TWI766147B - Colored photosensitive resin composition, color filter and image display device using the same - Google Patents

Abstract

[化學式2]

[化學式3]

The present invention provides a colored photosensitive resin composition, a color filter including the same, and an image display device. The colored photosensitive resin composition contains a photopolymerization initiator (A), and the photopolymerization initiator (A) includes a photopolymerization initiator (a1) having a light absorption rate of 0.1% or more at a wavelength of 365 nm, which is The compound represented by the chemical formula 1 or 2 can form the shape of the pattern into a tapered shape before the post-baking process in the color filter manufacturing process to prevent problems in the manufacturing process and prevent the formed pattern. Create a hole. In Chemical Formulas 1 and 2, R ₁ is represented by Chemical Formula 3, R ₂ is a hydrocarbon group with a molecular weight of 50 to 150, R ₃ is a substituted or unsubstituted diphenyl sulfide group, and the like. In Chemical Formula 3, R ₄ is a C1 to C8 alkylene group, a C6 to C20 aryl group, etc., and R ₅ is CN, a C1 to C8 alkyl group, a C3 to C8 ring structure, a C6 to C20 aryl group, or a C7 to C25 group Aralkyl. [Chemical formula 1]

[Chemical formula 2]

[Chemical formula 3]

Description

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

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

As a method of forming a color filter using a colored photosensitive resin composition, the following method is mainly used. The mask of the pattern is irradiated with light (hereinafter, referred to as exposure), developed to dissolve and remove the non-exposed portion, and post-baking is performed to obtain pixels of each color.

In addition, in recent years, in the technical field of color filters, in order to reduce the exposure amount, shorten the takt time, and in order to meet the recent demand for high color purity of image display devices, there is a trend to increase the number of colored photosensitive resin compositions. As the content (ratio) of the colorant in the color filter decreases, there may be problems such as decrease in adhesiveness and generation of residues when manufacturing a color filter as the content of components other than the colorant decreases.

In this regard, Korean Registered Patent No. 10-0875269 discloses a photosensitive resin composition for a color filter and a color filter using the photosensitive resin composition, wherein the photosensitive resin composition contains an alkali Soluble resin, acrylic photopolymerizable monomer, photopolymerization initiator, pigment and solvent, wherein the alkali-soluble resin is a) an ethylenically unsaturated monomer containing one or more double bonds represented by a specific chemical formula, b) having one The above carboxyl group ethylenically unsaturated monomer, and c) a copolymer of the ethylenically unsaturated monomer which can be copolymerized with the above-mentioned monomer b) can be produced without residue, excellent in adhesion, and made of ultra-fine A high-resolution color filter composed of pixels, however, when a color filter is manufactured using such a composition, the shape of the pattern is formed into a reverse slope shape before the subsequent heat treatment process (post-baking), and an error occurs in the process. The problem.

prior art literature Patent Literature

Patent Document 1: Korean Registered Patent No. 10-0875269 (2018.12.15.)

The present invention has been made to solve the above-mentioned problems, and its object is to provide a method that can form the shape of the pattern into the shape of a positive slope before performing the post-baking process, which is a high-temperature heat treatment in the color filter manufacturing process. A coloring photosensitive resin composition that does not cause a problem in a process, a color filter, and an image display device including the coloring photosensitive resin composition.

The colored photosensitive resin composition of the present invention for achieving the above object is characterized by containing a photopolymerization initiator (A), and the photopolymerization initiator (A) has a light absorption rate of 0.1 at a wavelength of 365 nm. % or more of the photopolymerization initiator (a1), the above-mentioned photopolymerization initiator (a1) is a compound represented by the following chemical formula 1 or chemical formula 2,

(In the above chemical formula 1 and chemical formula 2, R ₁ is each independently represented by the following chemical formula 3, R ₂ is a hydrocarbon group, the molecular weight is each independently 50 to 150, and R ₃ is each independently substituted or unsubstituted Phenyl thioether, substituted or unsubstituted carbazolyl, substituted or unsubstituted indyl)

[Chemical formula 3] -R ₄ -R ₅

(In the above chemical formula 3, R ₄ is a C1 to C8 alkylene group, a C6 to C20 aryl group, or a C7 to C25 aralkylene group, and R ₅ is each independently CN, C1 to C8 alkyl, C3 to C8 ring structure, C6 to C20 aryl group or C7 to C25 aralkyl group).

Moreover, the color filter of this invention contains the hardened|cured material of the said coloring photosensitive resin composition, It is characterized by the above-mentioned.

Moreover, the image display apparatus of this invention is characterized by including the above-mentioned color filter.

The colored photosensitive resin composition of the present invention has the advantages that the shape of the pattern can be formed into the shape of a positive slope before the post-baking process in the color filter manufacturing process, so that there is no problem in the manufacturing process.

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.

10: Substrate

11: Color Layer

11R: Coloring Patterns

20: Photomask

30: Light

FIGS. 1 to 3 are diagrams illustrating the manufacturing process of the color filter.

FIG. 4 is a diagram showing a method of measuring the slope length for distinguishing between the forward slope and the reverse slope.

In the present invention, when it is indicated that a certain member is "on" another member, it includes not only the case where a certain member is in contact with another member, but also the case where there are other members between the two members.

In the present invention, when it is indicated that a certain part "comprises" a certain element, unless otherwise stated, it means that other elements may be further included, rather than excluding other elements.

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

<Colored photosensitive resin composition>

The colored photosensitive resin composition of one aspect of the present invention contains a photopolymerization initiator (A), and the photopolymerization initiator (A) has a light absorptivity of 0.1% or more at a wavelength of 365 nm. The photopolymerization initiator (a1), the above-mentioned photopolymerization initiator (a1) is a compound represented by the following chemical formula 1 or chemical formula 2, so that the shape of the pattern can be changed before the post-baking process in the color filter manufacturing process. Since it is formed in the form of a tapered surface, there are advantages such as being able to prevent defects such as light leakage due to the formation of a reverse tapered surface in the final product after post-baking, and preventing the generation of holes in the formed pattern.

(In the above chemical formula 1 and chemical formula 2, R ₁ is each independently represented by the following chemical formula 3, R ₂ is a hydrocarbon group, and its molecular weight is each independently 50 to 150, and R ₃ is each independently substituted or unsubstituted diphenyl sulfide, substituted or unsubstituted carbazolyl, substituted or unsubstituted peryl)

[Chemical formula 3] -R ₄ -R ₅

(In the above chemical formula 3, R ₄ is a C1 to C8 alkylene group, a C6 to C20 aryl group, or a C7 to C25 aralkylene group, R ₅ is each independently CN, a C1 to C8 alkyl group, C3 to C8 ring structure, C6 to C20 aryl group or C7 to C25 aralkyl group).

The above-mentioned C1 to C8 alkyl groups include straight-chain or branched-chain types, for example, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, n-hexyl or n-octyl, etc.

The above-mentioned C6 to C20 aryl groups include phenyl, biphenyl, terphenyl, stilbene, naphthyl, anthracenyl, phenanthryl or pyrenyl and the like.

The above-mentioned C7 to C25 aralkyl group includes benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl or cinnamyl and the like.

Photopolymerization Initiator (A)

The colored photosensitive resin composition of one aspect of the present invention contains a photopolymerization initiator (A), and the photopolymerization initiator (A) has a light absorptivity of 0.1% or more at a wavelength of 365 nm. The photopolymerization initiator (a1), the above-mentioned photopolymerization initiator (a1) is a compound represented by the following chemical formula 1 or chemical formula 2, so that the shape of the pattern can be changed before the post-baking process in the color filter manufacturing process. Since it is formed in the form of a positive taper, it has advantages such as being able to prevent problems in the manufacturing process and preventing the formation of holes in the formed pattern.

The above-mentioned photopolymerization initiator (a1) can be synthesized and used by those of ordinary skill with knowledge of organic chemistry, or a commercially available product can be purchased and used.

The colored photosensitive resin composition of one Embodiment of this invention may further contain the photoinitiator (a2) other than the said photoinitiator (a1).

In this case, the photopolymerization initiator (a2) that can be further included is not particularly limited as long as it can polymerize the alkali-soluble resin and the above-mentioned photopolymerizable compound included together, and examples thereof include acetophenone-based and benzoin-based ones. , benzophenone series, thioxanthone series, triazine series, oxime series, onium salt series, nitrobenzyl tosylate series or benzoin tosylate series, etc. As the acetophenone-based compound of the present invention, diethoxyacetophenone, 2-methyl-2-morpholinyl-1-(4-methylphenylthio)propan-1-one, 2-Hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy yl)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one oligomers, etc., more preferably 2-methyl-2-morpholinyl-1-(4-methylphenylthio)propan-1-one. In addition, it is also possible to use a combination of various acetophenone-based compounds and other photopolymerization initiators. Examples of photopolymerization initiators other than the acetophenone-based compound include active radical generators, sensitizers, acid generators, and the like that generate active radicals by irradiation with light. As said active radical generator, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, an oxime type compound, etc. are mentioned. As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example. Examples of the benzophenone-based compound include benzophenone, methyl orthobenzoate, 4-phenylbenzophenone, 4-benzophenone-4'-methyldiphenyl Thioether, 3,3',4,4'-tetrakis(tertiary butylcarbonyl peroxide) benzophenone, 2,4,6-trimethylbenzophenone, etc. Examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichlorothioxanthone , 1-Chloro-4-propoxythioxanthone, etc. As the triazine-based compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 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-(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. Examples of the oxime-based compound include 2-(o-benzoic oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(4-methylsulfonyl -Phenyl)-butane-1,2-butane-2-oxime-O-acetate, 1-(4-methylsulfonyl-phenyl)-butane-1-one oxime-O- Acetate, Hydroxyimino-(4-Methylsulfonyl-phenyl)-ethyl acetate-O-acetate, Hydroxyimino-(4-Methylsulfonyl-phenyl)- Ethyl acetate-O-benzoate, etc. As the sensitizer, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2-bis(o-chlorophenyl)-4,4',5,5'- Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzophenone, 9,10-phenanthrenequinone, camphorquinone, phenylethyl Methyl aldol, titanocene compounds, etc. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyl Dimethylsulfonium p-toluenesulfonate, 4-acetyloxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimony salts, onium salts such as diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, and the like. In addition, among the above-mentioned compounds, there are also compounds that generate active radicals and acids at the same time. For example, the above-mentioned triazine-based photopolymerization initiator can also be used as the acid generator.

According to an embodiment of the present invention, the content of the photopolymerization initiator (a1) may be 70 to 100 parts by weight, preferably 90 parts by weight, relative to 100 parts by weight of the total photopolymerization initiator (A) containing it copies or more. When the content of the above-mentioned photopolymerization initiator (a1) satisfies the above-mentioned range, there are advantages such as being able to form a positive slope shape better.

According to one embodiment of the present invention, the content of the photopolymerization initiator (A) may be 0.1 to 30 parts by weight, preferably 0.1 to 30 parts by weight, relative to 100 parts by weight of the total solid content in the colored photosensitive resin composition containing it. 0.5 to 20 parts by weight. When content of the said photoinitiator (A) exists in the said range, there exists an advantage, such as the coloring photosensitive resin composition containing it having high sensitivity, shortening exposure time, improving productivity, and maintaining high resolution.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation adjuvant. The above-mentioned photopolymerization initiation adjuvant may be used in combination with a photopolymerization initiator (A), and can be used for accelerating the polymerization of the photopolymerizable compound polymerized by the photopolymerization initiator (A). As said photopolymerization initiation adjuvant, an amine type 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, 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylaminobenzoate Aniline, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamine) group) benzophenone, etc., among them, 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, etc. Examples of the thioxanthone-based compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-dichlorothioxanthone , 1-chloro-4-propoxythioxanthone, etc. The above-mentioned photopolymerization initiation assistants may be used alone or in combination of two or more.

In addition, as the above-mentioned photopolymerization initiation adjuvant, a commercially available product can also be used, and as a commercially available photopolymerization initiation adjuvant, for example, there are EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.). As a preferable combination of a photopolymerization initiator and a photopolymerization initiation assistant in the colored photosensitive resin composition of the present invention, diethoxyacetophenone/4,4'-bis(diethylamino) ) benzophenone, 2-methyl-2-morpholinyl-1-(4-methylphenylthio)propan-1-one/4,4'-bis(diethylamino)diphenyl Methanone, 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)benzophenone, 1-hydroxycyclohexylphenyl ketone/4,4' -Oligomer of bis(diethylamino)benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one/4 ,4'-bis(diethylamino)benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one/4 , a combination of 4'-bis(diethylamino)benzophenone, etc., more preferably 2-methyl-2-morpholinyl-1-(4-methylphenylthio)propane-1- Ketone/4,4'-bis(diethylamino)benzophenone combination. In the case where the photopolymerization initiator (A) and the photopolymerization initiator are used together as described above, the amount of the photopolymerization initiator used is preferably 10 mol per 1 mol of the photopolymerization initiator (A). below the ear, more preferably 0.01 to 5 moles.

The colored photosensitive resin composition of one embodiment of the present invention may contain, in addition to the above-mentioned photopolymerization initiator (A), a group selected from the group consisting of an alkali-soluble resin, a photopolymerizable compound, a colorant, a solvent, and an additive more than one of them.

Alkali Soluble Resin

As said alkali-soluble resin, the copolymer of a carboxyl group-containing monomer, the said carboxyl group-containing monomer, and the other monomer which can be copolymerized, etc. are mentioned, for example.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polyhydric carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated tricarboxylic acids. Here, as an unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid, etc. are mentioned, for example. As an unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, etc. are mentioned, for example. An unsaturated polyhydric carboxylic acid may be an acid anhydride, and maleic anhydride, itaconic anhydride, a citraconic anhydride, etc. are mentioned specifically,. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, and examples thereof include mono(2-acryloyloxyethyl) succinate, mono(2-acryloyloxyethyl) succinate. - Methacryloyloxyethyl) ester, mono(2-acryloyloxyethyl) phthalate, mono(2-methacryloyloxyethyl) phthalate, and the like. In addition, the unsaturated polyvalent carboxylic acid may also be a mono(meth)acrylate of a dicarboxylate polymer at its two terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl. based acrylates, etc. The above carboxyl group-containing monomers may be used alone or in combination of two or more.

Examples of other monomers that can be copolymerized with the carboxyl group-containing monomer include ethylenically unsaturated monomers containing double bonds, such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p- Vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-ethylene Aromatic vinyl compounds such as benzyl benzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene; methyl acrylate, methyl acrylate Methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate , isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, secondary butyl methacrylate, tertiary butyl acrylate, tertiary butyl methacrylate, 2-hydroxyethyl acrylate, methyl methacrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy methacrylate Propyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, methyl methacrylate 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic ring Hexyl ester, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-phenoxyethyl acrylate Esters, 2-phenoxyethyl methacrylate, methoxydiethylene ethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate Unsaturation such as cyclopentadienyl ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate Carboxylic acid 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, acrylic acid-3 -Aminopropyl methacrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate and other unsaturated carboxylic acid aminoalkanes base esters; glycidyl acrylate, glycidyl methacrylate and other unsaturated carboxylic acid glycidyl esters; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and other carboxylic acid vinyl esters; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, etc.; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, dicyanoidene; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl methacrylamide; maleic acid Unsaturated imines such as imine, N-phenylmaleimide, N-cyclohexylmaleimide; 1,3-butadiene, isoprene, chloroprene and other aliphatic Conjugated dienes; polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane have a single end of the polymer molecular chain. Acryloyl or monomethacryloyl macromonomers, etc. These monomers may be used alone or in combination of two or more.

The content of the carboxyl group-containing monomer unit in the above-mentioned alkali-soluble resin is usually 10 to 50% by weight, preferably 15 to 40% by weight, more preferably 10 to 50% by weight relative to 100% by weight of the total alkali-soluble resin. 25 to 40% by weight. When the content of the carboxyl group-containing monomer unit is within the above-mentioned range, the solubility in the developing solution is good, and a pattern can be accurately formed during development.

As said alkali-soluble resin, (meth)acrylic acid/(meth)acrylic acid methyl ester copolymer, (meth)acrylic acid/(meth)acrylic acid benzyl ester copolymer, (meth)acrylic acid/(meth)acrylic acid copolymer, (meth)acrylic acid/(meth)acrylic acid) are mentioned, for example (meth)acrylic acid-2-hydroxyethyl acrylate/benzyl (meth)acrylate copolymer, (meth)acrylic acid/(meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid/( Methyl meth)acrylate/polymethyl(meth)acrylate macromonomer copolymer, (meth)acrylic acid/(meth)acrylate/polystyrene macromonomer copolymer, (meth)acrylic acid / Benzyl (meth)acrylate/polymethyl (meth)acrylate macromonomer copolymer, (meth)acrylic acid/2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate/ Polystyrene macromonomer copolymer, (meth)acrylic acid/(meth)acrylate-2-hydroxyethyl/(meth)acrylate/poly(meth)acrylate macromonomer copolymer, ( Meth)acrylic acid/styrene/benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/mono(2-acryloyloxy) succinate/styrene/ Benzyl (meth)acrylate/N-phenylmaleimide copolymer, (meth)acrylic acid/mono(2-acryloyloxyethyl) succinate/styrene/(meth)acrylate Propyl ester/N-phenylmaleimide copolymer, (meth)acrylic acid/benzyl (meth)acrylate/N-phenylmaleimide/styrene/glycerol mono(meth)acrylate Copolymers, etc.

Among them, (meth)acrylic acid/(meth)acrylic acid benzyl ester copolymer, (meth)acrylic acid/(meth)acrylic acid benzyl ester/styrene copolymer, (meth)acrylic acid/(methyl) ) methyl acrylate copolymer, (meth)acrylic acid/(meth)methyl acrylate/styrene copolymer.

In this specification, (meth)acrylate means acrylate and (or) methacrylate.

According to an embodiment of the present invention, the acid value of the alkali-soluble resin may be 20 to 200 (mg KOH/gram). When the acid value is in the above-mentioned range, the solubility in the developing solution is improved, the non-exposed part is easily dissolved, and the sensitivity is increased. As a result, the pattern of the exposed part remains during development, and the film remaining ratio can be improved. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and it is usually obtained by titration using an aqueous potassium hydroxide solution.

In addition, according to an embodiment of the present invention, the polystyrene-equivalent weight average molecular weight (hereinafter, referred to as "" The weight average molecular weight") may be 3,000 to 200,000, preferably 5,000 to 100,000. When the weight average molecular weight is within the above-mentioned range, the hardness can be increased, the film retention rate can be increased, the solubility of the non-exposed portion in the developing solution can be improved, and the resolution can be improved.

According to an embodiment of the present invention, the content of the above-mentioned alkali-soluble resin may be 10 to 80 parts by weight, preferably 20 to 70 parts by weight relative to 100 parts by weight of the total solid content in the colored photosensitive resin composition containing it. parts by weight. When content of the said alkali-soluble resin exists in the said range, a pattern can be formed, and a resolution and a film retention rate can be improved.

photopolymerizable compound

The above-mentioned photopolymerizable compound is not particularly limited in the present invention as long as it is a compound that can be polymerized by light irradiation through active radicals, acids, etc. generated by a photopolymerization initiator, and may be selected depending on the number of functional groups. Monofunctional, bifunctional, trifunctional or higher polyfunctional polymerizable compounds, etc. are mentioned.

Specific examples of the above-mentioned monofunctional polymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, acrylic acid -2-hydroxyethyl ester, N-vinylpyrrolidone, etc.

Specific examples of the above-mentioned bifunctional polymerizable compound include 1,6-hexanediol (meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. , triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, butanediol dimethacrylate ester, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, poly Ethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, and the like.

Specific examples of the above-mentioned trifunctional or higher polyfunctional polymerizable compound include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, and ethoxylated trimethylol. Trifunctional polymerizable compounds such as propane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, glycerol propoxylated triacrylate, isocyanurate triacrylate, etc. ; Neotaerythritol tetra(meth)acrylate, dimethylolpropane tetra(methyl) Tetrafunctional polymerizable compounds such as acrylates; pentafunctional polymerizable compounds such as dipeotaerythritol penta(meth)acrylate and dipivalerythritol hexa(meth)acrylate, and the like.

Among them, the above-mentioned photopolymerizable compounds can be used alone or in combination of two or more kinds. Specifically, a polyfunctional polymerizable compound having a bifunctional or more functions is preferably used, and a polyfunctional polymerizable compound having a pentafunctionality or more can be preferably used in particular. , but not limited to this.

According to an embodiment of the present invention, the content of the photopolymerizable compound may be 5 to 50 parts by weight, preferably 7 to 50 parts by weight, relative to 100 parts by weight of the total solid content in the colored photosensitive resin composition containing the photopolymerizable compound. 45 parts by weight. When content of the said photopolymerizable compound exists in the said range, there exists an advantage, such as the intensity|strength and smoothness of a pixel part becoming favorable.

Colorant

The said colorant is a composition which can be variously applied according to the application of a color filter, and in this invention, the kind is not specifically limited.

The above-mentioned colorant may be any one of pigments, dyes or natural pigments, and as the above-mentioned pigments, pigments classified as pigments in the Colour Index (published by The Society of Dyers and Colourists) can be used. (pigment) compounds. The coloring agent of the present invention is preferably an organic pigment from the viewpoint of being excellent in heat resistance and color development.

Preferable specific examples of pigments usable 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 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 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. Pigment Yellow 214 and other yellow pigments; 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. 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Pigment Orange 73 and other orange pigments; 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. C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 265 and other red pigments; C.I. Pigment Blue 15, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. 15:6, C.I. Pigment Blue 60 and other blue pigments; 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. Pigment Violet 38 etc. ; C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58 and other green pigments; C.I. Pigment Brown 23, C.I. Pigment Brown 25 and other brown pigments; C.I. Pigment Black 1, C.I. Pigment Black 7 and other black pigments, etc.

Among them, it can preferably include 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. One or more pigments of C.I. Pigment Green 36.

The above-mentioned organic pigments and inorganic pigments may be used alone or in combination of two or more. For example, when a red pixel is formed, C.I. Pigment Red 254 and C.I. Pigment Yellow 139 are contained, when a green pixel is formed, C.I. Pigment Green 58, C.I. Pigment blue 15:6 is preferable for improving color reproducibility, but is not limited to this.

As long as the said dye has solubility with respect to an organic solvent, one or more types can be used without limitation. It is preferable to use a dye which has solubility in an organic solvent, and which can secure reliability such as solubility in an alkali developing solution and heat resistance and solvent resistance. As the above-mentioned dyes, dyes selected from acid dyes having acidic groups such as sulfonic acid or carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, etc., and derivatives thereof, can be used, In addition to this, azo-based, dibenzopyran (xanthene)-based acid dyes, and phthalocyanine-based acid dyes and derivatives thereof can also be selected. Examples of the above-mentioned dyes include compounds classified as dyes in the Dye Index (published by The Society of Dyers and Colourists), and conventional dyes described in Dyeing Notes (Staining Society).

Specific examples of the above dyes include C.I. solvent dyes: C.I. Solvent Yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 C.I. Solvent Red 8, 45, 49, 122, 125, 130 and other red dyes; C.I. Solvent Orange 2, 7, 11, 15, 26, 45, 56, 62 and other orange dyes; C.I. Solvent Blue 35, 37, 45, 59, 67 and other blue dyes; C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other green dyes, etc.

In addition, C.I. acid dyes include 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, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and other yellow dyes; 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, 382, 383, 394, 401, 412, 417, 418, 422, 426 and other red dyes; 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 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, 335, 340 and other blue dyes; C.I. acid Violet dyes such as Violet 6B, 7, 9, 17, 19; C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other greens Dyes, etc.

In addition, C.I. direct dyes include 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, 136, 138, 141 and other yellow dyes; 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, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 and other red dyes ; 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, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293 and other blue dyes; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and other purple dyes; C.I. Direct Green 25, 27 , 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other green dyes.

In addition, C.I. mordant dyes include yellow dyes such as C.I. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc. ; C.I. Medium 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 other red dyes; C.I. Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48 and other orange dyes; C.I. Medium 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 other blue dyes; C.I. Medium Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 Violet dyes such as C.I. Medium Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other green dyes, etc.

Content of the said coloring agent can be 10-70 weight part with respect to 100 weight part of total solids in the coloring photosensitive resin composition containing it, Preferably it can be 20-60 weight part. When content of the said coloring agent exists in the said range, the color density at the time of making into a color filter is sufficient, and the pattern with sufficient mechanical strength can be formed.

In this invention, the solid content of a coloring photosensitive composition means the sum total of the components after removing a solvent.

The organic pigments in the above-mentioned pigments can be subjected to the following treatments as necessary: surface treatment with a pigment derivative etc. into which an acidic group or a basic group is introduced; graft treatment with a polymer compound or the like on the surface of the pigment; particleization with sulfuric acid Micronization treatment such as refinement; washing treatment with organic solvent, water, etc. to remove impurities; or removal treatment such as ion exchange method with ionic impurities. The colorant is preferably uniform in particle size. When the colorant is a pigment, by adding a pigment dispersant and performing a dispersion treatment, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

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

Specific examples of the above-mentioned pigment dispersants include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants, and these may be used alone or in combination of two or more. used in combination.

The above-mentioned pigment dispersants are added for the purpose of decoagulation of the pigments and maintenance of stability, and pigment dispersants generally used in this field can be used without limitation. Preferably, an acrylate-based dispersion containing BMA (butyl methacrylate) or DMAEMA (N,N-dimethylaminoethyl methacrylate) can be used agent (hereinafter, referred to as acrylic dispersant). At this time, the above-mentioned acrylic dispersant can preferably be applied as a dispersant produced by the activity control method as mentioned in Korean Laid-Open Patent Publication No. 2004-0014311, as a market for the acrylate-based dispersant produced by the above-mentioned activity control method. Examples of commercially available products include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150, but are not limited to these, and these can be used alone or in combination of two or more.

As the above-mentioned dispersant, other resin-type pigment dispersants other than the above-mentioned acrylic dispersant may be used. Examples of the above-mentioned other resin-type pigment dispersants include conventional resin-type pigment dispersants, especially polyurethanes, polycarboxylates represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, and polycarboxylates. (partial) ammonium salts of acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyamidoamine phosphates, esters of hydroxyl-containing polycarboxylic acids and their Modified products, or oily dispersants such as amides or their salts formed by the reaction of polyesters with free carboxyl groups and poly(lower alkylene imines); (meth)acrylic acid- Water-soluble resins or water-soluble polymer compounds such as styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol or polyvinylpyrrolidone; poly Esters; modified polyacrylates; ethylene oxide/propylene oxide addition products and phosphate esters, etc. As a commercial item of the said resin-type dispersing agent, the brand name of BYK Chemical Co., Ltd.: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, 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; Lubrizol's trade names: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Chuanyan Fine Chemicals' trade names: HINOACT T-6000, HINOACT T-7000, HINOACT T -8000; Ajinomoto's trade names: AJISPER PB-821, AJISPER PB-822, AJISPER PB-823; Kyoeisha Chemical's trade names: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 et al. The resin-type pigment dispersants other than the above-mentioned acrylic dispersants may be used alone or in combination of two or more, or may be used in combination with the acrylic dispersants.

When the said colored photosensitive resin composition further contains a pigment dispersing agent, its content may be 1 weight part or less per 1 weight part of the coloring agent contained together, More preferably, it may be 0.05 weight part or more and 0.5 weight part or less. When the usage-amount of the said pigment dispersing agent is in the said range, the pigment of the state which disperse|distributed uniformly can be obtained.

solvent

The solvent of the present invention can be used without particular limitation as long as it is effective in dispersing or dissolving other components contained together, and for example, ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amides can be preferably used Wait.

Examples of the above ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol Alcohol monobutyl ether, diethylene 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 Cyrus acetate, Ethyl Cyrus acetate, Ethyl carbitol acetate ester, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxyamyl acetate, anisole, phenethyl ether or methyl anisole, etc. .

As said aromatic hydrocarbon, benzene, toluene, xylene, mesitylene etc. are mentioned, for example.

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

As said alcohol, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, or glycerol etc. are mentioned, for example.

Examples of the above esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl acetate Ethyl acetate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate , butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate ester, methyl 2-oxo-2-methylpropionate, ethyl 2-oxo-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2 -Ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate , 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate or γ-butyrolactone, etc.

As said amides, N,N- dimethylformamide, N,N- dimethylacetamide, etc. are mentioned, for example.

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

The above-mentioned solvents can be used alone or in a mixture of two or more kinds. Among them, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate or propylene glycol methyl ether can be preferably used. The content of the above solvents is relative to each other. It may be 10 to 90 parts by weight in all 100 parts by weight of the colored photosensitive resin composition containing it. When the content of the solvent is in the above range, the flatness is good when the colored photosensitive resin composition is applied, the color density is sufficient when the color filter is formed, and the display characteristics can be improved.

additive

The said coloring photosensitive resin composition may contain additives, such as an antifoamer, a surfactant, a thermal crosslinking agent, a tackifier, and an antioxidant, as needed in addition to the said component, in order to improve performance.

The above-mentioned surfactant is a component that can improve the adhesion between the substrate and the colored photosensitive resin composition. For example, fluorine-containing surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicones can be used. Various surfactants such as surfactants. These can be used alone or in combination of two or more.

Specific examples of fluorosurfactants include MAGAFAC F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 and F781 (trade names , DIC Corporation (DIC Corporation) products); FLUORAD FC430, FC431 and FC171 (trade name, Sumitomo 3M Limited (Sumitomo 3M Limited) products); 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 of Asahi Glass Co., Ltd.); SOLSPERSE 20000 (trade name, product of Lubrizol Japan Limited), etc.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, and trimethylolethane, and ethoxylates or propoxylates thereof (for example, propoxylated glycerol or ethyl acetate) Oxylated glycerol); PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 (trade name, BASF products) such as polyoxyethylene lauryl base ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol di Stearates, sorbitan fatty acid esters, etc.

Specific examples of the cationic surfactant include phthalocyanine-modified compounds such as EFKA-745 (trade name, manufactured by Morishita & Co., Ltd.); KP341 (trade name, Shin-Etsu Chemical Co., Ltd.) Company (Shin-Etsu Chemical Co., Ltd. products) such as organosiloxane polymers; POLYFLOW No.75, No.90, No.95 (trade name, Kyoeisha Chemical Co., Ltd. (Kyoeisha Chemical Co., Ltd.) ., Ltd.) products) and the like (meth)acrylic (co)polymer; W001 (trade name, Yusho Co., Ltd. products) and the like.

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

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

The said thermal crosslinking agent is a component which can make the crosslinking reaction by UV irradiation and heat processing generate|occur|produce smoothly at the time of forming a coating film from 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, etc. are mentioned.

The above-mentioned tackifier has the following advantages: it can improve the adhesion with inorganic substances that can be used as substrates, such as silicon compounds such as silicon, silicon oxide, and silicon nitride, or metals such as gold, copper, and aluminum, and can improve the adjustment and the substrate. capacity of the taper angle. 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 above-mentioned silane coupling agent is not particularly limited, and specific examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyl Trialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-methacryloyloxypropylalkane Dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β-(3,4-epoxycyclohexyl)ethyltrialkoxysilane, ethylene Trialkoxysilane, etc., preferably γ-glycidoxypropyltrialkoxysilane or γ-methacryloyloxypropyltrialkoxysilane, more preferably γ-glycidyl Oxypropyltrialkoxysilane. These can be used alone or in combination of two or more.

As an example of the said antioxidant, 2-tertiary butylphenol, 2,6-ditertiary butylphenol, 2,4-ditertiary butylphenol, 2-tertiary butylphenol, 2 ,6-di-tertiary butylphenol, 2,4-di-tertiary butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4-diisopropylphenol Propylphenol, 2-tertiary octylphenol, 2,6-ditertiary octylphenol, 2,4-ditertiary octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol , 2,4-dicyclopentylphenol, 2-tertiary butyl-p-cresol, 2,6-ditertiary pentylphenol, 2,4-ditertiary pentylphenol, 6-tertiary butyl -o-Cresol, 2,6-Di-tertiary dodecylphenol, 2,4-Di-tertiary-dodecylphenol, 2-Secondary-butyl-p-cresol, 2,6-Di-tertiary-octane 2,4-Ditertiary octylphenol, 6-tertiary butyl-o-cresol, 2-tertiary octyl-p-cresol, 2-tertiary dodecyl-p-cresol, 2 -Tertiary butyl-6-isopropylphenol, 6-tertiary octyl-o-cresol, 6-tertiary dodecyl-o-cresol, 4,4'-butylene bis(3-methylphenol) yl-6-tertiary butylphenol), octadecyl-3-(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate, 4,4'-butylene bis(6 -Tetra-butyl-3-methylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tributylphenol) tertiary butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propane acid ester], neotaerythritol-tetrakis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6 -Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-ethylphenol, 2,2'-di-methylbis(4-methyl)benzene yl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tertiarybutylphenyl)butane, 1,3,5-tris(4- Hydroxybenzyl)benzene, tetrakis[methylidene-3-(3,5'-ditert-butyl-4'-hydroxyphenylpropionate)]methane, etc., can be used 1 type or 2 or more types.

The manufacturing method of the colored photosensitive resin composition of this invention can use the method generally used in this field without limitation, for example, it can manufacture by the following method. The colorant is preliminarily mixed with a solvent and dispersed by 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, a pigment dispersant may be used as necessary, and a part or all of the alkali-soluble resin may be blended in some cases. The remaining alkali-soluble resin, photopolymerizable compound, and light are further added to the obtained dispersion liquid (hereinafter, also referred to as millbase) so as to have a predetermined concentration. A polymerization initiator, an additive, other components used as needed, a solvent added as needed, and a target coloring photosensitive resin composition can be obtained by mixing.

<Color filter>

A color filter according to another aspect of the present invention includes a cured product of the above-mentioned colored photosensitive resin composition, so that the shape of the pattern can be made into the form of a positive slope before the post-baking step in the manufacturing process, thereby preventing the manufacturing process It has the advantages of preventing problems in the pattern and preventing holes from being generated in the pattern when forming the pattern.

The color filter of the present invention can be manufactured by a manufacturing method generally used in the art without limitation. As an example, it can be described with reference to FIGS. 1 to 3, and the details are as follows.

In order to manufacture a color filter using the coloring photosensitive resin composition of this invention, it is necessary to form a coloring pattern, and for this, the said coloring photosensitive resin composition is pattern-treated. Specifically, referring to FIG. 1 , the color layer 11 formed of the colored photosensitive resin composition of the present invention is formed on the upper portion of the substrate 10 . In this case, the type of the above-mentioned substrate 10 is not particularly limited, and may be a substrate of the color filter itself, or may be a portion where the color filter is located in a display device or the like. The above-mentioned substrate 10 may be a glass plate, a silicon wafer, a plastic plate such as poly ether sulfone (PES), polycarbonate (PC), or the like. That is, the above-mentioned substrate 10 may be a silicon (Si), silicon oxide (SiOx) or glass substrate, or may be a polymer substrate. In this way, 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 subjected to spin coating, slit spin coating, slit coating, It coats on a board|substrate by coating methods, such as roll coating, spraying, and an inkjet system, and volatilizes volatile components, such as a solvent. Thereby, the color layer 11 which consists of the coloring photosensitive resin composition which consists of the solid content of a coloring photosensitive resin composition and contains little volatile component is formed. film thickness The degree is determined according to coating conditions such as the viscosity of the composition, the concentration of solid content, and the coating speed. When the composition of the present invention is used, a color layer 11 with a thickness of 0.5 to 5 microns can be obtained.

Next, referring to FIG. 2 , the colored layer 11 formed of the colored photosensitive resin composition on the base material 10 is exposed to light 30 (exposure). For exposure, for example, the above-mentioned color layer 11 is irradiated with light 30 in a predetermined pattern through the mask 20 . At this time, as the light 30, g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc. of ultraviolet rays are generally used. Light 30 passes according to the pattern of reticle 20 . The above-mentioned photomask 20 provides a light shielding layer for shielding light in a predetermined pattern on the surface of the glass plate. The light 30 is blocked by the light shielding layer. The portion of the glass plate not provided with the light-shielding layer is a light-transmitting portion through which light is transmitted. The color layer 11 is exposed to light in accordance with such a pattern of light-transmitting portions. The irradiation amount of the light 30 is appropriately selected according to the coloring photosensitive resin composition used.

The solubility of the portion irradiated with the light 30 is significantly smaller than that of the portion not irradiated with the light 30, and the difference in solubility between the two is maximized. Therefore, the developing operation is performed using such a 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 or the like is used. Referring to FIG. 3 , by such development, the non-irradiated regions of the color layer 11 formed on the substrate 10 that are not irradiated with the light 30 are removed. In contrast to this, the light 30 irradiated region irradiated with the light 30 remains to form the colored pattern 11R. After development, the layer is usually washed with water and dried to obtain a predetermined colored pattern 11R. In addition, after drying, heat treatment may be performed. The coloring pattern 11R formed by the heat treatment is cured, thereby improving the mechanical strength. In this way, 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.

<Video display device>

The image display device of another aspect of the present invention includes the above-mentioned color filter, and thus has advantages such as no problems in the manufacturing process and few defects. Specific examples of the image display device include liquid crystal displays (liquid crystal display devices; LCD, liquid crystal display), organic EL (electroluminescence) displays (organic EL display devices), liquid crystal projectors, display devices for game machines, mobile Display devices for mobile terminals such as telephones, display devices for digital cameras, and display devices for car navigation, etc., are particularly suitable for color display devices.

The above-mentioned image display device may include other components such as a light-emitting device such as a light source, a light guide plate, a liquid crystal display section including the color filter of the present invention, and the like, which may be included in a normal image display device, which is not limited in the present invention .

Below, in order to help the understanding of the present invention, preferred embodiments are provided. It is obvious to those skilled in the art that the following embodiments are only illustrative of the present invention, and can be implemented within the scope of the present invention and the scope of technical ideas. Various changes and modifications, of course, such changes and modifications also belong to the scope of the accompanying patent application. In the following Examples and Comparative Examples, unless otherwise specified, "%" and "part" indicating content are based on weight.

Examples and Comparative Examples

The coloring photosensitive resin composition was manufactured by mixing according to the composition and content of the following Table 1.

Experimental Example 1. Absorptivity of Photopolymerization Initiator and Molecular Weight Measurement of R2

Each photopolymerization initiator used in above-mentioned embodiment and comparative example is diluted according to 0.001% by weight in propylene glycol monomethyl ether acetate, utilizes ultraviolet-visible light spectrometer (UV-VIS Spectrophotometer, model name: UV-2550, Manufacturing company: Shimadzu (SHIMADZU) measured the absorbance at a wavelength of 365 nm, and recorded the results in the following Table 2, and calculated and recorded the chemical formula 1 or 2 of the present invention for each photopolymerization initiator. The molecular weight of the moiety corresponding to R ₂ .

Referring to the above Table 2, it can be confirmed that in the case of the photopolymerization initiators contained in the examples of the present invention, namely A-1 to A-4, the molecular weight of the part corresponding to R ₂ and the light at the wavelength of 365 nm Absorptivity is included within the scope of the present disclosure.

Manufacture example: Manufacture of color filter

Each coloring photosensitive resin composition manufactured by the said Example and a comparative example was apply|coated on a glass substrate by the spin coating method, and it was set|placed on a hotplate and maintained at the temperature of 100 degreeC for 3 minutes to form a thin film. Next, a test mask having a line/space pattern of 1 μm to 50 μm was placed on the above-mentioned film, and the distance between the film and the test mask was set to 100 μm, and ultraviolet rays were irradiated. At this time, the ultraviolet light source used a 1 kilowatt (KW, kilowatt) high-pressure mercury lamp including all the g, h, and i lines, and irradiated with an illuminance of 50 millijoules/square centimeter (mJ/cm ² ), and no special Optical filter. The above-mentioned ultraviolet-irradiated film was immersed in a KOH aqueous developing solution of pH 10.5 for 1 minute for development. The thin-film-coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220° C. for 30 minutes to produce a color filter. The film thickness of the color filter manufactured above was 2.0 μm.

Experimental Example 2. Pattern Taper Morphology

A scanning electron microscope (SEM, scanning electron microscope) was used to measure the length of the slope before the 220° C. heating process in the above-mentioned production example as shown in FIG. 4 , and the results are described in Table 3 below.

Experimental example 3. Pattern line width (sensitivity) evaluation

The line width of the pattern formed in the above-mentioned production example was measured using a scanning electron microscope (SEM). When the line width of the pattern was measured to be equal to or larger than the line width (100 μm) of the photomask, it was interpreted that the sensitivity of the colored photosensitive resin composition was sufficient and the line width was widened. At this time, the expanded line width (micrometer) with respect to the mask is described in Table 3 below.

Referring to Table 3 above, it was confirmed that in the cases of Examples 1 to 4 satisfying all the conditions of the present invention, compared with the cases of Comparative Examples 1 to 4 not satisfying at least one of the conditions of the present invention, the sensitivity was excellent, and it was possible to Form a positive slope.

Specifically, in the case of Comparative Examples 1, 2, and 4 using a photopolymerization initiator with a molecular weight of R ₂ outside the range disclosed in the present invention, it was confirmed that a reverse slope was formed and a process defect occurred, especially in the case of In the case of Comparative Example 2, which exceeds the range of the molecular weight of R ₂ disclosed in the present invention, it can be confirmed that patterning itself is impossible, and photopolymerization is used whose absorptivity at a wavelength of 365 nm is lower than the range disclosed in the present invention. In the case of Comparative Example 3 of the initiator, it was confirmed that the reverse slope was formed in the same manner, and the sensitivity was also poor.

10‧‧‧Substrate

11R‧‧‧Coloring Pattern

Claims (9)

A colored photosensitive resin composition comprising a photopolymerization initiator (A), the photopolymerization initiator (A) comprising a photopolymerization initiator (a1) having a light absorption rate of 0.1% or more at a wavelength of 365 nm ), the photopolymerization initiator (a1) is a compound represented by the following chemical formula 1 or chemical formula 2,

In Chemical Formula 1 and Chemical Formula 2, R ₁ is each independently represented by the following Chemical Formula 3, R ₂ is a hydrocarbon group whose molecular weight is each independently 50 to 150, and R ₃ is each independently substituted or unsubstituted Carbazolyl, substituted or unsubstituted perylene group, [Chemical formula 3]-R ₄ -R ₅ In chemical formula 3, R ₄ is C1-C8 straight-chain alkylene, C3-C8 branched alkylene base, C6 to C20 aryl extended or C7 to C25 extended aralkyl, R ₅ is each independently CN, C1 to C8 straight chain alkyl, C3 to C8 branched alkyl, C6 to C20 An aryl group or a C7 to C25 aralkyl group, wherein the content of the photopolymerization initiator (a1) is 70 to 100 parts by weight with respect to 100 parts by weight of the total photopolymerization initiator (A) containing it. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises at least one selected from the group consisting of: a photopolymerization initiator other than the photopolymerization initiator (a1) (a2), alkali-soluble resin, photopolymerizable compound, solvent and additive. The coloring photosensitive resin composition according to claim 1, wherein the content of the photopolymerization initiator (A) is 0.1 to 30 parts by weight relative to 100 parts by weight of the total solid content in the coloring photosensitive resin composition containing the photopolymerization initiator (A). parts by weight. The colored photosensitive resin composition according to claim 2, wherein the alkali-soluble resin has an acid value of 20 to 200 milligrams KOH/gram (mgKOH/g). The colored photosensitive resin composition according to claim 2, wherein the alkali-soluble resin has a weight average molecular weight of 3,000 to 200,000. The colored photosensitive resin composition according to claim 2, wherein the content of the alkali-soluble resin is 10 to 80 parts by weight with respect to 100 parts by weight of the total solid content in the colored photosensitive resin composition containing it. The coloring photosensitive resin composition according to claim 2, wherein the content of the photopolymerizable compound is 5 to 50 parts by weight with respect to 100 parts by weight of the total solid content in the coloring photosensitive resin composition containing the photopolymerizable compound. A color filter comprising the cured product of the colored photosensitive resin composition according to any one of claims 1 to 7. An image display device comprising the color filter according to claim 8.

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