KR20120105574A - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition and a color filter using the same are provided to improve the contrast ratio and the brightness of the composition. CONSTITUTION: A photo-sensitive resin composition includes a colorant with a dye represented by chemical formula 1. The composition further includes an acryl-based binder resin, a photo-polymerizable monomer, a photo-polymerization initiator, and a solvent. The colorant further includes a pigment. The pigment includes a green pigment, a yellow pigment, or the combination of the same. The weight ratio of the dye and the pigment is in a range between 1:99 and 99:1. A color filter is manufactured by using the composition.

Description

Photosensitive resin composition for color filters and color filter using the same {{PHOTOSENSITIVE RESIN COMPOSITION AND COLOR FILTER USING THE SAME}

The present substrate relates to a photosensitive resin composition for color filters and a color filter using the same.

Color filters are used in liquid crystal displays (LCDs), optical filters in cameras, and the like, and are manufactured by applying a fine region colored in three or more colors onto a solid-state imaging device or a transparent substrate. Such a colored thin film is usually formed by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like.

The pigment dispersion method is a method for forming a colored thin film by repeating a series of processes of applying, exposing, developing and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. The pigment dispersion method can improve heat resistance and durability, which are the most important properties of the color filter, and have the advantage of keeping the thickness of the film uniform.

However, there is a need for a method capable of preventing the reduction in contrast ratio and brightness caused by the particle size of the pigment.

In such a method, there is a method of enhancing the dispersion of the pigment to reduce the size of the pigment particles, but there are technical limitations.

Therefore, instead of increasing the degree of dispersion of the pigment, a method of replacing the pigment with a dye or adding a dye to the pigment dispersion has been developed.

One aspect of the present invention is to provide a photosensitive resin composition for color filters having a high contrast ratio and high brightness, and excellent in pattern formability, developability, chemical resistance and color reproducibility.

Another aspect of the present invention is to provide a color filter manufactured using the photosensitive resin composition for the color filter.

One aspect of the present invention provides a photosensitive resin composition for color filters comprising a colorant containing a dye represented by the following formula (1).

[Formula 1]

(In the formula 1,

X and Y are the same as or different from each other, and C1 to C20 alkyl group, C3 to C30 cycloalkyl group, C1 to C20 alkyl alcohol group, carboxylic acid group, C2 to C20 alkenyl alcohol group, C1 to C20 alkyl carboxylic acid group, or C2 To C20 alkenyl carboxylic acid group, or X and Y may be connected to each other to form a hydrocarbon ring,

R ¹ , R ² and Z are the same as or different from each other, halogen atom, C1 to C20 alkyl halogen group, sulfonic acid group, C1 to C20 alkyl sulfonic acid group, C2 to C20 alkenyl sulfonic acid group, sulfone imide group, C1 to C20 alkyl Sulfone imide groups, C1 to C20 alkyl alcohol groups, carboxylic acid groups, C2 to C20 alkenyl alcohol groups, C1 to C20 alkyl carboxylic acid groups, C2 to C20 alkenyl carboxylic acid groups, C1 to C20 alkoxyalkyl sulfonic acid groups, C2 to C20 C20 alkoxyalkenyl sulfonic acid group, C2 to C20 alkoxyalkynyl sulfonic acid group, C1 to C20 alkoxyalkyl carboxylic acid group, C2 to C20 alkoxyalkenyl carboxylic acid group, or C2 to C20 alkoxyalkynyl carboxylic acid group,

R ³ to R ⁶ are the same as or different from each other, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 To C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C3 to C30 cycloalkynyl group, or substituted or unsubstituted C6 to C30 aryl group,

W is a halogen atom, perchlorate (ClO ₄ ), or hexafluorophosphate (PF ₆ ).)

X and Y in Formula 1 may be connected to each other to form a hydrocarbon ring.

The dye represented by Chemical Formula 1 may include a dye represented by Chemical Formula 2-1 or Chemical Formula 2-2.

[Formula 2-1]

[Formula 2-2]

The photosensitive resin composition for color filters may further include an acrylic binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.

The color filter photosensitive resin composition is 1 to 40% by weight of the colorant; 1 to 30% by weight of the acrylic binder resin; 1 to 20% by weight of the photopolymerizable monomer; 0.01 to 10 wt% of the photopolymerization initiator; And the balance of the solvent. 　

The colorant may further include a pigment, and the pigment may include a green pigment, a yellow pigment, or a combination thereof.

The colorant may include the dye and the pigment in a weight ratio of about 1:99 to about 99: 1.

The acrylic binder resin may include a first ethylenically unsaturated monomer including (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof; And styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylic Copolymers of second ethylenically unsaturated monomers comprising laterate, vinyl acetate, vinyl benzoate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, or combinations thereof. .

The photopolymerizable monomer is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth Ta) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate or combinations thereof.

The photosensitive resin composition for color filters is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or an additive of a combination thereof.

Another aspect of the present invention provides a color filter manufactured using the photosensitive resin composition for color filters.

Other details of aspects of the invention are included in the following detailed description.

The photosensitive resin composition for color filters has a high contrast ratio and high brightness, and is excellent in pattern formability, developability, chemical resistance, and color reproducibility, and thus may be usefully used in color filters.

1 is a graph showing contrast ratios of color filters prepared from the photosensitive resin compositions for color filters of Examples 1 to 7 and Comparative Examples 1 and 2. FIG.
2 is a graph showing the transmittance of the photosensitive resin composition for color filters according to Examples 1, 2, 5, and 7 and Comparative Example 1. FIG.
3 is a graph showing the transmittance of the photosensitive resin composition for color filters according to Examples 3, 4 and 6 and Comparative Example 2.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, It means substituted with a substituent of C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C30 heteroaryl group or a combination thereof.

In addition, "hetero" means at least one hetero atom of at least one of N, O, S and P in the ring group unless otherwise specified in the present specification.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

The photosensitive resin composition for color filters according to one embodiment includes (A) a colorant, a (B) acrylic binder resin, (C) a photopolymerizable monomer, (D) a photopolymerization initiator, and (E) a solvent.

Each component is demonstrated concretely below.

(A) colorant

The colorant may include a dye represented by Formula 1 below.

[Formula 1]

X and Y in Formula 1 are the same or different from each other, C1 to C20 alkyl group, C3 to C30 cycloalkyl group, C1 to C20 alkyl alcohol group, carboxylic acid group, C2 to C20 alkenyl alcohol group, C1 to C20 alkyl carbo Acid groups, or C2 to C20 alkenyl carboxylic acid groups, or X and Y may be connected to each other to form a hydrocarbon ring, but is not limited thereto.

The hydrocarbon ring may be a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group Can be.

Among these, in order to efficiently implement green color, X and Y may be connected to each other to form a hydrocarbon ring.

R ¹ , R ² and Z in Formula 1 are the same or different from each other, a halogen atom, C1 to C20 alkyl halogen group, sulfonic acid group, C1 to C20 alkyl sulfonic acid group, C2 to C20 alkenyl sulfonic acid group, sulfonimide group , C1 to C20 alkyl sulfone imide group, C1 to C20 alkyl alcohol group, carboxylic acid group, C2 to C20 alkenyl alcohol group, C1 to C20 alkyl carboxylic acid group, C2 to C20 alkenyl carboxylic acid group, C1 to C20 alkoxyalkyl Sulfonic acid group, C2 to C20 alkoxyalkenyl sulfonic acid group, C2 to C20 alkoxyalkynyl sulfonic acid group, C1 to C20 alkoxyalkyl carboxylic acid group, C2 to C20 alkoxyalkenyl carboxylic acid group, or C2 to C20 alkoxyalkynyl carboxylic acid group It may be, but is not limited thereto.

R ³ to R ⁶ in Formula 1 are the same as or different from each other, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, substituted Or an unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, a substituted or unsubstituted C3 to C30 cycloalkynyl group, or a substituted or unsubstituted C6 to C30 aryl group, but is not limited thereto. It doesn't happen.

W in Chemical Formula 1 may be a halogen atom, perchlorate (ClO ₄ ), or hexafluorophosphate (PF ₆ ).

Specific examples of the dye may be a dye represented by the following formula 2-1 or 2-2, but is not limited thereto.

[Formula 2-1]

[Formula 2-2]

The dye may represent green.

The dye has excellent solubility, and the photosensitive resin composition including the dye may exhibit excellent brightness and pattern formability.

The colorant may be included in 1 to 40% by weight, specifically, 5 to 30% by weight based on the total amount of the photosensitive resin composition for the color filter. When the colorant is included in the above range can exhibit excellent contrast ratio and brightness.

In one embodiment, the above-mentioned dyes may be used alone or as a colorant, or may be used in combination with a pigment for improving durability.

The pigment may be used a green pigment, a yellow pigment or a combination thereof.

The dye may be used in combination with the pigment as it can achieve π-orbital interaction, hydrogen bonding and the like.

Examples of the green pigments include halogenated phthalocyanine green pigments, and examples of the halogenated phthalocyanine green pigments include copper halide phthalocyanine green pigments and zinc halide phthalocyanine green pigments.

Examples of the copper halide phthalocyanine green pigment include C.I. Green pigment 7, chlorinated copper bromide phthalocyanine pigment, C.I. Green pigment 36, C.I. Green pigment 37; and the like.

Examples of the zinc halide phthalocyanine green pigment include chlorinated zinc bromide phthalocyanine pigments. Green pigment 58; and the like.

The green pigments may be used alone or in combination. Preferably, the chlorinated copper bromide phthalocyanine pigment and the chlorinated zinc bromide phthalocyanine pigment may be used.

Examples of the yellow pigment that can be used for toning include C.I. Yellow pigment 138, C.I. Yellow pigment 139, C.I. Diazo-based yellow pigments such as yellow pigment 150 and the like can be used.

The yellow pigment may have an average particle diameter of 40 to 100 nm, specifically, may have an average particle diameter of 40 to 50 nm.

The dye and the pigment may be mixed and used in a weight ratio of 1:99 Pa to 99: 1, specifically, may be used in a weight ratio of 20:80 to 80:20. When mixed in the weight ratio range it can have excellent durability.

(B) acrylic binder resin

The acrylic binder resin is a first ethylenically unsaturated monomer 　 And a copolymer of a second ethylenically unsaturated monomer copolymerizable therewith, and a resin including at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.

The first ethylenically unsaturated monomer may be included in the amount of 5 to 50% by weight, specifically, 10 to 40% by weight with respect to the total amount of the acrylic binder resin.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the acrylic binder resin include (meth) acrylic acid / benzyl methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene copolymer, (meth) acrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate. Methacrylate copolymer, (meth) acrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but are not limited thereto, and these may be used alone or in combination of two or more thereof. have.

The weight average molecular weight of the acrylic binder resin may be 3,000 to 150,000 g / mol, specifically 5,000 to 50,000 g / mol, and more specifically 2,000 to 30,000 g / mol. 　　 When the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the black photosensitive resin composition are excellent, the viscosity is appropriate, and the adhesion to the substrate is excellent when manufacturing the light shielding layer.

The acid value of the acrylic binder resin may be 15 to 60 mgKOH / g, specifically 20 to 50 mgKOH / g. When the acid value of the acrylic binder resin is within the above range, the resolution of the pixel pattern is excellent.

The acrylic binder resin may be included in 1 to 30% by weight based on the total amount of the photosensitive resin composition for the color filter, specifically 　 It may be included in 3 to 20% by weight. When the acrylic binder resin is included in the above range, the viscosity of the photosensitive resin composition is appropriately maintained, and thus excellent in patternability, processability and developability in manufacturing a color filter and a light shielding layer.

(C) Photopolymerization  Monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-450 ^{® from} Toagosei Kagaku Kogyo Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nihon Kayaku Co., Ltd., KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 1 to 20% by weight, specifically 3 to 15% by weight, based on the total amount of the photosensitive resin composition for color filters. In the case where the photopolymerizable monomer is included in the above range, curing is sufficiently performed at the time of exposure in the pattern forming step to provide excellent reliability and excellent developability to an alkaline developer.

(D) Light curing Initiator

The photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned.

Examples of the benzophenone-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diiso Propyl thioxanthone, 2-chloro thioxanthone, etc. are mentioned.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal and the like.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-tri chloromethyl (Piperonyl) -6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, etc. are mentioned.

Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone and the like.

In addition to the compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator may be included in an amount of 0.01 to 10% by weight, and specifically 0.1 to 5% by weight, based on the total amount of the photosensitive resin composition for color filters. When the photopolymerization initiator is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and it is possible to prevent a decrease in transmittance due to the unreacted initiator.

(E) solvent

The solvent may be used materials having compatibility with the photopolymerizable monomer, the binder resin, the photopolymerization initiator, and the colorant, but do not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butylkenone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Acetate alkoxyalkyl esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.

Considering miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.

The solvent may be included in the balance relative to the total amount of the photosensitive resin composition for the color filter, specifically, may be included in 50 to 80% by weight. When the solvent is included in the above range, as the photosensitive resin composition for color filters has an appropriate viscosity, processability in manufacturing color filters is excellent.

(F) Other additives

The photosensitive resin composition for color filters may include malonic acid to prevent stains and spots upon application and to prevent leveling characteristics and to prevent generation of residue due to undeveloped. 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; It may further include other additives such as radical polymerization initiators.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and γ -Glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned, These can be used individually or in mixture of 2 or more types.

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like by BM Chemie; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. by Dai Nippon Inky Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Corporation; Asahi Grass Co., Ltd. Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc .; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to the desired physical properties.

The photosensitive resin composition may further include an epoxy compound in order to improve adhesion to a substrate.

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

The epoxy compound may be included in an amount of 0.01 to 5 parts by weight, and specifically 0.1 to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition for color filters. When the epoxy compound is included in the above range, it is excellent in adhesion, heat resistance and chemical resistance.

The photosensitive resin composition for color filters described above may have a transmittance of 75 to 95%. When having a transmittance within the above range it can be realized a clear green color when manufacturing the color filter.

Another embodiment provides a color filter manufactured using the photosensitive resin composition for color filters described above. The manufacturing method of the said color filter is as follows.

Using a suitable method such as spin coating or slit coating the photosensitive resin composition for color filters described above on a glass substrate on which nothing is applied and a glass substrate on which a protective film of SiN _x is applied in a thickness of 500 to 1500 kPa. And each of them is applied in a thickness of 3.1 to 3.4 mu m. After application, light is irradiated to form a pattern required for the color filter. After irradiating the light, the coating layer is treated with an alkaline developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. By repeating this process in accordance with the required number of R, G, and B colors, a color filter having a desired pattern can be obtained.

Further, in the above process, the image pattern obtained by the development can be further heated, cured by actinic ray irradiation or the like to further improve crack resistance, solvent resistance, and the like.

The color filter may have a high contrast ratio. Specifically, the color filter may have a value of 10000 or more when the Gy coordinate is 0.595.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Manufacturing example  1-1: Dye Manufacturing

5.9 g (17.0 mmol) of 3-allyl-1,1,2-trimethyl-1H-benzo [e] indolium perchlorate, 3-Zyl-1,1,2-trimethyl-1H-benzoindolium perchlorate, and (Z A mixture of 1.46 g (8.5 mmol) of 2-chloro-3- (hydroxymethylene) cyclohex-1-enecarbaldehyde ((Z) -2-chloro-3- (hydroxymethylene) cyclohex-1-enecarbaldehyde) Then, 1.53 g (18.7 mmol) of sodium acetate and 25 g of acetic anhydride were added and heated at 80 ° C. for 2 hours. The mixture was cooled to room temperature, poured into water, and stirred for 1 hour. When crystals were formed, the mixture was washed with water and methanol and dried to obtain 5.1 g of a compound represented by the following Chemical Formula 2-1.

(1H NMR: 1.7 (6H), 1.82 (1H), 2.82 (6H), 2.95 (2H), 3.53 (4H), 5.03 (4H), 5.78 (2H) 6.72 (2H), 7.30 (3H), 8.12 ( 2H))

[Formula 2-1]

Manufacturing example  1-2: dye manufacturer

In Preparation Example 1-1, 3- (2-hydroxyethyl) -1,1,2-trimethyl-1H-benzo indrium perchlorate (3- (2-hydroxyethyl) -1,1,2-trimethyl-1H- 8.84 g (25.0 mmol) of benzo [e] indolium perchlorate) and (Z) -2-chloro-3- (hydroxymethylene) cyclohex-1-enecarbaldihydride ((Z) -2-chloro-3- ( Preparation Example 1-1 was added to a mixture of 2.06 g (12.0 mmol) of hydroxymethylene) cyclohex-1-enecarbaldehyde) and 2.14 g (26.0 mmol) of sodium acetate and 25 g of acetic anhydride were added. In the same manner as in to obtain a compound represented by the formula (2-2).

(1H NMR: 1.7 (6H), 1.82 (1H), 2.82 (6H), 2.95 (2H), 3.53 (4H), 3.82 (4H), 4.78 (2H), 6.72 (2H), 7.30 (3H), 8.12 (2H))

[Formula 2-2]

Manufacturing example  2-1: Pigment Dispersion Preparation

CI green pigment 58 (DIC) 15% by weight, dispersant (BYK, LPN2001) 4% by weight, polybenzyl methacrylate resin (Sigma Aldrich) 4% by weight, and propylene glycol methyl ethyl acetate 77% by weight for 46 hours During the dispersion using a paint shaker (Asada Co., Ltd.), a green pigment pigment dispersion was prepared.

Manufacturing example  2-2: Pigment Dispersion Preparation

A yellow pigment dispersion was prepared in the same manner as in Preparation Example 2-1, except that C.I. Yellow Pigment 150 (Lanxess Corporation) was used instead of C.I. Green Pigment 58 (DIC Corporation) in Preparation Example 2-1.

Manufacturing example  2-3: Pigment Dispersion Preparation

A yellow pigment dispersion was prepared in the same manner as in Preparation Example 2-1, except that C.I. Yellow Pigment 138 (BASF Corporation) was used instead of C.I. Green Pigment 58 (DIC Corporation) in Preparation Example 2-1.

Example  1 to 7 lessons Comparative example  1 and 2: Preparation of photosensitive resin composition for color filters

Using the constituents mentioned below, the photosensitive resin composition for color filters according to Examples 1 to 7 and Comparative Examples 1 and 2 was prepared in the composition shown in Table 1 below.

Specifically, the initiator was dissolved in a solvent and stirred at room temperature for 2 hours, and then a photopolymerizable monomer and a binder resin were added thereto, followed by stirring at room temperature for 2 hours. Subsequently, the dye obtained in Preparation Examples 1-1 and 1-2 and the pigment dispersion obtained in Preparation Examples 2-1 to 2-3 were added to the reaction product obtained, followed by stirring at room temperature for 1 hour. Subsequently, the product was filtered once to remove impurities, thereby preparing a photosensitive resin composition for a color filter.

(A) colorant

(A-1) The dye synthesized in Preparation Example 1-1 was used.

(A-2) The dye synthesized in Preparation Example 1-2 was used.

(A'-1) The pigment dispersion prepared in Preparation Example 2-1 was used. At this time, the pigment solids is contained in 15% by weight based on the total amount of the pigment dispersion.

(A'-2) The pigment dispersion prepared in Preparation Example 2-2 was used. At this time, the pigment solids is contained in 15% by weight based on the total amount of the pigment dispersion.

(A'-3) The pigment dispersion prepared in Preparation Example 2-3 was used. At this time, the pigment solids is contained in 15% by weight based on the total amount of the pigment dispersion.

(B) acrylic binder resin

Acrylic acid / benzyl methacrylate copolymer (Miwon Corporation, NPR1520) was used.

(C) Photopolymerization  Monomer

DPHA from Dongyang Synthetic Co., Ltd. was used.

(D) Light curing Initiator

TPP from Nippon Kayaku Co., Ltd., a triazine compound, was used.

(E) solvent

Propylene glycol methylether acetate was used.

(Unit: wt%) Example Comparative example One 2 3 4 5 6 7 One 2 (A) colorant (A-1) 2 4 2 4 - - 15 - - (A-2) - - - - 4 4 - - - (A'-1) 28 26 23 21 26 21 - 30 25 (A'-2) 20 20 - - 20 - 20 20 - (A'-3) - - 25 25 - 25 - - 25 (B) acrylic binder resin 5 5 5 5 5 5 15 5 5 (C) photopolymerizable monomer 5 5 5 5 5 5 10 5 5 (D) photoinitiator 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) solvent 39.5 39.5 39.5 39.5 39.5 39.5 39.5 39.5 39.5

Evaluation 1: Contrast Ratio Evaluation

The contrast ratios of the color filters prepared from the photosensitive resin compositions for color filters of Examples 1 to 7 and Comparative Examples 1 and 2, respectively, were evaluated as follows, and the results are shown in Table 2 and FIG. 1.

Each of the photosensitive resin compositions for color filters prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was coated on a bare glass having a thickness of 2.0 to 2.5 탆 by using a spin coater . Soft-baking was performed at 80 ° C. for 150 seconds using a hot plate. Subsequently, after exposing at a power of 60 mJ using an exposure machine, a developing time of 60 seconds, a washing time of 60 seconds, and spin drying were performed for 25 seconds using a developing machine. The contrast ratio was expressed as the ratio of the value when the polarizers were parallel to the value when the glass substrate was mounted between two polarizers using a contrast ratio meter (CT-1 of Tsubosaka electronic Co., Ltd.).

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Contrast ratio with Gy coordinates of 0.595 13266 13368 12766 12868 12624 12223 12310 12305 11305 Luminance with Gy coordinates of 0.595 58.65 59.2 61.8 62.5 62.7 62.9 61.3 57.5 61.3

1 is a graph showing contrast ratios of color filters prepared from the photosensitive resin compositions for color filters of Examples 1 to 7 and Comparative Examples 1 and 2. FIG.

Referring to Table 2 and Figure 1, in the case of the photosensitive resin composition of Examples 1 to 7 including a dye according to one embodiment, compared to the case of Comparative Example 2 without using a dye, it was confirmed that the high contrast ratio Can be.

Evaluation 2: Permeability Evaluation

After the samples were prepared by spin coating the photosensitive resin compositions for color filters of Examples 1 to 7 and Comparative Examples 1 and 2 to a thickness of 1 μm on a glass substrate, the results were measured using a UV spectrometer. 2 and 3 are shown.

2 is a graph showing the transmittance of the photosensitive resin composition for color filters according to Examples 1, 2, 5 and 7 and Comparative Example 1, Figure 3 is a color filter according to Examples 3, 4 and 6 and Comparative Example 2 It is a graph which shows the transmittance | permeability of the photosensitive resin composition.

Referring to Figure 2, Examples 1, 2, 5 and 7 including a dye according to one embodiment, it can be seen that the high transmittance compared to the case of Comparative Example 1 without using a dye. In addition, referring to Figure 3, in the case of Examples 3, 4 and 6 including the dye according to the embodiment, it can be seen that shows a high transmittance, compared to the case of Comparative Example 2 without using the dye.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (12)

The photosensitive resin composition for color filters containing the coloring agent containing the dye represented by following formula (1).
[Formula 1]

(In Formula 1,
X and Y are the same as or different from each other, and C1 to C20 alkyl group, C3 to C30 cycloalkyl group, C1 to C20 alkyl alcohol group, carboxylic acid group, C2 to C20 alkenyl alcohol group, C1 to C20 alkyl carboxylic acid group, or C2 To C20 alkenyl carboxylic acid group, or X and Y may be connected to each other to form a hydrocarbon ring,
R ¹ , R ² and Z are the same as or different from each other, halogen atom, C1 to C20 alkyl halogen group, sulfonic acid group, C1 to C20 alkyl sulfonic acid group, C2 to C20 alkenyl sulfonic acid group, sulfone imide group, C1 to C20 alkyl Sulfone imide groups, C1 to C20 alkyl alcohol groups, carboxylic acid groups, C2 to C20 alkenyl alcohol groups, C1 to C20 alkyl carboxylic acid groups, C2 to C20 alkenyl carboxylic acid groups, C1 to C20 alkoxyalkyl sulfonic acid groups, C2 to C20 C20 alkoxyalkenyl sulfonic acid group, C2 to C20 alkoxyalkynyl sulfonic acid group, C1 to C20 alkoxyalkyl carboxylic acid group, C2 to C20 alkoxyalkenyl carboxylic acid group, or C2 to C20 alkoxyalkynyl carboxylic acid group,
R ³ to R ⁶ are the same as or different from each other, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 To C30 cycloalkyl group, substituted or unsubstituted C3 to C30 cycloalkenyl group, substituted or unsubstituted C3 to C30 cycloalkynyl group, or substituted or unsubstituted C6 to C30 aryl group,
W is a halogen atom, perchlorate (ClO ₄ ), or hexafluorophosphate (PF ₆ ).)
The method of claim 1,
X and Y in the formula (1) is connected to each other to form a hydrocarbon ring photosensitive resin composition for a color filter.
The method of claim 1,
The dye represented by the formula (1) is a photosensitive resin composition for a color filter comprising a dye represented by the following formula (2-1) or (2-2).
[Formula 2-1]

[Formula 2-2]

The method of claim 1,
The photosensitive resin composition for color filters is a photosensitive resin composition for color filters, further comprising an acrylic binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent.
5. The method of claim 4,
The photosensitive resin composition for color filters
1 to 40% by weight of the colorant;
1 to 30% by weight of the acrylic binder resin;
1 to 20% by weight of the photopolymerizable monomer;
0.01 to 10 wt% of the photopolymerization initiator; And
Residual solvent amount
Photosensitive resin composition for color filters containing.
The method of claim 1,
The colorant is a photosensitive resin composition for color filters further comprising a pigment.
The method according to claim 6,
The pigment is a photosensitive resin composition for a color filter comprising a green pigment, a yellow pigment or a combination thereof.
The method according to claim 6,
The colorant is a photosensitive resin composition for a color filter comprising the dye and the pigment in a weight ratio of 1:99 to 99: 1.
5. The method of claim 4,
The acrylic binder resin may include a first ethylenically unsaturated monomer including (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof; And styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylic A copolymer of a second ethylenically unsaturated monomer comprising a latex, vinyl acetate, vinyl benzoate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, or a combination thereof Photosensitive resin composition for color filters.
5. The method of claim 4,
The photopolymerizable monomer is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth ) Acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or a photosensitive resin composition for color filter that is a combination thereof.
The method of claim 1,
The photosensitive resin composition for color filters is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or the photosensitive resin composition for color filters which further contains the additive of these combinations.
The color filter manufactured using the photosensitive resin composition for color filters in any one of Claims 1-11.

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