KR102279575B1 - Colored photosensitive resin composition, color filter, and image display apparatus comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, a color filter, and an image display device having the same, and more particularly, comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,
The colorant includes the following Chemical Formula 1 and further comprises one of phthalocyanine blue pigments, and relates to a colored photosensitive resin composition capable of manufacturing a color filter having improved complexing properties and luminance properties.
In Formula 1, A ₁ to A ₁₆ are each independently one of Cl, Br, and H, and _{among A 1} to A ₁₆ , H is 1 to 6, Cl is 0 to 5, and Br is 7 to 13.
[Formula 1]

Description

Colored photosensitive resin composition, color filter, and image display device having the same {COLORED PHOTOSENSITIVE RESIN COMPOSITION, COLOR FILTER, AND IMAGE DISPLAY APPARATUS COMPRISING THE SAME}

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

A color filter is widely used in various display devices such as an imaging device and a liquid crystal display (LCD), and its application range is rapidly expanding. The color filter consists of a coloring pattern of three colors of red, green, and blue, or a coloring pattern of three colors of yellow, magenta, and cyan. is made of

The color pattern of each color filter is generally formed using a color photosensitive resin composition including a colorant such as a pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is generally performed by a lithography process.

Meanwhile, in recent years, various display devices including a solid-state imaging device such as a digital camera are required to have high luminance and high coloration in order to improve fairness and quality.

Korean Patent Application Laid-Open No. 10-2012-0113666 discloses C.I Pigment Green 7 and C.I. Although a resin composition using Pigment Yellow 138 and a yellow azo dye is disclosed, there is a problem that high colorability is not simultaneously satisfied.

In addition, Korean Patent Application Laid-Open No. 10-2012-0158517 discloses C.I Pigment Green 7 and C.I. Although disclosed with respect to a colored photosensitive resin composition containing Pigment Blue 15:3 or 15:4, there is a problem in that high luminance is not satisfied.

Korean Patent Publication No. 10-2012-0113666 Korean Patent Publication No. 10-2012-0158517

An object of this invention is to provide the coloring photosensitive resin composition excellent in brightness|luminance and colorability by including the coloring agent containing the pigment of a specific structure.

Another object of the present invention is to provide a color filter including the colored photosensitive resin composition and an image display device having the same to implement high luminance and high coloring properties.

The colored photosensitive resin composition according to an embodiment of the present invention for achieving the above object includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, and the colorant includes the colorant of Formula 1, and phthalocyanine blue It is characterized in that it further comprises one kind of pigment.

In addition, the present invention is characterized by a color filter made of the colored photosensitive resin composition and an image display device including the same.

The coloring photosensitive resin composition of this invention has the effect excellent in luminance and colorability by including the coloring agent containing the pigment of a specific structure.

The present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and the colorant includes a pigment represented by Formula 1, and thus a colored photosensitive resin composition having excellent luminance and colorability, a color filter, and a color filter comprising the same It relates to an image display device.

Hereinafter, the present invention will be described in detail.

The colorant is a component capable of expressing colors such as red, green, and blue so as to produce a pattern having a desired color, and the colorant according to the present invention has ZnPc (Zinc Phthalocyanine) as a basic structure as shown in Chemical Formula 1.

[Formula 1]

In Formula 1, A ₁ to A ₁₆ are each independently one of Cl, Br, and H, among A ₁ to A ₁₆ H is 1 to 6, Cl is 0 to 5, and Br is 7 to 13.

If necessary, the colorant according to the present invention is a component capable of expressing colors such as red/green/blue so as to produce a pattern having a desired color, and is selected from the group consisting of commonly used pigments and dyes. It may include one or more types, and may be manufactured in the form of a mill base. In this case, the colorant including the pigment of Formula 1 according to the present invention may have a color coordinate of x=0.1 to 0.35 when y=0.6 or more in the XYZ color system, and when y=0.5 to 0.6, x=0.2 to 0.3 It can have color coordinates of .

The color material includes Chemical Formula 1 as an essential component, and may further include one kind of phthalocyanine blue pigment. At this time, the phthalocyanine blue pigment is more specifically CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, such as pigments of the same color index (CI) number, respectively alone or two types The above combinations may be used, but the present invention is not limited thereto.

In addition, green, yellow organic pigments or inorganic pigments generally used in the art may be used. As the pigment, various pigments used in printing inks, inkjet inks, etc. may be used, and specifically, water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline Pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone (pyranthrone) pigment, diketopyrroropyrrole pigment, etc. are mentioned. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black Or a composite metal oxide etc. are mentioned. In particular, the organic and inorganic pigments include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists), and more specifically, the color index (CI) number of pigments, but are not necessarily limited thereto.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 , 180 and 185

C.I. Pigment Green 10, 15, 25, 36, 47 and 58

C.I Pigment Brown 28

C.I Pigment Blue 15:3, 15:4, 15:6

Each of the above pigments may be used alone or in combination of two or more.

In particular, among the yellow dyes exemplified above, C.I. Pigment Yellow 129, C.I. At least one pigment selected from Pigment Yellow 185 may be preferably used.

The content of the colorant is preferably 5 to 70% by weight, more preferably 10 to 50% by weight based on the solid content in the colored photosensitive resin composition.

If the content of the colorant is less than the above range, the color separation ability of the formed pattern may be reduced, and if the content of the colorant is exceeded, lithography performance may be deteriorated to cause problems such as residues or non-development. As the pigment, it is preferable to use a pigment dispersion in which the particle size is uniformly dispersed. As an example of a method for uniformly dispersing the particle diameter of the pigment, a method of dispersing treatment by containing a pigment dispersant may be mentioned. According to this method, a pigment dispersion in a state in which the pigment is uniformly dispersed in a solution can be obtained.

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

The binder resin according to the present invention is preferably a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The other copolymerizable monomer is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate unsaturated carboxylate compounds such as acrylates; unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane; 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-methyl-3-methacryloxyethyloxetane, etc. of unsaturated oxetane carboxylate compounds, and the like. These monomers can be used individually or in combination of 2 or more types, respectively.

It is preferable that it is 1.5-6.0, and, as for the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of binder resin, it is more preferable that it is 1.8-4.0. It is preferable that the molecular weight distribution of the binder resin is 1.5 to 6.0 because of excellent developability.

The binder resin is preferably contained in an amount of 5 to 90% by weight, more preferably in a range of 10 to 70% by weight, based on the solid content in the colored photosensitive resin composition.

At this time, when the content of the binder resin is included in the above range, the solubility in the developer is sufficient, so that it is difficult to generate a developing residue on the substrate of the non-pixel portion, and it is difficult to reduce the film of the pixel portion of the exposed portion during development. omission is good.

The photopolymerizable monomer according to the present invention is a monomer that can be polymerized by active radicals, acids, etc. generated from the photopolymerization initiator by irradiation with light.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaeryth Ritol acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1 and 4-butanediol dimethacrylate and 1,6-hexanediol dimethacrylate.

It is preferable that a photopolymerizable monomer is contained in 5-45 weight% with respect to solid content in the coloring photosensitive resin composition, and it is more preferable that it is contained in 10-35 weight%. When the content of the photopolymerizable monomer is included in the above range, the intensity or smoothness of the pixel portion is good.

The photopolymerization initiator according to the present invention may be used without particularly limiting its type as long as it can polymerize the alkali-soluble resin and the photopolymerizable compound. In particular, it is preferable to use an oxime compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, and the like.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and compounds represented by Formulas 2 to 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

In addition, as long as the effect of the present invention is not impaired, other photopolymerization initiators commonly used in this field may be additionally mixed and used, and examples thereof include triazine-based compounds and acetophenone-based compounds.

Specific examples of the triazine-based compound include 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-piperonyl-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 etc. are mentioned.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyl) oxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1 -one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl)-4, 4'5,5'-tetraphenyl-1,2'-biimidazole or the imidazole compound in which the phenyl group at the 4,4',5,5'-position is substituted by the carboalkoxy group, etc. are mentioned. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole are preferably used do.

As another photoinitiator, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, anthracene type compound, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra( tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. There is this.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. have.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

In addition, the photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent. When a photoinitiator adjuvant is used together with a photoinitiator, the photosensitive resin composition containing these will become more highly sensitive, and productivity can be improved.

As the photopolymerization initiation adjuvant, for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group may be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylamino 2-ethylhexyl benzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone), 4,4'-bis(diethyl) Aromatic amine compounds, such as amino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichloro and aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropanetris(3-mercaptopropionate), pentaerythritoltetrakis(3-mercaptobutyl rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like. can

The amount of the photopolymerization initiator used is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight, based on the solid content, based on the total amount of the alkali-soluble resin and the photopolymerizable compound. When the photopolymerization initiator is included in the above range, the colored photosensitive resin composition is highly sensitive and exposure time is shortened, so productivity is improved and high resolution can be maintained. The smoothness can be good.

In addition, when using the photopolymerization initiation adjuvant, the amount of the photopolymerization initiation adjuvant is preferably included in an amount of 0.1 to 50% by weight based on the solid content of the total amount of the alkali-soluble resin and the photopolymerizable compound, and 1 to 40% by weight. It is more preferable to be

When the photopolymerization initiation auxiliary agent is included within the above range, the sensitivity of the colored photosensitive resin composition may be increased, and productivity of a color filter formed using the composition may be improved.

As long as the solvent according to the present invention is effective for dispersing or dissolving other components included in the colored photosensitive resin composition, it can be used without particular limitation on the type thereof. In particular, ethers, aromatic hydrocarbons, ketones, alcohols, esters or amides etc. are preferable.

The solvent is specifically ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monomethyl ether acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, methyl ethyl ketone , acetone, methyl amyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-ethyl ethoxypropionate, 3- esters, such as methyl methoxypropionate, and cyclic esters, such as (gamma)-butyrolactone, etc. are mentioned.

Among the solvents exemplified above, in consideration of applicability and dryness, an organic solvent having a boiling point of 100°C to 200°C is preferable, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Esters, such as ethyl propionate and 3-methoxy methyl propionate, are mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy ethyl propionate, 3- Methyl methoxypropionate, etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types, respectively.

It is preferable that 60 to 90 weight% of the solvent in the coloring photosensitive resin composition of this invention is contained with respect to the coloring photosensitive resin composition whole quantity, and it is more preferable that it is contained 70 to 85 weight%. When the content of the solvent is included within the above range, the coating property may be improved when applied with an application device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet.

It is also possible to add additives, such as another high molecular compound, hardening|curing agent, surfactant, adhesion promoter, antioxidant, and aggregation inhibitor, to the coloring photosensitive resin composition of this invention in parallel as needed.

Specific examples of the other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. can be heard

The curing agent is used for deep curing and increasing mechanical strength, and specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A-based epoxy resin, hydrogenated bisphenol A-based epoxy resin, bisphenol F-based epoxy resin, hydrogenated bisphenol F-based epoxy resin, novolak-type epoxy resin, other aromatic epoxy resins, alicyclic epoxy resins , glycidyl ester-based resins, glycidylamine-based resins, or brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof, butadiene (co)polymer epoxides, isoprene A co)polymer epoxidized product, a glycidyl (meth)acrylate (co)polymer, triglycidyl isocyanurate, etc. are mentioned.

Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylenebisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The curing agent may be used in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing auxiliary compound includes, for example, polyhydric carboxylic acids, polyhydric carboxylic acid anhydrides, and acid generators. As the polyhydric carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. Specific examples of the epoxy resin curing agent include a trade name (Adekahadona EH-700) (manufactured by Adeka Industries, Ltd.), a trade name (Rikasiddo HH) (manufactured by Shin Nippon Ewha Co., Ltd.), a trade name (MH-700) (Shin Nippon Ewha Co., Ltd.) manufactured by Nippon Ewha Co., Ltd.) and the like. The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film-forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

The silicone-based surfactants include, for example, DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 manufactured by Dow Corning Toray Silicone as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4460 by GE Toshiba Silicone. , TSF-4452, and the like. The fluorine-based surfactants include, for example, Megapiece F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink Chemical Co., Ltd. as a commercially available product. Each of the surfactants exemplified above may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-( 3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethyl Toxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, etc. are mentioned.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.05 to 2% by weight in the solid content of the photosensitive resin composition.

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

Specific examples of the aggregation inhibitor include sodium polyacrylate.

The liquid crystal display device of the present invention includes a color filter of the present invention comprising a substrate and a color layer.

The liquid crystal display includes a configuration known to those skilled in the art, except that the color filter is provided.

Hereinafter, preferred examples are presented to aid the understanding of the present invention, but the following examples are merely illustrative of the present invention and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims.

The present invention provides a color filter made of a colored photosensitive resin composition. The color filter of the present invention includes a substrate and a colored pattern made of the colored photosensitive resin composition on the substrate.

The substrate is a transparent material, and a material with sufficient strength and support for the stability of the color filter is used. Preferably, a glass having excellent chemical stability and high strength may be used.

The colored pattern is prepared by coating the colored photosensitive resin composition on a substrate, photocuring and developing.

The thickness of the coloring pattern is not particularly limited, and may be, for example, 1 to 6 μm.

The coloring pattern may be formed, for example, by the following method.

First, the composition is applied on a substrate or a layer made of the solid content of the previously formed photosensitive resin composition, and volatile components such as a solvent are removed by prebaking from the applied photosensitive resin composition layer to obtain a smooth coating film. In this way, the obtained coating film is irradiated with an ultraviolet-ray through the mask for forming the target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that parallel rays are uniformly irradiated to the entire exposed portion and the mask and the substrate are precisely aligned. Moreover, the target pattern shape is obtained by making the coating film which hardening complete|finished contact with aqueous alkali solution after that, melt|dissolving an unexposed part, and developing.

The developing method may be any of a liquid addition method, a dipping method, and a spray method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of development. As a coating method, it implements by the spin coating, the casting|flow_spread coating method, the roll coating method, the slit-and-spin coating, or the slit coating method, etc. A colored photosensitive resin composition layer is formed by heating after heat-drying (prebaking) or drying under reduced pressure after application|coating and volatilizing volatile components, such as a solvent. Here, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The developing solution used for image development after patterning exposure is an aqueous solution containing an alkaline compound and surfactant normally. Any of an inorganic and organic alkaline compound may be sufficient as an alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, hydroxide

Potassium, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate,

Potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

Further, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. You may use these inorganic and organic alkaline compounds individually or in combination of 2 or more types, respectively.

The concentration of the alkaline compound in the alkaline developer is, for example, 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, and sorbitan fatty acid ester. , polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylarylsulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate; and the like. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride; quaternary ammonium salts; and the like.

These surfactants can be used individually or in mixture of 2 or more types.

The concentration of the surfactant in the alkaline developer is, for example, 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight.

After image development, it washes with water and can also post-baking for 10 to 60 minutes at 150-230 degreeC as needed.

In addition, the present invention provides an image display device including the color filter. As an image display device of the present invention, specifically, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for portable terminals such as mobile phones, and digital A display device such as a display device for a camera or a display device for a car navigation device, particularly a color display device, is suitable.

Hereinafter, preferred embodiments are presented to help the understanding of the present invention, but these examples are merely illustrative of the present invention and do not limit the appended claims, and are within the scope and spirit of the present invention. It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such variations and modifications fall within the scope of the appended claims.

Preparation of pigment dispersion composition

<Pigment dispersion composition M1>

12.0 parts by mass of the color material of Formula 1, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by mass of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours by a bead mill to prepare a pigment dispersion M1 .

<Pigment dispersion composition M2>

12.0 parts by mass of CI Pigment Yellow 185 as a pigment, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by mass of propylene glycol methyl ether acetate as a solvent Mix/disperse with a bead mill for 12 hours, and the pigment dispersion M2 was prepared.

<Pigment dispersion composition M3>

CI Pigment Blue 15:3 12.0 parts by mass as a pigment, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by mass of propylene glycol methyl ether acetate as a solvent. Dispersion M3 was prepared.

<Pigment dispersion composition M4>

CI Pigment Blue 15:4 12.0 parts by mass as a pigment, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by mass of propylene glycol methyl ether acetate as a solvent Mix/disperse with a bead mill for 12 hours to obtain a pigment Dispersion M4 was prepared.

<Pigment dispersion composition M5>

12.0 parts by mass of CI Pigment Green 58 as a pigment, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by mass of propylene glycol methyl ether acetate as a solvent Mix/disperse with a bead mill for 12 hours, and the pigment dispersion M5 was prepared.

<Pigment dispersion composition M6>

12.0 parts by mass of CI Pigment Green 7 as a pigment, 4.0 parts by mass of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by mass of propylene glycol methyl ether acetate as a solvent are mixed/dispersed with a bead mill for 12 hours, and the pigment dispersion M6 was prepared.

Synthesis of alkali-soluble resin

<Synthesis Example 1>

120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate, 3 parts of n-dodecyl mercapto were added, and nitrogen substitution was carried out. Thereafter, the temperature of the reaction solution was raised to 110° C. with stirring, followed by reaction for 6 hours. The alkali-soluble resin thus synthesized had a solid content acid value of 100.2 mgKOH/g and a weight average molecular weight Mw measured by GPC of about 15110.

Preparation of colored photosensitive resin composition

<Example 1>

16.2 parts of the <pigment dispersion composition M1>,

13.8 parts of the <pigment dispersion composition M2>,

7.5 parts of the <pigment dispersion composition M3>,

4.1 parts of the resin of <Synthesis Example 1>, 4.1 parts of an acrylated product of dipentaerythritol, 0.8 parts of Irgacure OXE01 (manufactured by BASF), and 53.5 parts of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

<Example 2>

16.9 parts of the <pigment dispersion composition M1>,

13.1 parts of the <pigment dispersion composition M2>,

7.5 parts of the <pigment dispersion composition M4>,

4.1 parts of the resin of <Synthesis Example 1>, 4.1 parts of an acrylated product of dipentaerythritol, 0.8 parts of Irgacure OXE01 (manufactured by BASF), and 53.5 parts of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

<Comparative Example 1>

31.0 parts of the <pigment dispersion composition M1>,

6.5 parts of the <pigment dispersion composition M2>,

<Synthesis Example 1> 4.1 parts of resin, 4.1 parts of an acrylated product of dipentaerythritol, 0.8 parts of Irgacure OXE01 (manufactured by BASF), and 53.5 parts of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

<Comparative Example 2>

19.3 parts of the <pigment dispersion composition M5>,

10.7 parts of the <pigment dispersion composition M2>,

7.5 parts of the <pigment dispersion composition M3>,

4.1 parts of the resin of <Synthesis Example 1>, 4.1 parts of an acrylated product of dipentaerythritol, 0.8 parts of Irgacure OXE01 (manufactured by BASF), and 53.5 parts of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

<Comparative Example 3>

19.8 parts of the <pigment dispersion composition M6>,

10.2 parts of the <pigment dispersion composition M2>,

7.5 parts of the <pigment dispersion composition M3>,

4.1 parts of the resin of <Synthesis Example 1>, 4.1 parts of an acrylated product of dipentaerythritol, 0.8 parts of Irgacure OXE01 (manufactured by BASF), and 53.5 parts of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

test example

(1) Manufacture of color filter

Color filters were prepared using the colored photosensitive resin compositions prepared in Examples 1 to 2 and Comparative Examples 1 to 4.

Specifically, each of the colored photosensitive resin compositions was coated on a 2-inch square glass substrate (“EAGLE XG”, manufactured by Corning, Inc.) by spin coating, placed on a heating plate, and maintained at a temperature of 100° C. for 3 minutes to form a thin film did it Then, a test photomask having a pattern for changing the transmittance in a range of 1 to 100% stepwise and a line/space pattern of 1 μm to 50 μm is placed on the thin film, and the interval from the test photomask is 100 μm, and the ultraviolet rays was investigated. In this case, the ultraviolet light source was irradiated with an illuminance of 100 mJ/cm 2 using a 1KW high-pressure mercury lamp containing all of the g, h, and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet light was developed by immersing it in a KOH aqueous solution developing solution of pH 10.5 for 2 minutes. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to prepare a color filter.

(2) Measurement of development speed and adhesion

development speed

The time taken for the unexposed part to completely dissolve in the developer during development was measured and shown in Table 1 below.

adhesion

When the generated pattern was evaluated through an optical microscope, the degree of tearing on the pattern as follows was evaluated and shown in Table 1 below.

○: No tearing in pattern

△: 1-3 pieces torn in pattern

×: 4 or more torn in the pattern

××: 10 or more torn in the pattern

× × ×: No pattern formation

composition Development speed (sec) adhesion Example 1 18 ○ Example 2 19 ○ Comparative Example 1 40 X X X Comparative Example 2 35 X Comparative Example 3 21 △

As can be seen in Table 1, Examples 1 to 2 belonging to the scope of the present invention have a faster development speed than Comparative Examples 1 to 3, and there is no tear in the pattern, so it can be seen that the adhesiveness is excellent.

(3) Measurement of chromaticity and film thickness

Chromaticity and film thickness were measured using the same color filter as in <Experimental Example 1> except that the test photomask was not used.

Chromaticity was measured using a chromaticity meter (OSP-200 manufactured by Olympus Co., Ltd.) prepared in the same manner as in <Experimental Example 1> except that the test photomask was not used, and is shown in Table 2.

The film thickness is shown in Table 2 by measuring the color filter prepared in the same manner as in <Experimental Example 1> and not using the test photomask using a surface profile measuring device (DEKTAK 6M, manufactured by Veeco).

composition film thickness luminance Example 1 2.5 O (satisfied) Example 2 2.5 O (satisfied) Comparative Example 1 3.1 X (bad) Comparative Example 2 3.2 X (bad) Comparative Example 3 3.4 X (bad)

(Gx=0.2000, Gy=0.7100)

As can be seen in Table 2, Examples 1 to 2 belonging to the scope of the present invention have higher luminance than Comparative Examples 1 to 3.

Claims (8)

In the colored photosensitive resin composition,
The composition includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,
The colorant includes Formula 1 below, and further includes one of phthalocyanine blue pigments,
The colorant is a colored photosensitive resin composition, characterized in that it contains 5 to 70% by weight based on the solid content in the colored photosensitive resin composition.
[Formula 1]

(In Formula 1,
A ₁ to A ₁₆ are each independently one of Cl, Br, and H, and _{among A 1} to A ₁₆ , H is 1 to 6, Cl is 0 to 5, and Br is 7 to 13.) According to claim 1,
The phthalocyanine blue pigment is CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 and 15:6 colored photosensitive resin composition, characterized in that used individually or in combination of two or more types. delete According to claim 1,
Colored photosensitive resin composition, characterized in that it has a color coordinate of x = 0.1 to 0.35 when y = 0.6 or more in the XYZ color system. According to claim 1,
Colored photosensitive resin composition, characterized in that it has a color coordinate of x = 0.2 to 0.3 when y = 0.5 to 0.6 in the XYZ color system. According to claim 1,
The photopolymerization initiator is a colored photosensitive resin composition, characterized in that it is included in an amount of 0.1 to 40% by weight based on the total weight of the alkali-soluble resin and the photopolymerizable compound based on the solid content. A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 2 or 4 to 6, characterized in that it is formed. An image display device comprising the color filter of claim 7 .