JP6763990B2 - Colored photosensitive resin composition, color filter and image display device containing the same - Google Patents

Description

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

As a method of forming a color filter using the colored photosensitive resin composition, a coating film of the colored photosensitive resin composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern is formed in advance, and a predetermined pattern is formed. A method is mainly used in which pixels of each color are obtained by irradiating light through a photomask having a photomask (hereinafter referred to as exposure), developing the mixture to dissolve and remove an unexposed portion, and then post-baking. There is.

Recently, in the technical field of color filters, the goal is to reduce the exposure amount and shorten the tact time, and in order to meet the recent demand for high color purification of image display devices. The content (ratio) of the colorant in the colored photosensitive resin composition tends to increase, and therefore, the content of components other than the colorant decreases, and the adhesion decreases during the production of the color filter. Problems such as the generation of residues can occur.

In connection with this, Patent Document 1 includes an alkali-soluble resin, an acrylic photopolymerizable monomer, a photopolymerization initiator, a pigment and a solvent, and the alkali-soluble resin is a) represented by a specific chemical formula 1 An ethylenically unsaturated monomer containing more than one kind of double bond; b) an ethylenically unsaturated monomer having one or more kinds of carboxyl groups; and c) an ethylenically unsaturated monomer copolymerizable with the monomer of b) above. A photosensitive resin composition for a color filter, which is characterized by being a copolymer of the above, has no residue, has excellent adhesion, and can produce a high-resolution color filter composed of ultrafine pixels, and a color using the same. Although the filter is described, when a color filter is manufactured using such a composition, the shape of the pattern is formed in the form of an inverse taper before the post-heat treatment step (post-baking), and a process error occurs. There is a problem that occurs.

Korean Patent Registration No. 10-0875269

The present invention is for solving the above-mentioned problems, and an object of the present invention is to be able to form a pattern form after a post-baking process belonging to a high heat treatment in a color filter manufacturing process in a forward taper form. Therefore, it is an object of the present invention to provide a colored photosensitive resin composition which does not cause a process problem, a color filter containing the same, and an image display device.

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

Further, the color filter of the present invention is characterized by containing a cured product of the above-mentioned colored photosensitive resin composition.

Further, the image display device of the present invention is characterized by including the above-mentioned color filter.

The colored photosensitive resin composition of the present invention has an advantage that problems in the manufacturing process do not occur by enabling the pattern form to be realized in the form of a forward taper after the post-baking step in the color filter manufacturing step.

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

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

FIG. 1 is a drawing showing an example of a manufacturing process of a color filter. FIG. 2 is a drawing showing an example of a manufacturing process of a color filter. FIG. 3 is a drawing showing an example of a manufacturing process of a color filter.

When any member is said to be "above" another member in the present invention, this is not only when the arbitrary member is in contact with the other member, but also between the two members. Including the case where is present.

When any component in the present invention is said to "contain" a component, this does not exclude other components, but may further include other components, unless otherwise stated. Means.

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

<Colored photosensitive resin composition>
The uniform colored photosensitive resin composition of the present invention contains a non-reactive alkali-soluble resin and a photopolymerization initiator (A), and the photopolymerization initiator (A) has two oxime groups in one molecule. By containing the photopolymerization initiator (a1) containing the above, it is possible to realize the pattern form in the form of a forward taper after the post-baking step in the color filter step. There is an advantage that a problem in the process does not occur, and there is an advantage that it is possible to prevent the formation of holes in the formed pattern.

Non-reactive alkali-soluble resin The colored photosensitive resin composition according to the uniform of the present invention embodies the shape of the color pattern formed during the production of the color filter in the shape of a forward taper by containing the non-reactive alkali-soluble resin. There is an advantage that it is possible to do.

According to one embodiment of the present invention, the glass transition temperature of the non-reactive alkali-soluble resin may be 0 ° C. or lower, and the weight average molecular weight may be 3,000 to 12,000. At this time, the weight average molecular weight means a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC; tetrahydrofuran is referred to as an elution solvent). The weight average molecular weight may be preferably 6,000 to 10,000, but when the weight average molecular weight is within the range presented in the present invention, the hardness of the pattern is improved and the residual film ratio (film) is improved. It has the advantages of improving the remaining ratio) and improving the solubility and resolution of the unexposed portion of the developer.

Further, according to one embodiment of the present invention, the non-reactive alkali-soluble resin may specifically contain no epoxy group or unsaturated double bond in the molecule.

According to one embodiment of the present invention, the non-reactive alkali-soluble resin having a glass transition temperature of 0 ° C. or lower contains 10 to 50 weights of a repeating unit derived from a compound having a glass transition temperature of 0 ° C. or lower as a homopolymer. It can be contained in%, preferably 15 to 40% by weight, and the compound specifically contains ethyl acrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, n-acrylate. It may be, but is not limited to, one or more selected from the group consisting of hexyl and lauryl (meth) acrylate.

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, unsaturated tricarboxylic acids, and other unsaturated polycarboxylic acids having one or more carboxyl groups in the molecule. Examples include carboxylic acid. Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like. The unsaturated polyvalent carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic acid anhydride, and citraconic acid anhydride. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl), phthalate. Examples thereof include acid mono (2-acryloyloxyethyl) and phthalate mono (2-methacryloyloxyethyl). Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxypolymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. The carboxyl group-containing monomer can be used alone or in combination of two or more.

Examples of other monomers copolymerizable with the carboxyl group-containing monomer include ethylenically unsaturated monomers containing a double bond, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, and p. -Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl Aromatic vinyl compounds such as ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and inden; 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-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-Hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 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-phenoxyethyl methacrylate, methoxydiethylene methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadiethyl methacrylate, 2-hydroxy-3-phenoxy Butyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol Unsaturated carboxylic acid esters such as nomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2 -Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate; glycidyl Unsaturated carboxylic acid glycidyl esters such as acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether. Ethers; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; acrylamide, methacrylicamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylicamide Unsaturated amides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene and the like; polystyrene, polymethylacrylate, polymethyl Examples thereof include methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and giant monomers having a monoacryloyl group or a monomethacryloyl group at the end of the polymer molecular chain of polysiloxane. These monomers can be used alone or in admixture of two or more.

Specifically, the non-reactive alkali-soluble resin is (meth) acrylate / methyl (meth) acrylate / 2-ethylhexyl (meth) acrylate copolymer, (meth) acrylate / benzyl (meth) acrylate / ( 2-Ethylhexyl acrylate copolymer, (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / 2-ethylhexyl (meth) acrylate copolymer, (meth) acrylate / Benzyl (meth) acrylate / N-phenylmaleimide / (meth) acrylate 2-ethylhexyl copolymer, (meth) acrylate / (meth) acrylate 2-ethylhexyl / styrene / benzyl (meth) acrylate copolymer, ( Meta) Acrylic acid / Mono succinate (2-acryloyloxyethyl) / Styrene / 2-ethylhexyl (meth) Acrylate copolymer, (meth) Acrylate / benzyl (meth) acrylate / 2-ethylhexyl (meth) acrylate / Gglycerol mono (meth) acrylate copolymer and the like can be mentioned, but the present invention 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 developing solution is improved, the unexposed portion is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed portion remains during development. There is an advantage that the residual film ratio can be improved. At this time, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and is usually titrated using an aqueous potassium hydroxide solution. Demanded by.

According to one embodiment of the present invention, the non-reactive alkali-soluble resin can be contained 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 resin, which is preferable. It may be included in 20-70 parts by weight. When the content of the alkali-soluble resin is within the above range, there is an advantage that a color pattern can be formed and the resolution and the residual film ratio can be improved.

Photopolymerization initiator (A)
The uniform colored photosensitive resin composition of the present invention contains a photopolymerization initiator (a1) containing two oxime groups in one molecule, so that the pattern morphology is formed after the post-baking step during the production of the color filter. It has the advantage of being embodied in the form of a forward taper.

Further, according to one embodiment of the present invention, the molecular weight of the photopolymerization initiator (a1) may be 400 to 750. When the above molecular weight is satisfied, there is an advantage that the realization of the forward taper can be facilitated.

Specifically, the photopolymerization initiator (a1) may contain one or more selected from the group consisting of compounds represented by the following chemical formulas 1 to 7.

[Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

[Chemical formula 6]

[Chemical formula 7]

The above-mentioned photopolymerization initiator (a1) of the present invention can be synthesized and used by an ordinary engineer having knowledge of organic chemistry by an ordinary method, or a commercially available product can be purchased and used.

According to one embodiment of the present invention, the colored photosensitive resin composition of the present invention can further contain a photopolymerization initiator (a2) other than the above-mentioned photopolymerization initiator (a1).

The photopolymerization initiator (a2) can be used without any special limitation as long as it can polymerize a photopolymerizable compound described later. For example, acetophenone-based, benzoin-based, benzophenone-based, and thioxanthone-based. , Triazine type, oxime type, onium salt type, nitrobenzyltosylate type, benzointosilate type and the like. Examples of the acetphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like. Benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-[ There are 4- (1-methylvinyl) phenyl] propan-1-one oligomers and the like, with 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one being more preferred. In addition, a plurality of acetophenone compounds and other photopolymerization initiators can be used in combination. Examples of the photopolymerization initiator other than the acetophenone-based compound include an active radical generator, a sensitizer, and an acid generator that generate active radicals by irradiating with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds and the like. Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3', 4,4'-tetra (t-butylperoxycarbonyl). ) Benzophenone, 2,4,6-trimethylbenzophenone and the like. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. Examples of triazine-based compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -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- (fran-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 ( Examples thereof include trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine. Examples of oxime compounds include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (4-methylsulfanyl-phenyl) -butane-1,2-. Butane-2-oxime-O-acetate, 1- (4-methylsulfanyl-phenyl) -butane-1-one oxime-O-acetate, hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-acetate , Hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate and the like. Examples of the sensitizer include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-bi. Examples thereof include imidazole, 10-butyl-2-chloroacrydone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglycoxylate, and titanosen compounds. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, and 4-acetoxyphenylmethylbenzylsulfonium hexafluoro. Onium salts such as antimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylates, benzointosylates and the like can be mentioned. Be done. In addition, some of the compounds generate active radicals and acids at the same time. For example, the triazine-based photopolymerization initiator can be used as an acid generator.

The content of the entire photopolymerization initiator (A) described above can be contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total solid content of the colored photosensitive resin composition containing the same, preferably 0. It may be included in 5 to 20 parts by weight. When the content of the photopolymerization initiator (A) is within the above range, the sensitivity is improved and the exposure time to light is shortened, so that the productivity can be improved and the high resolution is maintained. There is an advantage that it can be done.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation aid, if necessary. The photopolymerization initiator may be used in combination with the above-mentioned photopolymerization initiator (A), and is used to promote the polymerization of the photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator (A). can do. Examples of the photopolymerization initiation aid include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds. Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. , 4-Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethyl) Examples thereof include methylamino) benzophenone, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene and the like. .. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like. The above-mentioned photopolymerization initiator can be used alone or in combination of two or more. A commercially available product can be used as the photopolymerization initiation aid, and examples of the commercially available photopolymerization initiator include EAB-F (Hodogaya Chemical Industry Co., Ltd. product). Preferred combinations of the photopolymerization initiator and the photopolymerization initiator for the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone and 2-methyl-2-morpholino-1. -(4-Methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-phenylpropane-1-one / 4,4'-bis (diethylamino) benzophenone, 2-Hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketone / 4,4' -Bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4'-bis (diethylamino) benzophenone, 2-benzyl Examples thereof include a combination of -2-dimethylamino-1- (4-morpholinophenyl) butane-1-one / 4,4'-bis (diethylamino) benzophenone, and more preferably 2-methyl-2-morpholino-1-. Examples include a combination of (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone. When both the photopolymerization initiator and the photopolymerization initiator are used as described above, the photopolymerization initiator is preferably used in an amount of 10 mol or less per mol of the photopolymerization initiator, and 0.01 to 5 It is more preferable to use it in moles.

The colored photosensitive resin composition according to one embodiment of the present invention may further contain one or more selected from the group consisting of colorants, photopolymerizable compounds, solvents and additives.

Colorant The colorant has a configuration that can be applied in various ways depending on the use of the color filter, and the type thereof is not particularly limited in the present invention.

The colorant may be any one of pigments, dyes and natural pigments, and the pigments are compounds classified as Pigments by the Color Index (The Society of Dyers and Colorists). Can be used. As the colorant of the present invention, an organic pigment is preferable from the viewpoint of excellent heat resistance and color development.

Specific examples of preferable pigments that can be used in the present invention include
C. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment Yellow 53, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 173, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 214 and other yellow pigments;
C. I. Pigment Orange 13, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 42, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 65, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73 and other orange pigments;
C. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 105, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I. Pigment Red 176, C.I. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 209, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 224, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I. I. Red pigments such as Pigment Red 265;
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Blue pigments such as Pigment Blue 60;
C. I. Pigment Violet 1, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Violet color pigments such as Pigment Violet 38;
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Green pigments such as Pigment Green 58;
C. I. Pigment Brown 23, C.I. I. Pigment brown 25 and other brown pigments;
C. I. Pigment Black 1, C.I. I. Examples thereof include black pigments such as Pigment Black 7.

Among these, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Red 177, C.I. I. Pigment Red 209, C.I. I. Pigment Red 254, C.I. I. Pigment Violet 23, C.I. I. Pigment Blue 15: 6 and C.I. I. It preferably contains one or more pigments selected from Pigment Green 36.

The organic pigment and the inorganic pigment may be used alone or in combination of two or more. For example, in forming the red pixel, C.I. I. Pigment Red 254 and C.I. I. In containing Pigment Yellow 139 and forming green pixels, C.I. I. Pigment Green 58, C.I. I. Pigment Yellow 150 or C.I. I. In containing Pigment Yellow 138 and forming blue pixels, C.I. I. The inclusion of Pigment Blue 15: 6 is preferable, but not limited to, in order to improve the color reproduction.

As long as the dye of the present invention has solubility in an organic solvent, one or more kinds can be used without limitation. It is preferable to use a dye that has solubility in an organic solvent and can secure reliability such as solubility in an alkaline developer, heat resistance, and solvent resistance. As the dye, an acid dye having an acidic group such as sulfonic acid or carboxylic acid, a salt of an acid dye and a nitrogen-containing compound, a sulfonamide of an acid dye, or a derivative thereof can be used. In addition, azo-based, xanthene-based, and phthalocyanine-based acid dyes and derivatives thereof can also be selected. Examples of the dye include compounds classified as dyes in the Color Index (The Society of Dyers and Colorists Publishing) and known dyes described in dyeing notes (Color Dyeing Co., Ltd.).

Specific examples of the dye include C.I. 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. Examples thereof include green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35.

In addition, C.I. I. As an acid dye
C. I. 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, Yellow dyes such as 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. 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, Red dyes such as 382, 383, 394, 401, 421,417, 418, 422,426;
C. I. Acid oranges 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173 and other orange dyes;
C. I. 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;
C. I. Violet color dyes such as Acid Violet 6B, 7, 9, 17, 19;
C. I. Examples thereof include green dyes such as acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109.

In addition, C.I. I. As a direct dye
C. I. 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, Yellow dyes such as 136, 138, 141;
C. I. 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, Red dyes such as 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 and other orange dyes;
C. I. 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, Blue dyes such as 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Violet color dyes such as Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Examples thereof include green dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82.

In addition, C.I. I. As a modern dye
C. I. Yellow dyes such as Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dye;
C. I. Modern Blue 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43 , 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like;
C. I. Violet color dyes such as Modant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Examples thereof include green dyes such as Modant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

The colorant is preferably contained 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 containing the same. When the content of the colorant is within the above range, the color density when produced in the color filter is sufficient, and a pattern having sufficient mechanical strength can be formed.

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

Of the pigments, organic pigments are, if necessary, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, graft treatment on the surface of the pigment with a polymerizable compound or the like, and a sulfate atomization method (refinement). ), Etc., cleaning treatment with an organic solvent or water to remove impurities, or removal treatment of ionic impurities by an ion exchange method or the like. The colorant preferably has a uniform particle size. When the colorant is a pigment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by containing the pigment dispersant and performing the dispersion treatment.

The pigment is preferably used in the form of a pigment dispersion having a uniformly dispersed particle size. An example of a method for uniformly dispersing the particle size of a pigment is a method of containing a pigment dispersant and performing a dispersion treatment. According to this method, a pigment in a state where the pigment is uniformly dispersed in a solution. A dispersion can be obtained.

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

The pigment dispersant is added for deagglomeration and maintenance of stability of the pigment, and those generally used in the art can be used without limitation. It is preferable to contain an acrylate-based dispersant (hereinafter referred to as an acrylic dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate). At this time, it is preferable to apply the acrylic dispersant produced by the living control method as disclosed in Japanese Patent Publication No. 2004-00143131, but the acrylate produced by the living control method. Commercially available products of the system dispersant include, but are not limited to, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, etc., but they may be used alone or individually. Two or more types can be used in combination.

As the dispersant, other resin type pigment dispersants may be used in addition to the acrylic dispersant described above. Examples of the other resin type pigment dispersant include known resin type pigment dispersants, particularly polyurethane, polycarboxylic acid ester represented by polyacrylate, unsaturated polyamide, polycarboxylic acid, and polycarboxylic acid. (Partial) amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and modified products thereof, or Oily dispersants such as amides or salts thereof formed by the reaction of polyesters with free carboxyl groups with poly (lower alkyleneimines); (meth) acrylic acid-styrene copolymers, (meth) acrylic acids. -(Meta) acrylate ester copolymer, styrene-maleic acid copolymer, water-soluble resin or water-soluble polymer compound such as polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylate; addition product of ethylene oxide / propylene oxide and phosphate ester, etc. Can be mentioned. As commercially available products of the above-mentioned resin-type dispersants, as cationic resin dispersants, for example, trade names of BYK Chemi, Inc .: 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's trade 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; Product Names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Product Names of Kawaken Fine Chemicals: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Product Names of Ajinomoto Co., Inc. (AJISPUR) PB-821, Ajispar PB-822, Ajispar PB-823; Product names of Kyoeisha Chemical Co., Ltd .: Floren DOPA-17HF, Floren DOPA-15BHF, Floren DOPA-33, Floren DOPA-44 and the like. .. In addition to the acrylic dispersant described above, other resin type pigment dispersants can be used alone or in combination of two or more, and can also be used in combination with the acrylic dispersant.

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

Photopolymerizable 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 the photopolymerization initiator by irradiation with light, and depends on the number of functional groups. Examples thereof include monofunctional, bifunctional, and trifunctional or higher polymerizable compounds.

Specific examples of the monofunctional polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like.

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. Bisphenol A bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, butylene glycol dimethacrylate, hexanediol di (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, ethoxylate neopentyl glycol diacrylate, propoxylate neopentyl glycol diacrylate and the like.

Specific examples of the trifunctional or higher polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, and propoxylate trimethylolpropane tri (meth) acrylate. ) Trifunctional polymerizable compounds such as acrylate, glyceryl propoxylate triacrylate, isocyanurate triacrylate; tetrafunctional polymerizable compounds such as pentaerythritol tetra (meth) acrylate and dimethylolpropane tetra (methyl) acrylate; dipentaerythritol penta ( Examples thereof include pentafunctional or higher functional polymerizable compounds such as meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Of these, the photopolymerizable compounds can be used alone or in admixture of two or more, and specifically, bifunctional or higher polyfunctional polymerizable compounds can be preferably used, particularly. A polyfunctional polymerizable compound having five or more functionalities can be preferably used, but the present invention is not limited thereto.

The photopolymerizable compound may be contained 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 containing the compound. When the photopolymerizable compound is included in the above range, there is an advantage that the strength and smoothness of the pixel portion can be improved.

Solvents The solvents of the present invention can be used without particular limitation as long as they are effective in dispersing or dissolving other constituents contained together, for example, ethers, aromatic hydrocarbons, etc. Ketones, alcohols, esters, amides and the like can be preferably 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, diethylene glycol monomethyl ether, and 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 Examples thereof include cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, anisole, phenetol and methyl anisole.

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

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

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

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 esters, methyl lactate, and lactic acid. Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2-methyl Ethyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Examples thereof include methyl, ethyl 2-oxobutate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and γ-butyrolactone.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide and the like.

Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.

The above-mentioned solvents can be used alone or in combination of two or more, and among them, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether can be preferably used. The content of the solvent described above may be contained in an amount of 10 to 90 parts by weight based on 100 parts by weight of the entire colored photosensitive resin composition containing the solvent. When the content of the solvent is within the above range, the flatness is good when the colored photosensitive resin composition is applied, and when the color filter is formed, the color density is sufficient, so that the display characteristics can be improved. There are advantages.

Additives In addition to the above-mentioned components, the colored photosensitive resin composition is added with an antifoaming agent, a surfactant, a thermal cross-linking agent, an adhesive strength enhancer, an antioxidant, etc., if necessary, in order to improve the performance. Additional agents can be included.

The surfactant is a component capable of improving the adhesion between the substrate and the colored photosensitive resin composition, for example, a fluorine-containing surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant and silicone. Various surfactants such as surfactants can be used. These can be used alone or in combination of two or more.

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 name, DIC). Corporation products), FLUORAD FC430, FC431 and FC171 (trade name, Sumitomo 3M Limited product), SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383 , S393 and KH-40 (trade name, Asahi Glass Co., Ltd. product), SOLSPERSE 20000 (trade name, Fluoro Japan Limited product) and the like.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates or propoxylates thereof (eg, glycerol propoxylates or glycerin ethoxylates); PLURONIC L10, L31, L61, L62, 10R5. , 17R2 and 25R2, and polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, polyoxyethylene oleyl ethers, polyoxyethylene octyls such as TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, BASF product). Examples thereof include phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.

Specific examples of the cationic surfactant include phthalocyanine-modified compounds such as EFKA-745 (trade name, Morishita & Co., Ltd. product) and KP341 (trade name, Shin-Etsu Chemical Co., Ltd. product). Organosiloxane polymer such as POLYFLOW No. 75, No. 90, No. Examples thereof include (meth) acrylic acid-based (co) polymers such as 95 (trade name, Kyoeisha Chemical Co., Ltd. product), W001 (trade name, Yusho Co., Ltd. product) and the like.

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

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

The heat-crosslinking agent is a component capable of smoothly performing a cross-linking reaction using UV irradiation and heat treatment when forming a coating film with a colored photosensitive resin composition, and can improve heat resistance. For example, polyacrylate resin, epoxy resin, phenol resin, melamine resin, organic acid, amine compound, anhydrous compound and the like can be mentioned.

The adhesive strength enhancer can improve the adhesion to an inorganic substance that can be a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum, and is a base material. There is an advantage that the ability to adjust the taper angle with and can be improved. For example, a silane coupling agent or a thiol-based compound can be mentioned, and a silane coupling agent can 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-glycidoxy. Propylalkyldialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrialkoxysilane, vinyltrialkoxysilane and the like, preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloxypropyltrialkoxysilane, more preferably γ-glycidoxypropyltrialkoxysilane. Silane can be mentioned. These can be used alone or in combination of two or more.

Examples of the antioxidants are generally 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, 2-sec-butylphenol, 2,6-di. -Se-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-amyl Phenol, 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) Examples thereof include benzene and tetrakis [methylene-3- (3,5'-di-t-butyl-4'-hydroxyphenylpropionate)] methane, and an antioxidant represented by the following chemical formula 8 is preferably used. These can be used alone or in combination of two or more.

[Chemical formula 8]

(In the above chemical formula 8, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are independently linear or cyclic alkyl groups or hydrogens having 1 to 10 carbon atoms.)

The method for producing a colored photosensitive resin composition of the present invention can be applied without limitation to a method usually used in the industry, and for example, it can be produced by the following method. The colorant is mixed with a solvent in advance and dispersed using a bead mill or the like until the average particle size of the coloring material becomes about 0.2 μm or less. At this time, a pigment dispersant can be used if necessary, and a part or all of the alkali-soluble resin may be blended. The residue of the alkali-soluble resin, photopolymerizable compounds and photopolymerization initiators, additives, other components used as needed, and added as needed to the obtained dispersion (hereinafter sometimes referred to as mil-based). The desired colored photosensitive resin composition can be obtained by further adding and mixing the above-mentioned solvent to a predetermined concentration.

<Color filter>
The color filter according to another aspect of the present invention contains the cured product of the above-mentioned colored photosensitive resin composition, so that the shape of the pattern is manufactured in the form of a forward taper after the post-baking step during the manufacturing process. There is an advantage that it is possible to prevent a problem from occurring inside, and it is possible to prevent a hole from being generated in the formed pattern.

The color filter of the present invention can be manufactured by applying a manufacturing method usually used in the industry without any special limitation. An example thereof will be described below with reference to FIGS. 1 to 3. is there.

In order to produce a color filter using the colored photosensitive resin composition of the present invention, a colored pattern must be formed, and for this purpose, the colored photosensitive resin composition can be patterned. Specifically, referring to FIG. 1, a color layer 11 made of the colored photosensitive resin composition of the present invention is formed on the upper part of the substrate 10. At this time, the type of the substrate 10 is not particularly limited, and the color filter itself may be the substrate, or may be a portion where the color filter is located in a display device or the like. The substrate 10 may be a glass plate, a silicon wafer, a plastic plate such as PES (Poly Ether Sulfone) or PC (Poly Carbonate), or the like. That is, the substrate 10 may be a silicon (Si), silicon oxide (SiOx) or glass substrate, or a polymer substrate. As described above, in order to form the color layer 11 composed of the colored photosensitive resin composition on the substrate 10, for example, the colored photosensitive resin composition diluted with a solvent is spun, spin after slitting, slitting, rolling, and spraying. After coating on a substrate by a coating method such as an inkjet method, volatile components such as a solvent are volatilized. As a result, the color layer 11 made of the colored photosensitive resin composition is formed, but the color layer 11 is made of a solid component of the colored photosensitive resin composition and contains almost no volatile component. The thickness of the film surface is determined by coating conditions such as the viscosity of the composition, the concentration of solid content, the coating speed, etc., and when the composition of the present invention is used, a color layer having a thickness of 0.5 to 5 μm is used. 11 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. In order to expose, for example, the color layer 11 is irradiated with light 30 in a predetermined pattern through a photomask 20. At this time, as the light 30, usually, ultraviolet g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm) and the like are used. The light 30 passes by the pattern of the photomask 20. The photomask 20 provides a light-shielding layer on the surface of a glass plate that shields light rays in a predetermined pattern. The light 30 is shielded by a light-shielding layer. The portion of the glass plate to which the light-shielding layer is not provided is a light projecting portion through which light rays pass. The color layer 11 is exposed by such a pattern of the light projecting portion. The irradiation amount of the light 30 is appropriately selected depending on the colored photosensitive resin composition used.

The portion irradiated with the light 30 has a much smaller solubility than the portion not irradiated with the light 30, and the difference in solubility between the two is maximized. Therefore, the developing operation is performed by utilizing such a difference. Go through. For development, for example, the colored photosensitive resin composition layer after exposure is immersed in a developer. As the developing agent, an aqueous solution of an alkaline compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, tetramethylammonium hydroxide or the like is used. With reference to FIG. 3, of the color layer 11 formed on the substrate 10 by such development, the light 30 unirradiated region that is not irradiated by the light 30 is removed. On the contrary, the light 30 irradiation region irradiated by the light 30 remains to form the coloring pattern 11R. After development, the layer is usually washed with water and dried to obtain a predetermined colored pattern 11R. In addition, heat treatment can be carried out after drying. The colored pattern 11R formed by the heat treatment is cured, and its mechanical strength is improved. Since the mechanical strength of the coloring pattern 11R can be improved by the heat treatment in this way, 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>
The image display device according to another aspect of the present invention has an advantage that defects are less likely to occur because problems do not occur in the manufacturing process by including the color filter described above. Specifically, the image display device includes 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 mobile terminal such as a mobile phone, and a digital display. Examples include display devices such as camera display devices and car navigation display devices, and color display devices are particularly suitable.

The image display device can include other configurations that can be normally 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 unit including a color filter according to the present invention. The invention does not limit this.

Hereinafter, preferred examples will be presented in order to clarify the understanding of the present invention, but the following examples merely illustrate the present invention, and various changes are made within the scope of the present invention and the technical idea. And amendments are apparent to those skilled in the art, and it is not surprising that such modifications and amendments fall within the appended claims. In the following examples and comparative examples, "%" and "part" indicating the content are based on weight unless otherwise specified.

Examples and Comparative Examples The colored photosensitive resin compositions were produced by mixing with the configurations and contents as shown in Table 1 below.

[Chemical formula 9]

[Chemical formula 10]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

Production Example: Production of Color Filter After each of the colored photosensitive resin compositions produced in the above Examples and Comparative Examples is applied on a glass substrate by a spin coating method, it is placed on a heating plate and placed at 100 ° C. A thin film was formed by maintaining the temperature for 3 minutes. Next, 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 ultraviolet light source was irradiated with an illuminance of 50 mJ / cm ² using a 1 KW high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution developing solution having a pH of 10.5 for 1 minute for development. The glass plate on which the thin film was applied was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C. for 30 hours to produce a color filter. The thickness of the color filter film produced above was 2.0 μm.

Experimental example 1. Pattern taper form Of the above production examples, the taper form after the 220 ° C. heating step is measured with a scanning electron microscope (SEM), the results are judged as shown in Table 2 below, and the results are shown in Table 3 below. did.

Experimental example 2. Evaluation of Pattern Line Width (Sensitivity) The line width of the pattern formed in the above production example was measured using a scanning electron microscope (SEM). When the line width of the pattern is measured to be the line width (100 μm) or more of the photomask, it is evaluated that the sensitivity of the colored photosensitive resin composition is improved and the line width is expanded. At this time, the measured line width (μm) is shown in Table 3 below.

Referring to Table 3 above, the color filters produced by using the colored photosensitive resin compositions of Examples 1 to 4 satisfying all the conditions of the present invention do not satisfy any of the conditions of the present invention. It was more sensitive than No. 4, and it was confirmed that the tapered form of the pattern was manufactured in the forward tapered form.

Specifically, the colored photosensitive resin compositions of Comparative Examples 1 and 3 that do not use the photopolymerization initiator presented in the present invention can form a forward taper, but by confirming a line width of 100 μm or less. It can be confirmed that the sensitivity is not good, and the colored photosensitive resin compositions of Comparative Examples 2 and 4 that do not use the alkali-soluble resin presented in the present invention have a line width of 100 μm or more and have sufficient sensitivity. However, it was confirmed that there was a problem that a reverse taper was formed.

10 Substrate 11 Color layer 11R Color pattern 20 Photomask 30 Light

Claims (11)

Contains non-reactive alkali-soluble resin and photopolymerization initiator (A)
The photopolymerization initiator (A) is seen containing one of the two including a photopolymerization initiator oxime group in the molecule (a1),
A colored photosensitive resin composition characterized in that the glass transition temperature (Tg) of the non-reactive alkali-soluble resin is 0 ° C. or lower . The colored photosensitive resin composition according to claim 1, wherein the non-reactive alkali-soluble resin does not contain an epoxy group or an unsaturated double bond in the molecule. The colored photosensitive resin according to claim 1, wherein the non-reactive alkali-soluble resin contains 10 to 50% by weight of repeating units derived from a compound having a glass transition temperature of 0 ° C. or lower as a homopolymer. Resin composition. The compound is characterized by comprising one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl acrylate and lauryl (meth) acrylate. The colored photosensitive resin composition according to claim 3. The colored photosensitive resin composition according to claim 1, wherein the non-reactive alkali-soluble resin has a weight average molecular weight of 3,000 to 12,000. The coloring according to claim 1, wherein the non-reactive alkali-soluble resin is contained 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 resin. Photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (a1) has a molecular weight of 400 to 750. The colored photosensitive resin composition further comprises one or more selected from the group consisting of a colorant, a photopolymerizable compound, a photopolymerization initiator (a2) other than the photopolymerization initiator (a1), a solvent and an additive. The colored photosensitive resin composition according to claim 1, further comprising. The colored photosensitive resin composition according to claim 1, wherein the acid value of the non-reactive alkali-soluble resin is 20 to 200 mgKOH / g. A color filter comprising the colored photosensitive resin composition according to any one of claims 1 to 9. An image display device including the color filter according to claim 10.