TWI719016B - 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 specifically, relates to a colored photosensitive resin composition capable of producing a color filter with improved colorability and brightness characteristics The colored photosensitive resin composition includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The colorant includes the pigment represented by Chemical Formula 1, that is, CI Pigment Green 59, and further includes Phthalo One of the cyan blue pigments.

Description

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

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

Color filters are widely used in various display devices such as imaging elements and liquid crystal display devices (LCDs), and their application range is rapidly expanding. The above-mentioned color filter is composed of three colors of red (Red), green (Green) and blue (Blue), or three colors of yellow (Yellow), magenta (Magenta) and cyan (Cyan). constitute.

Each colored pattern of the above-mentioned color filter is usually formed using a coloring photosensitive resin composition containing 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 above-mentioned colored photosensitive resin composition is usually implemented by a photolithography process.

On the other hand, in recent years, various display devices including solid-state imaging devices such as digital cameras are required to have high brightness and high colorability in order to improve processability and quality.

Korean Patent Publication No. 10-2012-0113666 discloses a resin composition using C.I. Pigment Green 7 and C.I. Pigment Yellow 138 and a yellow azo dye, but there is a problem that it cannot satisfy high colorability at the same time.

In addition, Korean Patent Publication No. 10-2012-0158517 discloses that it contains C.I. Pigment Green 7 and C.I. Pigment Blue 15:3 or 15:4 coloring photosensitive resin composition, but there is a problem that it cannot satisfy high brightness.

Prior art literature

Patent literature

Patent Document 1: Korean Patent Publication No. 10-2012-0113666

Patent Document 2: Korean Patent Publication No. 10-2012-0158517

The object of the present invention is to provide a colored photosensitive resin composition with excellent brightness and color rendering properties by including a coloring agent containing a pigment with a specific structure.

In addition, an object of the present invention is to provide a color filter including the above-mentioned colored photosensitive resin composition and an image display device including the color filter and capable of realizing high brightness and high colorability.

The colored photosensitive resin composition according to one embodiment of the present invention for achieving the above-mentioned object is characterized by comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant includes the chemical formula 1. The indicated pigment, that is, CI Pigment Green 59, further contains one phthalocyanine blue pigment.

In addition, the present invention is characterized by a color filter manufactured from the above-mentioned colored photosensitive resin composition and an image display device including the color filter.

The coloring photosensitive resin composition of the present invention contains a coloring agent containing a pigment of a specific structure, thereby having the effect of excellent brightness and coloring properties.

Fig. 1 is a graph showing the transmission spectrum of the coloring agent mentioned in the present invention.

The present invention relates to a colored photosensitive resin composition, a color filter and an image provided with the same For a display device, the colored photosensitive resin composition includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant includes the pigment represented by Chemical Formula 1, that is, CI Pigment Green 59 (hereinafter, Also known as "G59"), and further contains one of the phthalocyanine blue pigments, so that the brightness and coloring properties are excellent.

Hereinafter, the present invention will be explained in detail.

The coloring agent is a component that can express colors such as red, green and blue in order to produce a pattern with a target color. The coloring agent according to the present invention is used as the pigment represented by the chemical formula 1 and contains CI Pigment Green 59 and ZnPc (phthalocyanine Zinc (Zinc Phthalocyanine) is the basic structure. When the colorant of the present invention contains the pigment represented by the following chemical formula 1, that is, C.I. Pigment Green 59, it has the advantage of high color reproduction.

_{A 1} to A _{16 of the} above chemical formula 1 are each independently one of Cl, Br, and H. In A ₁ to A ₁₆ , H is 1 to 6, Cl is 0 to 5, and Br is to 13.

If necessary, the coloring agent according to the present invention may contain one or more selected from the group consisting of commonly used pigments and dyes as components capable of expressing colors such as red/green/green in order to produce a pattern with a target color, or The form of lacquer paste. In this case, regarding the coloring agent containing the pigment of the chemical formula 1 according to the present invention, in the CIE 1931 color space, it may have a color coordinate of x=0.1 to 0.35 when y=0.6 or more, and may have a color coordinate of y=0.5 to 0.6. x=0.2 to 0.3 color coordinates.

The colorant includes the pigment represented by the chemical formula 1, namely, C.I. Pigment Green 59 As an essential component, one of the phthalocyanine blue pigments may be further included. At this time, regarding the phthalocyanine blue pigment, more specifically, CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and other color index (CI) pigments can be separately It is used alone or in combination of two or more, but it is not limited to this.

CI Pigment Green 58 (G58) has the advantage of high brightness, but in order to achieve high colorability, the content of pigments will be increased. If more pigments are contained in the composition, the developability will decrease and the pattern formed by the composition will peel off. It is dangerous, and the problem of sensitivity reduction may occur.

However, the present invention uses the pigment represented by the above chemical formula 1, that is, G59 as a colorant, so that even if the content of the pigment is small, a resist design with high color reproduction can be realized.

On the other hand, when the resin composition contains C.I. Pigment Green 7 (G7), even if the pigment content is reduced, high colorability can be expressed, which is advantageous for use, but there is a problem of low brightness. However, the pigment represented by the above chemical formula 1 contained in the colored photosensitive resin composition of the present invention, that is, G59 exhibits a transmission spectrum and color coordinates similar to CI Pigment Green 7, and is added to the colored photosensitive resin composition And play the function of excellent brightness. It can be confirmed from Fig. 1 that G59 represented by Chemical Formula 1 has a transmission spectrum at a wavelength of 400 nm to 610 nm similarly to C.I. Pigment Green 7.

In this specification, Tmax means the wavelength when the transmittance of the pigment is the maximum, and T _50% means the wavelength when the transmittance of the pigment is 50% or more of the maximum.

The Tmax of the aforementioned C.I. Pigment Green 59 may be 500 to 530 nm. In this case, it is preferable from the viewpoint of excellent colorability.

In addition, the T _{50% of the} aforementioned CI Pigment Green 59 may be 445 to 580 nm. In this case, it is preferable from the viewpoint of excellent colorability.

Further, green and yellow organic pigments or inorganic pigments generally used in this technology can be used. Various pigments used in printing inks, inkjet printer inks, etc. can be used as the above-mentioned pigments. Specifically, water-soluble azo pigments, insoluble azo pigments, and phthalocyanines can be mentioned. Pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinone-based pigments, anthraquinone pigments ( anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc. Examples of the above-mentioned inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, they include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and carbon black. And other metal oxides or composite metal oxides. In particular, as the above-mentioned organic pigments and inorganic pigments, specific examples include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specific examples include the following color index (CI) numbers Pigments, but not limited to this.

CI 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

The above-mentioned pigments can be used alone or in combination of two or more kinds.

In particular, among the yellow pigments exemplified above, one or more pigments selected from C.I. Pigment Yellow 129 and C.I. Pigment Yellow 185 can be preferably used.

Regarding the content of the colorant, it is preferably 5 to 70% by weight, and more preferably 10 to 50% by weight, relative to the solid content in the colored photosensitive resin composition.

If the content of the colorant is less than the above range, the color resolution of the formed pattern will be reduced. If it exceeds the above range, problems such as residual residue or undeveloped due to reduced lithography performance will occur. For the above-mentioned pigment, it is preferable to use a pigment dispersion liquid having a uniform particle size. As an example of the method for uniformly dispersing the particle size of the pigment, a method of adding a pigment dispersant for dispersion treatment, etc. can be mentioned. According to this method, the pigment can be uniformly dispersed in the solution. Pigment dispersion liquid in a loose state.

Specific examples of the above-mentioned pigment dispersants include cationic, anionic, nonionic, amphoteric, polyester, polyamine, etc. surfactants, etc., each of which can be used alone or in combination of two or more. .

As a commercially available product of the above-mentioned pigment dispersant, DISPERBYK-2001 of BYK Company can be cited, but it is not limited thereto.

The alkali-soluble resin according to the present invention is preferably a copolymer of a monomer having a carboxyl group and other monomers copolymerizable therewith.

The above-mentioned other copolymerizable monomers are monomers having carbon-carbon unsaturated bonds. Specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methyl acrylate , Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, methacrylic acid Unsaturated carboxylic acid ester compounds such as benzyl ester; unsaturated carboxylic acid amino alkyl ester compounds such as amino ethyl acrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl methacrylate; vinyl acetate, propionic acid Vinyl carboxylate compounds such as vinyl esters; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; 3-methyl-3-acryloyloxymethyloxetane, 3- Methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxy Methyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-methyl-3-methylpropenyloxyethyl oxetane, 3 -Ethyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane and other unsaturated oxetane carboxylate compounds Wait. These monomers can be used individually or in combination of 2 or more types.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the alkali-soluble resin is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. If the molecular weight distribution of the alkali-soluble resin is 1.5 to 6.0, the developability is excellent, so it is preferable.

With respect to the solid content in the colored photosensitive resin composition, the alkali-soluble resin preferably contains 5 to 90% by weight, more preferably 10 to 70% by weight.

At this time, when the content of the alkali-soluble resin is within the above range, the solubility in the developer is sufficient, the non-pixel portion is less likely to produce development residue on the substrate, and the film of the pixel portion of the exposed portion is less likely to be reduced during development. The defect of the non-pixel part is good.

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

As specific examples of the above-mentioned photopolymerizable monomers, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol diacrylate can be mentioned. , Neopentyl glycol diacrylate, isopentaerythritol acrylate, isopentaerythritol diacrylate, isopentaerythritol triacrylate, diisopentaerythritol diacrylate, diisopentaerythritol triacrylate, Diisopentaerythritol pentaacrylate, diisopentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, two Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Ester etc.

With respect to the solid content in the colored photosensitive resin composition, the photopolymerizable monomer preferably contains 5 to 45% by weight, more preferably 10 to 35% by weight. When the content of the above-mentioned photopolymerizable monomer is included in the above-mentioned range, the intensity or smoothness of the pixel portion is good.

Regarding the photopolymerization initiator according to the present invention, as long as it can polymerize the above-mentioned alkali-soluble resin and photopolymerizable compound, it can be used without particular limitation in its kind. In particular, it is preferable to use an oxime compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, and the like.

As specific examples of the above-mentioned oxime compound, o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and compounds represented by the following chemical formulas 2 to 4, etc. may be mentioned.

[Chemical formula 2]

In addition, as long as the effect of the present invention is not impaired, other photopolymerization initiators commonly used in the art may be further mixed and used. Examples thereof include triazine-based compounds, acetophenone-based compounds, and Imidazole compounds.

As specific examples of the above-mentioned triazine compound, 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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan- 2-yl)vinyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3, 5-triazine and so on.

As a specific example of the above-mentioned acetophenone compound, diethoxy phenethyl can be mentioned. Ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzil dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylphenylthio)-2-morpholinopropane-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl) )Phenyl]propan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc.

As a specific example of the above-mentioned biimidazole-based compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis( 2,3-Dichlorophenyl)-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 4,4',5,5' phenyl group via alkoxy Carbonyl substituted imidazole compounds, etc. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) )-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2 '-Biimidazole.

Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds, and these can be used alone or in combination of two or more.

Examples of the above-mentioned benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

As the above-mentioned benzophenone-based compound, there are, for example, benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzophenone-4'-methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

As the aforementioned thioxanthone compound, for example, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone Tonone and so on.

Examples of the above-mentioned anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene and so on.

In addition, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzalkonium, 9,10- Phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, etc. are used as other photopolymerization initiators.

In addition, a photopolymerization initiation auxiliary agent and the above-mentioned photopolymerization initiator may be used in combination. If a photopolymerization initiator and a photopolymerization initiation aid are used in combination, the photosensitive resin composition containing them can have higher sensitivity and improve productivity.

As the photopolymerization initiation assistant, one or more compounds selected from the group consisting of, for example, an amine compound, a carboxylic acid compound, and an organic sulfide having a thiol group can be preferably used.

Specific examples of the above-mentioned amine compounds include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzene. Ethyl formate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-di Methyl p-toluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler’s ketone), 4,4'-bis(diethylamino)benzophenone, etc. Group amine compound. As the amine compound, an aromatic amine compound is preferably used.

As specific examples of the above-mentioned carboxylic acid compound, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Acetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, Aromatic heteroacetic acids such as naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

As specific examples of the above-mentioned organic sulfide having a thiol group, 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutanoyloxy)butane, 1,3,5-tris(3 -Mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), iso Pentaerythritol tetra (3-mercaptobutyrate), isopentaerythritol tetra (3-mercaptopropionate), diisopentaerythritol hexa (3-mercaptopropionate), tetraethylene glycol bis (3- Mercaptopropionate) and so on.

Regarding the usage amount of the above-mentioned photopolymerization initiator, based on the solid content, relative to The total amount of the alkali-soluble resin and the photopolymerizable compound is preferably 0.1 to 40% by weight, and more preferably 1 to 30% by weight in terms of% by weight. When the above-mentioned photopolymerization initiator is contained in the above-mentioned range, the colored photosensitive resin composition is highly sensitive and the exposure time is shortened. Therefore, the productivity can be improved, the high resolution can be maintained, and the composition can be formed using the above-mentioned composition. The intensity of the pixel portion or the smoothness of the surface of the pixel portion becomes better.

In addition, in the case of using the above-mentioned photopolymerization initiation aid, the amount of the above-mentioned photopolymerization initiation aid, based on the solid content, preferably contains 0.1 to 50 with respect to the total amount of the alkali-soluble resin and the photopolymerizable compound. % By weight, more preferably 1 to 40% by weight.

When the aforementioned photopolymerization initiation aid is contained within the aforementioned range, the sensitivity of the colored photosensitive resin composition becomes higher, and the productivity of a color filter formed using the composition can be improved.

Regarding the solvent according to the present invention, as long as it is effective for dispersing or dissolving the other components contained in the colored photosensitive resin composition, it can be used without particular limitation, and is particularly preferably ethers, aromatic hydrocarbons, ketones, and alcohols. Class, esters or amines, etc.

Regarding the above-mentioned solvents, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether can be specifically exemplified. Diethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, methyl cellosolve Acetate, ethyl cellosolve acetate and other glycol alkyl ether acetates, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Alkylene glycol alkyl ether acetates, methoxybutyl acetate and methoxypentyl acetate and other alkoxyalkyl acetates, benzene, toluene, xylene, mesitylene, etc. Aromatic hydrocarbons, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylenedi Alcohols such as alcohol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, cyclic esters such as γ-butyrolactone, etc.

Among the solvents exemplified above, when considering coating properties and drying properties, it may be better Examples include organic solvents with a boiling point of 100°C to 200°C, more preferably alkylene glycol alkyl ether acetates, ketones, ethyl 3-ethoxypropionate or 3-methoxypropionic acid Esters such as methyl esters, further preferably exemplified by propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxypropane Methyl acid and so on. These solvents can be used individually or in combination of 2 or more types.

Relative to the total amount of the colored photosensitive resin composition, the solvent in the colored photosensitive resin composition of the present invention preferably contains 60 to 90% by weight, more preferably 70 to 85% by weight. When the content of the solvent is within the above range, when using a roll coater, spin coater, slit spin coater, slit coater (sometimes called die coater), inkjet When a coating device such as a printer performs coating, the coating properties can be improved.

In the colored photosensitive resin composition of the present invention, additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, and anticoagulants may be used in combination as necessary.

As specific examples of the above-mentioned other polymer compounds, curable resins such as epoxy resins and maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyacrylic acid halothane, etc. can be mentioned. Thermoplastic resins such as esters, polyesters, polyurethanes, etc.

The above-mentioned curing agent is used to improve deep curing and mechanical strength. Specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

Among the above curing agents, specific examples of epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, Novolac type epoxy resins, other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives and cyclic epoxy resins of these epoxy resins Aliphatic, alicyclic or aromatic epoxy compounds other than oxygen resins and brominated derivatives, butadiene (co)polymer epoxides, isoprene (co)polymer epoxides, (methyl) )Glycidyl acrylate (co)polymer, triglycidyl isocyanurate Wait.

Among the above curing agents, specific examples of oxetane compounds include carbonate dioxetane, xylene dioxetane, adipate dioxetane, and p-benzene. Diformate dioxetane, cyclohexane dicarboxylic acid dioxetane, etc.

The above-mentioned curing agent can be used in combination with a curing auxiliary compound, which together with the curing agent can cause the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound to ring-open and polymerize. Regarding the above-mentioned curing auxiliary compound, there are, for example, polycarboxylic acids, polycarboxylic anhydrides, acid generators, and the like. For the above-mentioned polycarboxylic acid anhydrides, commercially available epoxy resin curing agents can be used. As specific examples of the epoxy resin curing agent mentioned above, trade name (ADEKA HARDENER EH-700) (manufactured by ADEKA Kogyo Co., Ltd.), trade name (RIKACID HH) (manufactured by Shin Nippon Rika Co., Ltd.), trade name (MH-700) (manufactured by Shin Nihon Rika Co., Ltd.), etc. The curing agents exemplified above can be used alone or in combination of two or more kinds.

The above-mentioned surfactant can be used in order to further improve the film formability of the photosensitive resin composition, and a fluorine-based surfactant, an organosilicon-based surfactant, or the like can be preferably used.

Regarding the aforementioned organosilicon-based surfactants, for example, as commercially available products, there are DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Organosilicon, and TSF-4440, TSF-4300, TSF-4300, etc. of GE Toshiba Organosilicon TSF-4445, TSF-4446, TSF-4460, TSF-4452, etc. Regarding the above-mentioned fluorine-based surfactants, for example, as commercially available products, there are MEGAFAC F-470, F-471, F-475, F-482, F-489, etc. of Dainippon Ink Chemical Industry Co., Ltd. The surfactants exemplified above can be used alone or in combination of two or more kinds.

As specific examples of the above adhesion promoter, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris(2-methoxyethoxy)silane, N-(2-amino group) can be mentioned. Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, etc.

The adhesion promoters exemplified above can be used alone or in combination of two or more kinds. The adhesion promoter preferably contains 0.01 to 10% by weight, and more preferably contains 0.05 to 2% by weight with respect to the solid content of the photosensitive resin composition.

As specific examples of the above antioxidants, 2,2'-thiobis(4-methyl-6-tertiary butylphenol), 2,6-di-tertiarybutyl-4-methylphenol can be cited Wait.

As a specific example of the above-mentioned anticoagulant, sodium polyacrylate etc. can be mentioned.

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

The above-mentioned liquid crystal display device includes, in addition to the above-mentioned color filter, a structure known to those skilled in the art of the present invention.

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

The substrate is a transparent material, and for the stability of the color filter, a material with sufficient strength and support is used. It is better to use glass with excellent chemical stability and high strength.

The said colored pattern is manufactured by apply|coating the said colored photosensitive resin composition on a board|substrate, and photocuring and developing.

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

The above-mentioned colored pattern can be formed, for example, by the following method.

First, the above composition is coated on a substrate or a layer formed of the solid components of the photosensitive resin composition, and volatile components such as solvents are removed from the coated photosensitive resin composition layer by prebaking. A smooth coating film is obtained. The coating film thus obtained, by using Irradiate ultraviolet rays on the mask forming the target pattern. At this time, it is preferable to uniformly irradiate the entire exposure part with parallel light, and use devices such as a mask positioner or a stepper to implement precise position alignment of the mask and the substrate. In addition, afterwards, the cured coating film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed part and develop, thereby obtaining the target pattern shape.

Regarding the development method, a liquid addition method, a dipping method, a spray method, etc. may be used. In addition, during development, the substrate can be tilted to any angle. As the coating method, for example, it is implemented by a spin coating method, a cast coating method, a roll coating method, a slit spin coating method, or a slit coating method. After application, heat drying (pre-baking) or heating after drying under reduced pressure is used to volatilize volatile components such as a solvent to form a colored photosensitive resin composition layer. Among them, the heating temperature is usually 70 to 200°C, preferably 80 to 130°C. The developer used in the development after patterning exposure is an aqueous solution usually containing an alkaline compound and a surfactant. Regarding the basic compound, both inorganic and organic basic compounds may be used. As specific examples of inorganic alkaline compounds, sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, silicon Potassium acid, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia water, etc.

In addition, as specific examples of organic basic compounds, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoiso Propylamine, diisopropylamine, ethanolamine, etc. These inorganic and organic basic compounds can be used alone or in combination of two or more kinds.

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

Regarding the surfactant in the alkali developer, it may be any one of a nonionic surfactant, an anionic surfactant, or a cationic surfactant. As specific examples of nonionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene derivatives, oxyethylene/oxypropylene Block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Ethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, etc.

Specific examples of anionic surfactants include higher alcohol sulfates such as sodium lauryl sulfate or sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate; Alkyl aryl sulfonates such as sodium alkylbenzene sulfonate or sodium dodecyl naphthalene sulfonate; etc. As specific examples of the cationic surfactant, amine salts such as stearylamine hydrochloride or lauryltrimethylammonium chloride; quaternary ammonium salts; and the like can be mentioned.

These surfactants can be used alone or in combination of two or more kinds.

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

After development, it is washed with water, and if necessary, it can be baked at 150 to 230°C for 10 to 60 minutes.

In addition, the present invention provides an image display device including the above-mentioned color filter. The image display device of the present invention is specifically suitable for portable devices such as liquid crystal displays (liquid crystal display devices; LCD), organic EL displays (organic EL display devices), liquid crystal projectors, display devices for game consoles, and portable phones. Display devices such as terminal display devices, digital camera display devices, and car navigation display devices are particularly suitable for color display devices.

In the following, in order to facilitate the understanding of the present invention, preferred embodiments are provided, but these embodiments are only used to illustrate the present invention and do not limit the scope of the accompanying patent application. Those familiar with the art should understand that in the present invention Within the scope and scope of technical ideas, various changes and modifications can be made to the embodiments, and such changes and modifications should also belong to the scope of the attached patent application. Hereinafter, the "%" and "parts" indicating the content are based on weight unless otherwise mentioned.

Pigment dispersion composition manufacturing <Pigment dispersion composition M1>

Using a sand mill, use 12.0 parts by weight of C.I. Pigment Green 59 as the pigment dispersant 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were mixed/dispersed for 12 hours to produce pigment dispersion liquid M1.

<Pigment dispersion composition M2>

Using a sand mill, mix 12.0 parts by weight of CI Pigment Yellow 185 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent for 12 It is mixed/dispersed for hours, thereby manufacturing pigment dispersion liquid M2.

<Pigment dispersion composition M3>

Using a sand mill, mix 12.0 parts by weight of CI Pigment Blue 15:3 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent The mixing/dispersion was carried out for 12 hours, thereby manufacturing the pigment dispersion liquid M3.

<Pigment dispersion composition M4>

Using a sand mill, 12.0 parts by weight of CI Pigment Blue 15:4 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent The mixing/dispersion was performed for 12 hours, thereby manufacturing the pigment dispersion liquid M4.

<Pigment dispersion composition M5>

Using a sand mill, 12.0 parts by weight of CI Pigment Green 58 as a pigment, 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, and 84 parts by weight of propylene glycol methyl ether acetate as a solvent were used for 12 It was mixed/dispersed for hours to produce pigment dispersion liquid M5.

<Pigment dispersion composition M6>

Using a sand mill, use 12.0 parts by weight of C.I. Pigment Green 7 as a pigment, and 4.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, as a solvent 84 parts by weight of propylene glycol methyl ether acetate were mixed/dispersed for 12 hours to produce pigment dispersion liquid M6.

Synthesis of alkali-soluble resin <Synthesis Example 1>

Put 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of AIBN, and 13.0 parts by weight of acrylic acid into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. Parts, 10 parts by weight of benzyl methacrylate, 57.0 parts by weight of 4-methylstyrene, 20 parts by weight of methyl methacrylate, 3 parts by weight of n-dodecyl mercaptan, and nitrogen replacement. After that, stirring was performed, and the temperature of the reaction liquid was raised to 110°C, and the reaction was performed for 6 hours. The acid value of the solid content of the alkali-soluble resin synthesized in this way is 100.2 mgKOH/g, and the weight average molecular weight Mw measured by GPC is about 15,110.

Manufacture of colored photosensitive resin composition <Example 1>

16.2 parts by weight of the above-mentioned pigment dispersion composition M1, 13.8 parts by weight of the above-mentioned pigment dispersion composition M2, 7.5 parts by weight of the above-mentioned pigment dispersion composition M3, 4.1 parts by weight of the resin of Synthesis Example 1, and diisoprene hexaacrylic acid Ester (KAYARAD DPHA; manufacturing company: Nippon Kayaku Co., Ltd.) 4.1 parts by weight, Irgacure OXE01 (Irgacure OXE01, manufactured by BASF) 0.8 parts by weight, and 53.5 parts by weight of propylene glycol monomethyl ether acetate are mixed to produce Color photosensitive resin composition.

<Example 2>

16.9 parts by weight of the above-mentioned pigment dispersion composition M1, 13.1 parts by weight of the above-mentioned pigment dispersion composition M2, 7.5 parts by weight of the above-mentioned pigment dispersion composition M4, 4.1 parts by weight of the resin of Synthesis Example 1, and diisoprene hexaacrylic acid Ester (KAYARAD DPHA; manufacturing company: Nippon Kayaku Co., Ltd.) 4.1 parts by weight, Yanjiagoo OXE01 (manufactured by BASF) 0.8 parts by weight, and 53.5 parts by weight of propylene glycol monomethyl ether acetate are mixed to produce color photosensitive Resin composition.

<Comparative Example 1>

31.0 parts by weight of the above-mentioned pigment dispersion composition M1, 6.5 parts by weight of the above-mentioned pigment dispersion composition M2, 4.1 parts by weight of the resin of Synthesis Example 1, and diisoprene hexaacrylate (KAYARAD DPHA; manufacturing company: Nippon Kayaku (Company) 4.1 parts by weight, 0.8 parts by weight of Yanjiaco OXE01 (manufactured by BASF), and 53.5 parts by weight of propylene glycol monomethyl ether acetate were mixed to produce a colored photosensitive resin composition.

<Comparative Example 2>

19.3 parts by weight of the above-mentioned pigment dispersion composition M5, 10.7 parts by weight of the above-mentioned pigment dispersion composition M2, 7.5 parts by weight of the above-mentioned pigment dispersion composition M3, 4.1 parts by weight of the resin of Synthesis Example 1, and diisoprene hexaacrylic acid Ester (KAYARAD DPHA; manufacturing company: Nippon Kayaku Co., Ltd.) 4.1 parts by weight, Yanjiagoo OXE01 (manufactured by BASF) 0.8 parts by weight, and 53.5 parts by weight of propylene glycol monomethyl ether acetate are mixed to produce color photosensitive Resin composition.

<Comparative Example 3>

19.8 parts by weight of the above-mentioned pigment dispersion composition M6, 10.2 parts by weight of the above-mentioned pigment dispersion composition M2, 7.5 parts by weight of the above-mentioned pigment dispersion composition M3, 4.1 parts by weight of the resin of Synthesis Example 1, and diisoprene hexaacrylic acid Ester (KAYARAD DPHA; manufacturing company: Nippon Kayaku Co., Ltd.) 4.1 parts by weight, Yanjiagoo OXE01 (manufactured by BASF) 0.8 parts by weight, and 53.5 parts by weight of propylene glycol monomethyl ether acetate are mixed to produce colored photosensitive Resin composition.

Test example

(1) Manufacturing of color filters: Example 1 and Comparative Example 2

The color filter was manufactured using the colored photosensitive resin composition manufactured in the above-mentioned Example 1 and Comparative Example 2.

The coloring photosensitive resin composition of the above-mentioned Example 1 or Comparative Example 2 was coated on a glass substrate at a coating speed of 200, 300, and 400RPM by a spin coating method. After that, it was placed on a hot plate and maintained at a temperature of 100°C for 3 minutes. Then, as an ultraviolet light source, a 1 kW high-pressure mercury lamp containing all g, h, and i lines ^{was irradiated with an illuminance of 100 mJ/cm 2} and heated in a heating oven at 220° C. for 20 minutes to manufacture a color filter.

(2) Manufacturing of color filters: Example 2 and Comparative Examples 1 and 3

The color filter was manufactured using the colored photosensitive resin composition manufactured in the above-mentioned Example 2 and Comparative Examples 1 and 3.

Specifically, each of the above-mentioned colored photosensitive resin compositions was coated on a 2 inch x 2 inch glass substrate (made by Corning Incorporated, "EAGLE XG") by a spin coating method, and then placed on a hot plate, Maintain a temperature of 100°C for 3 minutes to form a thin film. Next, on the above film, a test mask with a pattern that gradually changes the transmittance in the range of 1 to 100% and a line/space pattern of 1 μm to 50 μm is placed, and the distance between the test mask and the test mask is 100 μm. Expose ultraviolet rays. At this time, the ultraviolet light source, comprising g, h, i-line of 1kW high pressure mercury lamp is irradiated to all of 100mJ / cm ² of illumination, especially without using the optical filter. The film irradiated with ultraviolet rays was immersed in a pH 10.5 aqueous KOH developing solution for 2 minutes for development. After the above-mentioned film-coated glass plate was washed with distilled water, it was dried by blowing nitrogen gas, and heated in a heating oven at 200° C. for 25 minutes to manufacture a color filter.

(3) Measurement of developing speed and adhesion

Developing speed

The time required for the non-exposed part to be completely dissolved in the developer solution during development was measured and shown in Table 1 below.

Tightness

When the formed pattern was evaluated by an optical microscope, it was evaluated by the degree of peeling phenomenon on the following pattern, and it is shown in Table 1 below.

○: There is no peeling on the pattern

△: 1 to 3 cracks on the pattern

×: 4 to 9 cracks on the pattern

××: More than 10 peelings on the pattern

×××: The pattern could not be formed

It can be seen from Table 1 above that, compared with Comparative Examples 1 to 3, Examples 1 to 2 belonging to the scope of the present invention have a faster development speed and no peeling on the pattern, so that the adhesion is excellent.

(4) Measurement of chromaticity (color coordinates), brightness, film thickness and sensitivity

Chroma, brightness and film thickness

The chromaticity and film thickness were measured using a color filter manufactured in the same manner as in Test Example 2 above except that the test mask was not used.

Regarding chromaticity (color coordinates) and brightness, a color filter (manufactured by Olympus Corporation, OSP-200) was used to measure a color filter manufactured in the same manner as in Test Example 2 above except that the test mask was not used, and it was shown in Table 2.

Brightness evaluation criteria

O: above 47.0, suitable for

X: less than 47.0, not suitable

Regarding the film thickness, the color filter manufactured in the same manner as in Test Example 2 above was measured with a surface profile meter (manufactured by Veeco, DEKTAK 6M) except that the test mask was not used, and the color filter is shown in Table 2.

Sensitivity determination

90%時之最小曝光量表示為靈敏度，將根據下述評價基準之結果記載於表2。 Use a pattern mask with a stepwise change in transmittance in the range of 1 to 100%. Except for this, proceed in the same way as the above-mentioned brightness measurement method. Set (film thickness before development/film thickness after development) × 100%)

The minimum exposure at 90% is expressed as sensitivity, and the results based on the following evaluation criteria are shown in Table 2.

<Evaluation criteria>

When the sensitivity is less than 60 (mJ/cm ² ) and the pattern remains: ○

When the sensitivity is above 60 (mJ/cm ² ) and the pattern remains: ×

It can be seen from Table 2 above that, compared with Comparative Examples 1 to 3, Examples 1 to 2 belonging to the scope of the present invention have higher brightness and sensitivity.

(5) Measured according to the color coordinates of the coated RPM

The color coordinates of the colored layer of the color filter manufactured in the manufacture of the above-mentioned (2) color filter were measured with a microspectrometer OSP-SP2000, and the results are shown in Table 3 below.

It can be confirmed from Table 3 above that when compared with Comparative Example 2, for the case of Example 1, at a coating speed of 300 to 500 RPM, it satisfies the preferred color coordinates including the range of x=0.1 level Range, showing more excellent coloring properties.

Claims (8)

A colored photosensitive resin composition, characterized in that it contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the colorant contains the pigment represented by the following chemical formula 1, namely, CI pigment Green 59, the colorant excludes CI Pigment Green 7, and further contains one of the phthalocyanine blue pigments, and the molecular weight distribution of the alkali-soluble resin, that is, the weight average molecular weight (Mw)/number average molecular weight (Mn) is 1.5 to 6.0; and

In the chemical formula 1, A ₁ to A ₁₆ are each independently one of Cl, Br, and H. In A ₁ to A ₁₆ , H is 1 to 6, Cl is 0 to 5, and Br is 7 to 13 pieces. According to the colored photosensitive resin composition of claim 1, wherein, for the phthalocyanine blue pigment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are each used alone or Use a combination of two or more types. The colored photosensitive resin composition of claim 1, wherein the colorant is contained in an amount of 5 to 70% by weight relative to 100 parts by weight of solid content in the colored photosensitive resin composition. Such as the colored photosensitive resin composition of claim 1, wherein In the CIE 1931 color space, it has color coordinates of x=0.1 to 0.35 when y=0.6. Such as the colored photosensitive resin composition of claim 1, wherein when y=0.5 to 0.6 in the CIE 1931 color space, x=0.2 to 0.3 color coordinates. The colored photosensitive resin composition of claim 1, wherein the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight based on the solid content relative to the total weight of the alkali-soluble resin and the photopolymerizable compound. A color filter characterized in that it is formed using the colored photosensitive resin composition according to any one of claims 1 to 6. An image display device characterized in that it includes a color filter as in claim 7.

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