KR101788092B1 - Photosensitive resin composition, black matrix and color filter using the same - Google Patents

Abstract

(상기 화학식 1에서, 각 치환기는 명세서에 정의된 바와 같다.)(A) an acrylic binder resin comprising a monomer represented by the following formula (1); (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent, wherein the monomer represented by the following general formula (1) is contained in an amount of 5% by weight to 25% by weight based on the total amount of the acrylic binder resin, and a light shielding layer and a color filter using the same.
[Chemical Formula 1]

(Wherein each substituent is as defined in the specification).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a light-shielding layer, and a color filter using the same. BACKGROUND ART [0002]

The present invention relates to a photosensitive resin composition, a light-shielding layer and a color filter using the same.

A color filter is used for a liquid crystal display, an optical filter of a camera, and the like, and is manufactured by coating a fine area colored with three or more hues on a solid-state imaging element or a transparent substrate. Such a colored thin film is usually formed by a pigment dispersion method or the like.

The colored photosensitive resin composition used in the production of the color filter according to the pigment dispersion method generally comprises a binder resin, a photopolymerizable compound, a photopolymerization initiator, a coloring agent such as a pigment, a solvent, and other additives.

On the other hand, the pigments used in the pigment dispersion method have limitations in securing excellent luminance and taper characteristics, and therefore efforts have been made to improve the brightness and taper characteristics by improving the binder resin, which is a component other than the pigment. In particular, it is common to use a cadmium-based binder resin in order to lower the taper. However, since a cadmium-based binder resin has a problem of deteriorating the luminance characteristic, a study to improve the luminance and taper characteristics by using a binder resin instead of a cadmium- It continues.

One embodiment is to provide a photosensitive resin composition having excellent brightness and taper characteristics.

Another embodiment is to provide a light-shielding layer using the photosensitive resin composition.

Another embodiment is to provide a color filter including the light shielding layer.

One embodiment includes (A) an acrylic binder resin comprising a monomer represented by the following formula (1); (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent, wherein the compound represented by the following general formula (1) is contained in an amount of 5% by weight to 25% by weight based on the total amount of the acrylic binder resin.

[Chemical Formula 1]

In Formula 1,

R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C10 alkenyl group,

L ¹ is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group.

Each of R ¹ to R ³ is independently a hydrogen atom, and L ¹ may be a substituted or unsubstituted C 1 to C 10 alkylene group.

The monomer represented by the formula (1) may be contained in an amount of 7 to 20% by weight based on the total amount of the acrylic binder resin.

The monomer represented by Formula 1 may have a glass transition temperature (T _g ) of 50 ° C to 100 ° C.

The acrylic binder resin may further comprise a monomer represented by the following formula (2), a monomer represented by the following formula (3), or a combination thereof.

(2)

(3)

In the above Formulas 2 and 3,

R ⁴ and R ⁵ are each independently a substituted or unsubstituted C1 to C10 alkyl group,

n and m are each independently an integer of 0 to 5;

The acrylic binder resin may further comprise a monomer represented by the following general formula (4).

[Chemical Formula 4]

In Formula 4,

R ⁶ to R ⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

The dispersion degree of the acrylic binder resin may be 1.8 to 2.2.

The weight average molecular weight of the acrylic binder resin may be 8,000 g / mol to 20,000 g / mol.

The coloring agent may include a pigment.

The photosensitive resin composition comprises (A) 1 to 40% by weight of the acrylic binder resin; (B) 1 wt% to 30 wt% of the photopolymerizable compound; (C) 0.1 to 15% by weight of the photopolymerization initiator; (D) 1% to 10% by weight of the colorant; And (E) the solvent balance.

The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.

Another embodiment provides a light-shielding layer made using the photosensitive resin composition.

Another embodiment provides a color filter comprising the light shielding layer.

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

Since the photosensitive resin composition has excellent taper and luminance characteristics, it can be usefully used for a color filter.

1 is a SEM photograph of a cross-section of a composition according to Example 1. Fig.
2 is a SEM photograph of a cross section of the composition according to Example 2. Fig.
3 is a SEM photograph of a cross section of the composition according to Example 3. Fig.
4 is a SEM photograph of the cross section of the composition according to Comparative Example 1. Fig.
5 is a SEM photograph of a cross-section of a composition according to Comparative Example 2. Fig.
6 is a SEM photograph of the cross section of the composition according to Comparative Example 3. Fig.
7 is a SEM photograph of the cross section of the composition according to Comparative Example 4. Fig.

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 otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, A thio group, an ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, an amidino group, a hydrazino group, a hydrazino group, a carbonyl group, a carbamyl group, C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C4 to C20 cycloalkenyl group, C5 to C20 cycloalkynyl group, Substituted with a substituent of a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C30 heteroaryl group, or a combination thereof.

Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S and P is included in the ring group.

&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.

"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.

Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.

One embodiment includes (A) an acrylic binder resin comprising a monomer represented by the following formula (1); (B) a photopolymerizable compound; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent.

[Chemical Formula 1]

In Formula 1,

R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C10 alkenyl group, L ¹ is a substituted or unsubstituted C1 to C10 alkylene group, Unsubstituted C2 to C10 alkenylene group. For example, each of R ¹ to R ³ may independently be a hydrogen atom, and L ¹ may be a substituted or unsubstituted C 1 to C 10 alkylene group.

Each component will be described in detail below.

(A) Acrylic binder resin

The acrylic binder resin includes the monomer represented by the formula (1), and the monomer represented by the formula (1) is contained in an amount of 5 to 25% by weight, for example, 7 to 20% by weight based on the total amount of the acrylic binder resin. When the monomer represented by Formula 1 is contained in the above range in relation to the total amount of the acrylic binder resin, the photosensitive resin composition containing the acrylic binder resin may have a tapered angle of 35 to 45 degrees, Can be improved.

When the photosensitive resin composition is coated on a substrate such as a TFT to form a coating film, if the taper angle exceeds 45 deg., The liquid crystal driving may be influenced due to a step between RGB colors. If the taper angle is less than 35 deg, And the light leakage phenomenon may occur.

The glass transition temperature (T _g ) of the monomer represented by the general formula (1) may be a low temperature of 100 ° C or lower, for example, 50 ° C to 100 ° C. When the glass transition temperature of the monomer represented by the general formula (1) is within the above range, the taper angle can be maintained at 35 to 45 degrees.

The acrylic binder resin may further comprise a monomer represented by the following formula (2), a monomer represented by the following formula (3), or a combination thereof.

(2)

(3)

In the general formulas (2) and (3)

R ⁴ and R ⁵ are each independently a substituted or unsubstituted C1 to C10 alkyl group,

n and m are each independently an integer of 0 to 5;

The acrylic binder resin may further comprise a monomer represented by the following general formula (4).

[Chemical Formula 4]

In Formula 4,

R ⁶ to R ⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group.

For example, the acrylic binder resin in the photosensitive resin composition may be present in the form of a copolymer of the monomer represented by Formula 1, at least one of the monomers represented by Formulas 2 to 4 and another ethylenically unsaturated compound . The ethylenically unsaturated compound may be an ethylenically unsaturated compound containing at least one carboxyl group, and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, benzyl methacrylate, and combinations thereof.

The dispersion degree of the acrylic binder resin may be 1.8 to 2.2. The degree of dispersion means a value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). When the dispersion degree of the acrylic binder resin is within the above range, excellent taper and luminance characteristics can be maintained, and the occurrence of developing residue (scum) can be minimized, and the characteristics such as resolution, sensitivity and residual film ratio can be improved.

The weight average molecular weight of the acrylic binder resin may be 8,000 g / mol to 20,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate in the production of a color filter.

The acid value of the acrylic binder resin may be from 100 mgKOH / g to 150 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 contained in an amount of 1 wt% to 40 wt%, for example, 1 wt% to 20 wt% with respect to the total amount of the photosensitive resin composition. When the acrylic binder resin is contained within the above range, the color filter is excellent in developability in the production of a color filter, and the cross-linkability is improved, whereby an excellent surface smoothness can be obtained.

(B) Photopolymerization  compound

The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.

By having the above-mentioned ethylenically unsaturated double bond, the photopolymerizable compound can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.

Specific examples of the photopolymerizable compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Acrylate such as 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 tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di 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 compound are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ^®, the same M-111 ^®, the same M-114 ^®; KAYARAD TC-110S ^® and TC-120S ^{® from} Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of ^{V-158 ®, V-2311} ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ^®, copper or the like M-240 ^®, the same M-6200 ^®; KAYARAD HDDA ^® , HX-220 ^® and R-604 ^{® from} Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of ^{社V-260 ®, V-} 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ^®, the same M-400 ^®, the same M-405 ^®, the same M-450 ^®, Dong M -7100 ^® , copper M-8030 ^® , copper M-8060 ^® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ^®, copper DPCA-20 ^{®, ®} copper -30, -60 ^® copper, copper ^® -120 and the like; 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 compound may be treated with an acid anhydride so as to give better developing properties.

The photopolymerizable compound may be contained in an amount of 1 wt% to 30 wt%, for example, 5 wt% to 15 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable compound is contained within the above-mentioned range, the pattern forming process sufficiently cures upon exposure to light, which is excellent in reliability and developability in an alkaline developer.

(C) Light curing Initiator

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

Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) (Trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like.

Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) Acetate and the like.

The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.

The photopolymerization initiator may be contained in an amount of 0.1 wt% to 15 wt%, for example, 0.1 wt% to 8 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.

(D) Colorant

The colorant may include a pigment, a dye, or a combination thereof. For example, the colorant may comprise a pigment.

The above-mentioned pigments can be used both as organic pigments and as inorganic pigments.

The pigment may be a red pigment, a green pigment, a blue pigment, a yellow pigment, a black pigment, or the like.

Examples of the red pigment include C.I. Red pigment 254, C.I. Red pigment 255, C.I. Red pigment 264, C.I. Red pigment 270, C.I. Red pigment 272, C.I. Red pigment 177, C.I. Red pigment 89 and the like. Examples of the green pigment include C.I. Green pigment 36, C.I. Halogen-substituted copper phthalocyanine pigments such as green pigment 7 and the like; Green pigment 58 and the like. Examples of the blue pigments include C.I. Blue pigment 15: 6, C.I. Blue pigment 15, C.I. Blue pigment 15: 1, C.I. Blue pigment 15: 2, C.I. Blue pigment 15: 3, C.I. Blue pigment 15: 4, C.I. Blue pigment 15: 5, C.I. Blue pigment 16, and the like. Examples of the yellow pigments include C.I. Yellow pigments 139 and the like, C.I. Quinophthalone-based pigments such as yellow pigment 138 and the like, C.I. And yellow complex pigments such as yellow pigment 150 and the like. Examples of the black pigment include aniline black, perylene black, titanium black, and carbon black. These pigments can be used singly or in combination of two or more thereof, but are not limited to these examples.

Among them, the black pigment can be used to efficiently perform light shielding of the light shielding layer. When the black pigment is used, it may be used in combination with a color correcting agent such as an anthraquinone pigment, a perylene pigment, a phthalocyanine pigment or an azo pigment.

A dispersant may be used together with the photosensitive resin composition to disperse the pigment. Specifically, the pigment may be surface-treated in advance with a dispersant, or may be used in the form of a pigment dispersion by adding a dispersant together with the pigment when the photosensitive resin composition is prepared.

As the dispersing agent, a nonionic dispersing agent, an anionic dispersing agent, a cationic dispersing agent and the like can be used. Specific examples of the dispersing agent include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adduct, alcohol alkylene oxide adduct, sulfonic acid ester, sulfonic acid salt, carboxylic acid ester, carboxylic acid Salts, alkylamide alkylene oxide adducts, and alkylamines. These may be used singly or in combination of two or more.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.

The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, and therefore, the stability, developability and patternability of the light-shielding layer are excellent.

The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used in the pretreatment, the primary particle size of the pigment can be reduced.

The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.

The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.

Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.

The pigment after the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the pigment is within the above range, it is possible to effectively form a fine pattern with excellent heat resistance and light resistance.

The colorant, for example, the pigment may be contained in an amount of 1 to 10% by weight, for example, 1 to 5% by weight based on the total amount of the photosensitive resin composition. When the pigment is included in the above range, the color reproducibility is excellent and the pattern is excellent in hardenability and adhesion.

(E) Solvent

The solvent may be a material that has compatibility with the acrylic binder resin, the photopolymerizable compound, the photopolymerization initiator, and the colorant but does not react.

The solvent is not particularly limited, but specific examples thereof 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- ; 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 methylhydroxyacetate, ethylhydroxyacetate and butylhydroxyacetate; Alkoxyalkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, and ethoxy ethyl 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-methyl ethyl propionate, hydroxy ethyl acetate and methyl 2-hydroxy-3-methyl butanoate; Or ethyl pyruvate. Examples of the ketone acid esters include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. These may be used alone or in combination of two or more.

In view of the miscibility and reactivity of the solvent, glycol ethers such as ethylene glycol monoethyl ether and the like; 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 alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.

The solvent may be contained in an amount of from about 40% by weight to about 90% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the color filter is excellent.

(F) Other additives

The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent spots and spots upon application, to improve the leveling performance, 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.

The additive can be easily adjusted according to desired properties.

The coupling agent may be a silane coupling agent. Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and these may be used singly or in combination of two or more Can be mixed and used.

The silane coupling agent may be used in an amount of 0.01 part by weight to 1 part by weight based on 100 parts by weight of the photosensitive resin composition.

The photosensitive resin composition may further contain a fluorine-based surfactant, if necessary.

Examples of the fluorine-based surfactant include F-482, F-484, F-478 and the like of DIC Co., but are not limited thereto.

It is more preferable that the fluorine-based surfactant is contained in an amount of 0.01 to 5% by weight, for example, 0.1 to 2% by weight based on the total amount of the photosensitive resin composition. If it is out of the above range, a foreign matter may be generated after development, which is not preferable.

According to another embodiment, there is provided a light-shielding layer produced using the above-mentioned photosensitive resin composition. The method of manufacturing the light-shielding layer is as follows.

(1) Coating and Film Formation Step

The above-mentioned photosensitive resin composition is coated on a predetermined pretreated substrate to a desired thickness, for example, a thickness of 2.0 탆 by a spin or slit coat method, a roll coating method, a screen printing method, an applicator method or the like , And heated at 90 DEG C for 150 seconds to remove the solvent to form a coating film.

(2) Exposure and development step

The pattern thus obtained was subjected to pattern exposure with a GAP pattern of 50 mJ and 200 쨉 m using an exposure machine to form a pattern. The pattern was then developed under the conditions of a developing temperature of 25 캜, a developing time of 60 seconds, a washing time of 60 seconds, do.

(3) Post-processing step

The image pattern obtained by the above-mentioned development is cured by post-baking (post-baking) at 230 DEG C for 20 minutes using a convection oven.

Another embodiment provides a color filter manufactured using the above-described photosensitive resin composition.

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

(Preparation of acrylic binder resin)

Manufacturing example  1 to 3 and Comparative Manufacturing Example  1 to 4

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a photopolymerization initiator and the monomers shown in the following Table 1 were added to the flask equipped with a condenser and a stirrer, and then propylene glycol (PGMEA, solvent) were added to the above photopolymerization initiator and 200 parts by weight based on 100 parts by weight of the total amount of the monomers shown in the following Table 1, followed by stirring gently in a nitrogen atmosphere. The reaction solution was heated to 85 캜 and stirred for 6 hours to prepare an acrylic binder resin. The solid content concentration of the acrylic binder resin solution obtained by the above method was 30% by weight, and the weight average molecular weight was as shown in Table 1 below. Here, the weight average molecular weight is an average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography).

(Unit: parts by weight) Production Example 1 Production Example 2 Production Example 3 Comparative Preparation Example 1 Comparative Production Example 2 Comparative Production Example 3 Comparative Production Example 4 Benzyl methacrylate 16.0 9.0 3.0 23.0 16.0 19.0 0.0 Acrylic acid 20.0 20.0 20.0 20.0 20.0 20.0 20.0 4-hydroxybutyl acrylate 7.0 14.0 20.0 0.0 0.0 4.0 27.0 Phenylmaleimide 25.0 25.0 25.0 25.0 25.0 25.0 25.0 Isobornyl methacrylate 32.0 32.0 32.0 32.0 39.0 32.0 28.0 Weight average molecular weight (g / mol) 15000 15500 15500 15800 15500 15300 15600 The dispersion degree (PDI) 2.0 2.0 2.1 2.0 2.0 2.1 2.0 Acid value (mg KOH / g) 128 130 129 130 130 130 130

(Preparation of photosensitive resin composition)

Example  1 to Example  3 and Comparative Example  1 to Comparative Example  4

The following photopolymerization initiator was dissolved in the following solvent with the composition shown in Table 2 below, followed by stirring at room temperature for 30 minutes or longer. The acrylic binder resin and photopolymerizable compound prepared in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 4 were added and stirred at room temperature for 1 hour. After the addition of the fluorine-containing surfactant and the pigment, the entire resin composition was finally stirred at room temperature for 2 hours or more. The solution was filtered three times to remove impurities to prepare photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 4. The components used in the production of the photosensitive resin composition are as follows.

(A) Acrylic binder resin

(A-1) The acrylic binder resin of Production Example 1

    (A-2) The acrylic binder resin of Production Example 2

(A-3) The acrylic binder resin of Production Example 3

    (A-4) The acrylic binder resin of Comparative Production Example 1

(A-5) The acrylic binder resin of Comparative Production Example 2

(A-6) The acrylic binder resin of Comparative Production Example 3

(A-7) The acrylic binder resin of Comparative Production Example 4

(B) Photopolymerization  compound

    Dipentaerythritol hexaacrylate (DPHA)

(C) Light curing Initiator

    Oxime compound (IRGACURE OXE-02, BASF)

(D) a coloring agent (pigment)

G58 (SKHass) and Y138 (SANYO)

(E) Solvent

Propylene glycol monomethyl ether acetate (PGMEA)

(F) Additive

Fluorine-based surfactant (F-554, DIC)

(Unit: wt%) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Acrylic binder resin A-1 10.00 * - - - - - - A-2 - 10.00 * - - - - - A-3 - - 10.00 * - - - - A-4 - - - 10.00 * - - - A-5 - - - - 10.00 * - - A-6 - - - - - 10.00 * - A-7 - - - - - - 10.00 * (B) a photopolymerizable compound 10.00 10.00 10.00 10.00 10.00 10.00 10.00 (C) a photopolymerization initiator 1.00 1.00 1.00 1.00 1.00 1.00 1.00 (D) Colorant 3.00 ** 3.00 ** 3.00 ** 3.00 ** 3.00 ** 3.00 ** 3.00 ** (E) Solvent 75.45 75.45 75.45 75.45 75.45 75.45 75.45 (F) Additive 0.55 0.55 0.55 0.55 0.55 0.55 0.55 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00

(* The binder content is on a solid basis, ** the colorant content is the pigment only content)

Rating 1: Taper  angle

Sectional views of the patterned photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 4 were observed by SEM. The results are shown in Table 3 and Figs. 1 to 7.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Tapered angle 44 ° 34 ' 42 ° 12 ' 39 ° 56 ' 78˚ 15 ' 73 ° 47 ' 78 ° 20 ' 42 ° 17 '

Evaluation 2: Luminance

Each of the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4 was coated on a glass substrate having a thickness of 1 mm and degreased and cleaned to a thickness of 1 占 퐉 to 2 占 퐉 and then coated on a hot plate at 90 占 폚 And dried for 3 minutes to obtain a coating film. The obtained coating film was cooled, irradiated with light at an exposure dose of 50 mJ / cm ² (based on 365 nm), and then dried in a hot air circulating drying oven at 230 ° C for 30 minutes. The luminance was measured through a spectrometer (MCPD3000, manufactured by Otsuka Electronics Co., Ltd.), and the results are shown in Table 4 below.

Luminance (Y) Example 1 14.80 Example 2 14.93 Example 3 14.78 Comparative Example 1 14.40 Comparative Example 2 14.28 Comparative Example 3 14.85 Comparative Example 4 14.32

Through Tables 3, 4 and 1 to 7, in Examples 1 to 3 using the acrylic binder resin according to the present invention, taper and luminance characteristics of the photosensitive resin compositions of Comparative Examples 1 to 4 Is excellent.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (13)

(A) an acrylic binder resin comprising a monomer represented by the following formula (1), a monomer represented by the following formula (2) and a monomer represented by the following formula (4);
(B) a photopolymerizable compound;
(C) an oxime-based compound as a photopolymerization initiator;
(D) a colorant; And
(E) Solvent
Lt; / RTI >
The monomer represented by the following formula (1) is contained in an amount of 7 to 14% by weight based on the total amount of the acrylic binder resin,
The dispersion degree of the acrylic binder resin is 1.8 to 2.2.
[Chemical Formula 1] < EMI ID =

In the above formulas (1), (2) and (4)
R ¹ to R ³ are each independently a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C2 to C10 alkenyl group,
R ⁴ is a substituted or unsubstituted C1 to C10 alkyl group,
R ⁶ to R ⁹ are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
L ¹ is a substituted or unsubstituted C1 to C10 alkylene group or a substituted or unsubstituted C2 to C10 alkenylene group,
n is an integer of 0 to 5;
The method according to claim 1,
Each of R ¹ to R ³ is independently a hydrogen atom,
Wherein L < ¹ > is a substituted or unsubstituted C1 to C10 alkylene group.
delete The method according to claim 1,
The monomer represented by the formula (1) has a glass transition temperature (T _g ) of 50 ° C to 100 ° C.
delete delete delete The method according to claim 1,
Wherein the acrylic binder resin has a weight average molecular weight of 8,000 g / mol to 20,000 g / mol.
The method according to claim 1,
Wherein the coloring agent comprises a pigment.
The method according to claim 1,
The photosensitive resin composition
(A) 1 to 40% by weight of the acrylic binder resin;
(B) 1 wt% to 30 wt% of the photopolymerizable compound;
(C) 0.1 to 15% by weight of the oxime compound;
(D) 1% to 10% by weight of the colorant; And
(E) the solvent remaining amount
.
The method according to claim 1,
The photosensitive resin composition may include malonic acid; 3-amino-1,2-propanediol; A coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; And at least one additive selected from a radical polymerization initiator.
A light-shielding layer produced by using the photosensitive resin composition of any one of claims 1, 2, 4, and 8 to 11.
A color filter comprising the light-shielding layer of claim 12.

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