed in the solution can be obtained by containing a pigment dispersant to perform dispersion treatment.

The pigment is preferably used in the form of a pigment dispersion in which the particle size is uniformly dispersed. As an example of a method for uniformly dispersing the particle size of the pigment, a method of dispersing treatment by containing a pigment dispersant can be mentioned. According to this method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, and these may be used alone or in combination of two or more.

The pigment dispersant is added for deagglomeration and stability of the pigment, and those generally used in the art may be used without limitation. It may be preferable to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant), preferably including BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant prepared by the living control method as presented in Korean Patent Application Laid-Open No. 2004-0014311. As a commercial product of the acrylate-based dispersant manufactured through the living control method, DISPER BYK -2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc. may be mentioned, but are not limited thereto, and these may be used alone or in combination of two or more.

As the dispersant, a pigment dispersant of a resin type other than the above-mentioned acrylic dispersant may be used. The pigment dispersants of other resin types include known resin type pigment dispersants, in particular polyurethane, polycarboxylic acid esters typified by polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially) Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamidephosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or free ) oily dispersants such as amides or salts thereof formed by the reaction of a polyester having a carboxyl group with poly(lower alkyleneimine); water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; modified polyacrylates; and ethylene oxide/propylene oxide adducts and phosphate esters. As a commercially available product of the above-mentioned resin type dispersant, as a cationic resin dispersant, for example, BYK (Big) Chemi Corporation's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK- 164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; BASF brand names: 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 from Lubirzol: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Trade names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Trade names of Ajinomoto Corporation: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Trade names of Kyoeisha Chemical Corporation: FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, fluorene DOPA-44, etc. are mentioned. Pigment dispersants of other resin types other than the above acrylic dispersants may be used alone or in combination of two or more, or may be used in combination with an acrylic dispersant.

When the colored photosensitive resin composition further includes a pigment dispersant, the content may be preferably 1 part by weight or less, and more preferably 0.05 parts by weight or more and 0.5 parts by weight or less, per 1 part by weight of the colorant included together. When the amount of the pigment dispersant used is within the above range, a pigment in a uniformly dispersed state can be obtained.

photopolymerization compound

The photopolymerizable compound is not particularly limited in the present invention as long as it is a compound that can be polymerized by active radicals, acids, etc. generated from a photopolymerization initiator by irradiation of light, and is monofunctional, bifunctional, trifunctional or more depending on the number of functional groups A polymeric compound etc. are mentioned.

Specific examples of the monofunctional polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N- Vinylpyrrolidone etc. are mentioned.

Specific examples of the bifunctional polymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. Acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, butylene glycol dimethacrylate, hexanedioldi(meth)acrylate, diethylene glycol di( Meth) acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxy Late neopentyl glycol diacrylate, propyl oxylate neopentyl glycol diacrylate, etc. are mentioned.

Specific examples of the trifunctional or higher polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylate trimethylolpropane tri(meth)acrylate, propyloxylate trimethylolpropane trifunctional polymerizable compounds such as tri(meth)acrylate, glycerylpropyloxylate triacrylate, and isocyanurate triarylate; tetrafunctional polymerizable compounds such as pentaerythritol tetra(meth)acrylate and dimethylolpropanetetra(methyl)acrylate; 5-functional polymerizable compounds, such as dipentaerythritol penta (meth)acrylate and dipentaerythritol hexa (meth)acrylate, etc. are mentioned.

Among them, the photopolymerizable compound may be used alone or in mixture of two or more, and specifically, a polyfunctional polymerizable compound having a bifunctional or higher function may be preferably used. may be used, but is not limited thereto.

The photopolymerizable compound may be included in an amount of 5 to 50 parts by weight, preferably 7 to 45 parts by weight, based on 100 parts by weight of the total solid content of the colored photosensitive resin composition including the same. When the photopolymerizable compound is included in the range, there is an advantage that the intensity or smoothness of the pixel portion may be improved.

solvent

The solvent of the present invention may be used without particular limitation as long as it is effective in dispersing or dissolving other components included together, for example, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides, etc. are preferred. can be used

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate , methoxybutyl acetate, methoxypentyl acetate, anisole, phenetol, or methylanisole.

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone or cyclohexanone. can

Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerin.

Examples of the esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl ester. Liquor, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate , 3-oxyethyl propionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-ethoxymethylpropionate, 3-ethoxypropionate ethyl, 2-oxypropionate methyl, 2-oxypropionate ethyl, 2-oxy Propyl propionate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxy propyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-oxy-2-methyl propionate, 2- Ethyl oxy-2-methylpropionate, 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo and methyl butanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, or γ-butyrolactone.

Examples of the amides include N,N-dimethylformamide or N,N-dimethylacetamide.

As another solvent, N-methylpyrrolidone, dimethyl sulfoxide, etc. are mentioned, for example.

The above-mentioned solvents may be used alone or in mixture of two or more, and among them, 3-ethoxy ethyl propionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether may be preferably used, and The content may be included in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total colored photosensitive resin composition including the same. When the content of the solvent is within the above range, there is an advantage that flatness is good when the colored photosensitive resin composition is applied, and the color concentration is sufficient when a color filter is formed, so that display characteristics can be improved.

additive

The colored photosensitive resin composition may further include additives such as an antifoaming agent, a surfactant, a thermal crosslinking agent, an adhesion promoter, and an antioxidant to improve performance, if necessary, in addition to the above-described components.

The surfactant is a component capable of improving the adhesion between the substrate and the colored photosensitive resin composition, for example, various surfactants such as fluorine-containing surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants. can be used These can be used individually or in mixture of 2 or more types.

Specific examples of the fluorine-containing surfactant include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade names, manufactured by DIC Corporation); FLUORAD FC430, FC431 and FC171 (trade names, products of Sumitomo 3M Limited), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 and KH- 40 (trade name, product of Asahi Glass Co., Ltd.), SOLSPERSE 20000 (trade name, product of Lubrizol Japan Limited), etc. are mentioned.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane and trimethylol ethane and their ethoxylates or propoxylates (eg, glycerol propoxylate or glycerin ethoxylate); polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, such as PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade names, manufactured by BASF); Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. are mentioned.

Specific examples of the cationic surfactant include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.), organo such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) siloxane polymers; (meth)acrylic acid-based (co)polymers such as POLYFLOW No.75, No.90, and No.95 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), W001 (trade name, manufactured by Yusho Co., Ltd.), etc. can be heard

Specific examples of the anionic surfactant include W004, W005, W017 (trade name, manufactured by Yusho Co., Ltd.) and the like.

Specific examples of silicone surfactants include TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade names, manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, 4300, 4445, 4460 and 4452 ( trade name, Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (trade name, product of Shin-Etsu Chemical Co., Ltd.), BYK307, 323 and 330 (trade name, product of BYK Chemie), etc. are mentioned.

The thermal crosslinking agent is a component that can smoothly generate a crosslinking reaction through UV irradiation and heat treatment when forming a coating film with the colored photosensitive resin composition, and can improve heat resistance. For example, a polyacrylate resin, an epoxy resin, a phenol resin, a melamine resin, an organic acid, an amine compound, an anhydride compound, etc. are mentioned.

The adhesion promoter can improve adhesion to an inorganic material that can be a substrate, for example, a silicon compound such as silicon, silicon oxide, silicon nitride, or a metal such as gold, copper, aluminum, etc., and can reduce the taper angle with the substrate. It has the advantage of improving the control ability. For example, a silane coupling agent or a thiol-based compound may be mentioned, and a silane coupling agent may be preferably used.

The type of the silane coupling agent is not particularly limited, and specific examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, and γ-glycidoxypropylalkyl. Dialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxy) Cyclohexyl) ethyltrialkoxysilane, vinyl trialkoxysilane, etc. are mentioned, Preferably it is gamma -glycidoxypropyl trialkoxysilane or gamma -methacryloxypropyl trialkoxysilane, More preferably, it is gamma -glycy It is doxypropyltrialkoxysilane. These can be used individually or in mixture of 2 or more types.

Examples of the antioxidant are generally 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-sec-butylphenol, 2,6- Di-sec-butylphenol, 2,4-di-sec-butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4-diisopropylphenol, 2-t-octylphenol, 2 ,6-di-t-octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2-t-butyl -p-cresol, 2,6-di-t-amylphenol, 2,4-di-t-amylphenol, 6-t-butyl-o-cresol, 2,6-di-t-dodecylphenol , 2,4-di-t-dodecylphenol, 2-sec-butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6-sec- Butyl-o-cresol, 2-t-octyl-p-cresol, 2-t-dodecyl-p-cresol, 2-t-butyl-6-isopropylphenol, 6-t-octyl-o- Cresol, 6-t-dodecyl-o-cresol, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), octadecyl-3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate, 4,4'-butylidenebis(6-tetra-butyl-3-methylphenol), 4,4'-thio-bis(3-methyl-6-t- butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5) -di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-ethylphenol, 2, 2'-methylenebis(4-methyl-6-t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5- tris(4-hydroxybenzyl)benzene and tetrakis[methylene-3-(3,5'-di-t-butyl-4'-hydroxyphenylpropionate)]methane, etc. are mentioned, Preferably Antioxidants represented by the following Chemical Formula 8 may be used, and one or two or more thereof may be used.

[Formula 8]

(In Formula 8,

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a linear or cyclic alkyl group having 1 to 10 carbon atoms or hydrogen).

The method for preparing the colored photosensitive resin composition of the present invention may be applied without limitation to a method commonly used in the art, but, for example, it may be prepared by the following method. The coloring agent is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle diameter of the coloring material is about 0.2 µm or less. At this time, if necessary, a pigment dispersant may be used, and some or all of the alkali-soluble resin may be blended. To the obtained dispersion (hereinafter sometimes referred to as mill base), the remainder of the alkali-soluble resin, a photopolymerizable compound and a photoinitiator, additives, other components used as needed, and, if necessary, additional solvents are added to a predetermined concentration. By adding and mixing, the target coloring photosensitive resin composition can be obtained.

<Color filter>

The color filter according to another aspect of the present invention includes the cured product of the above-described colored photosensitive resin composition, thereby preventing problems during the manufacturing process by manufacturing the shape of the pattern in the form of a forward taper after the post-baking step during the manufacturing process This can be done, and there is an advantage in that it is possible to prevent a hole from being generated in the pattern formation number pattern.

The color filter of the present invention can be manufactured by applying a manufacturing method commonly used in the art without any particular limitation, but an example will be described with reference to FIGS. 1 to 3 as follows.

In order to manufacture a color filter using the colored photosensitive resin composition of the present invention, a colored pattern must be formed. For this, the colored photosensitive resin composition may be pattern-treated. Specifically, referring to FIG. 1 , the color layer 11 made of the colored photosensitive resin composition of the present invention is formed on the substrate 10 . At this time, the type of the substrate 10 is not particularly limited, and may be a color filter itself substrate, or may be a portion on which a color filter is located in a display device or the like. The substrate 10 may be a glass plate, a silicon wafer, and a plastic plate such as Poly Ether Sulfone (PES) or Poly Carbonate (PC). That is, the substrate 10 may be a silicon (Si), silicon oxide (SiOx), a glass substrate, or a polymer substrate. In this way, in order to form the color layer 11 made of the colored photosensitive resin composition on the substrate 10, for example, the colored photosensitive resin composition diluted with a solvent is spin, slit after spin, slit, roll, spray, After coating on a substrate by a coating method such as an inkjet method, volatile components such as a solvent are volatilized. Thereby, the color layer 11 made of the colored photosensitive resin composition is formed. The color layer 11 is made of the solid components of the colored photosensitive resin composition and contains almost no volatile components. The thickness of the film surface is determined by application conditions such as the viscosity of the composition, the concentration of solids, and the application rate, and when the composition of the present invention is used, the color layer 11 having a thickness of 0.5 to 5 μm can be obtained.

Next, referring to FIG. 2 , the color layer 11 made of the colored photosensitive resin composition is exposed (exposed) to the light 30 on the substrate 10 . For exposure, for example, the color layer 11 is irradiated with light 30 in a predetermined pattern through the photomask 20 . At this time, as the light 30, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) of ultraviolet rays, etc. are usually used. Light 30 is passed through according to the pattern of photomask 20 . The photomask 20 provides a light-blocking layer that blocks light in a predetermined pattern on the surface of the glass plate. The light 30 is shielded by the light blocking layer. The portion of the glass plate where this light-shielding layer is not provided is a light-transmitting portion through which light rays pass. According to the pattern of the light transmitting part, the color layer 11 is exposed. The irradiation amount of the light 30 is appropriately selected according to the colored photosensitive resin composition used.

The portion to which the light 30 is irradiated has a much smaller solubility than the portion to which the light 30 is not irradiated, and thus the difference in solubility between the two is maximized, and thus development is performed using this difference. For development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As the developer, an aqueous solution of an alkali compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide and the like is used. Referring to FIG. 3 , an area not irradiated with the light 30 that is not irradiated by the light 30 among the color layers 11 formed on the substrate 10 by this phenomenon is removed. On the contrary, the light 30 irradiated area irradiated by the light 30 remains and constitutes the colored pattern 11R. After development, the layer is washed with plain water and dried to obtain a predetermined colored pattern 11R. In addition, you may heat-process after drying. The colored pattern 11R formed by the heat treatment is hardened, and its mechanical strength is improved. As described above, since the mechanical strength of the colored pattern 11R can be improved by heat treatment, it is preferable to use a colored photosensitive composition containing a curing agent. The heating temperature is usually 180°C or higher, preferably 200 to 250°C.

<Image display device>

Since the image display apparatus according to another aspect of the present invention includes the above-described color filter, there is no problem in the manufacturing process, so there is an advantage in that the occurrence of defects is small. The image display device is specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, a display for a digital camera and display devices such as a device and a display device for car navigation, and in particular, a color display device may be suitable.

The image display device may include other components that may be included in an image display device, such as a light emitting device such as a light source, a light guide plate, and a liquid crystal display including a color filter according to the present invention, but the present invention is not limited thereto. does not

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. , it is natural that such variations and modifications fall within the scope of the appended claims. In the following Examples and Comparative Examples, "%" and "part" indicating the content are by weight unless otherwise specified.

Example and comparative example

A colored photosensitive resin composition was prepared by mixing the composition and content as shown in Table 1 below.

Example
One Example
2 Example
3 Example
4 comparative example
One comparative example
2 comparative example
3 comparative example
4 Colorant ^{1 )} 25.2 25.2 25.2 25.2 25.2 25.2 25.2 25.2 Alkali-soluble resin 2-1 11.2 11.2 - - 11.2 - - - 2-2 - - 11.2 11.2 - - - - 2-3 - - - - - 11.2 11.2 - 2-4 - - - - - - - 11.2 Photopolymerizable compound ^{3 )} 5.1 5.1 5.1 5.1 5.1 5.1 5.1 5.1 photopolymerization initiator 4-1 1.0 - 1.0 - - 1.0 - 1.0 4-2 - 1.0 - 1.0 - - - - 4-3 - - - - 1.0 - 1.0 - Additive ^{5 )} 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 solvent ^{6 )} 57.3 57.3 57.3 57.3 57.3 57.3 57.3 57.3 1) CI Pigment Blue 15:6
2-1) Formula 9 monomer; weight ratio (a ₁ ):(b ₁ ):(c ₁ ):(d ₁ ) = 10:25:15:50; acid value = 100 KOHmg/g; The polystyrene equivalent weight average molecular weight is 9,000; solid content = 35%, solvent = propylene glycol monomethyl ether acetate; Tg (glass transition temperature) = -18 °C
2-2) Formula 10 monomer; weight ratio (a ₂ ):(b ₂ ):(c ₂ ):(d ₂ ) = 10:25:15:50; acid value = 100 KOHmg/g; The polystyrene equivalent weight average molecular weight is 9,500; solid content = 35%, solvent = propylene glycol monomethyl ether acetate; Tg (Glass Transition Temperature) = -20℃
2-3) Formula 11 monomer; weight ratio (a ₃ ):(b ₃ ):(c ₃ ):(d ₃ ) = 10:50:15:25; acid value = 100 KOHmg/g; The polystyrene equivalent weight average molecular weight is 10,200; solid content = 35%, solvent = propylene glycol monomethyl ether acetate; Tg (Glass Transition Temperature) = -25℃
2-4) a monomer of formula 12; weight ratio (a ₄ ):(b ₄ ):(c ₄ ):(d ₄ ) = 10:25:15:50; acid value = 100 KOHmg/g; The polystyrene equivalent weight average molecular weight is 9,600; solid content = 35%, solvent = propylene glycol monomethyl ether acetate; Tg (Glass Transition Temperature) = 110 °C
3) Dipentaerythritol hexaacrylate (DPHA, Japan Chemicals)
4-1) a compound of formula 3; molecular weight 440
4-2) a compound of Formula 4; molecular weight 420
4-3) a compound of formula 13; Molecular weight 445 (OXE01, BASF)
5) SH8400 (Dow Corning Toray Silicon Corporation)
6) Propylene glycol monomethyl ether acetate

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

production example : Manufacture of color filters

Each of the colored photosensitive resin compositions prepared in Examples and Comparative Examples was coated on a glass substrate by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film. Then, a test photomask having a line/space pattern of 1 µm to 50 µm was placed on the thin film, and the distance from the test photomask was set to 100 µm, and ultraviolet rays were irradiated. At this time, the UV light source was irradiated with an illuminance of 50 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a developing solution of an aqueous KOH solution having a pH of 10.5 for 1 minute. The glass plate coated with this thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220° C. for 30 hours to prepare a color filter. The film thickness of the color filter prepared above was 2.0 μm.

Experimental example 1. Pattern taper ( taper ) form

Among the preparation examples, the shape of the taper after the 220°C heating process was measured with a scanning electron microscope (SEM), and the results were determined as shown in Table 2 below, and the results are shown in Table 3 below.

○ (net taper) × (reverse taper)

Experimental example 2. Pattern line width (sensitivity) evaluation

The line width of the pattern formed in Preparation Example was measured using a scanning electron microscope (SEM). When the line width of the pattern is measured to be greater than or equal to the line width (100 μm) of the photomask, it is evaluated that the sensitivity of the colored photosensitive resin composition is improved and the line width is enlarged. At this time, the measured line width (㎛) is described in Table 3 below.

Example
One Example
2 Example
3 Example
4 comparative example
One comparative example
2 comparative example
3 comparative example
4 pattern taper shape ○ ○ ○ ○ ○ × ○ × Pattern line width (sensitivity) 106㎛ 109㎛ 105㎛ 108㎛ 93㎛ 108㎛ 95㎛ 107㎛

Referring to Table 3, the color filters manufactured using the colored photosensitive resin compositions of Examples 1 to 4 satisfying all the conditions of the present invention are more sensitive than Comparative Examples 1 to 4 which do not satisfy any of the conditions of the present invention. was excellent, and it was confirmed that the tapered shape of the pattern was manufactured in a purely tapered shape.

Specifically, the colored photosensitive resin compositions of Comparative Examples 1 and 3, which do not use the photopolymerization initiator presented in the present invention, can form a net taper, but have poor sensitivity by checking a line width of 100 μm or less. The colored photosensitive resin compositions of Comparative Examples 2 and 4 not using the alkali-soluble resin presented in the present invention had sufficient sensitivity with a line width of 100 μm or more, but it was confirmed that there was a problem in that a reverse taper was formed.

10: substrate
11: color layer
11R: color pattern
20: photo mask
30: light

Claims (12)

A non-reactive alkali-soluble resin containing a repeating unit derived from a maleimide-based monomer and a photopolymerization initiator (A),
The photoinitiator (A) is a colored photosensitive resin composition comprising a photoinitiator (a1) containing two oxime groups in one molecule. According to claim 1,
The glass transition temperature (Tg) of the non-reactive alkali-soluble resin is colored photosensitive resin composition, characterized in that less than 0 ℃. According to claim 1,
The non-reactive alkali-soluble resin is a colored photosensitive resin composition, characterized in that it does not contain an epoxy group or an unsaturated double bond in the molecule. 3. The method of claim 2,
The non-reactive alkali-soluble resin is a colored photosensitive resin composition, characterized in that it contains 10 to 50% by weight of a repeating unit derived from a compound having a glass transition temperature of 0° C. or less of a homopolymer. 5. The method of claim 4,
The compound is ethyl acrylate, n-butyl acrylate, (meth) acrylate 2-ethylhexyl, acrylic acid n-hexyl and (meth) colored photosensitive resin composition, characterized in that it comprises at least one selected from the group consisting of lauryl acrylate. According to claim 1,
The color photosensitive resin composition, characterized in that the weight average molecular weight of the non-reactive alkali-soluble resin is 3,000 to 12,000. According to claim 1,
The non-reactive alkali-soluble resin is a colored photosensitive resin composition, characterized in that it is included in an amount of 10 to 80 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition containing the same. According to claim 1,
The color photosensitive resin composition, characterized in that the molecular weight of the photoinitiator (a1) is 400 to 750. According to claim 1,
The colored photosensitive resin composition further comprises one or more selected from the group consisting of a colorant, a photopolymerizable compound, a photoinitiator (a2) other than the photoinitiator (a1), a solvent, and an additive. Colored photosensitive resin composition, characterized in that it further comprises. According to claim 1,
The non-reactive alkali-soluble resin has an acid value of 20 to 200 KOHmg/g, characterized in that the colored photosensitive resin composition. A color filter comprising the colored photosensitive resin composition of any one of claims 1 to 10. An image display device comprising the color filter of claim 11 .

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