KR20190078310A - Black photosensitive resin composition, black matrix using the same and display device - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition comprising: (A) a binder resin; (B) a photopolymerizable monomer; (C) a photoinitiator; (D) a pigment dispersion including carbon black; (E) an inorganic material; and (F) a solvent, wherein the inorganic material is contained in 5 wt% or less with respect to the total amount of the black photosensitive resin composition, to a light shielding layer manufactured using the same, and to a display device comprising a light blocking layer.

Description

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

The present invention relates to a black photosensitive resin composition, a light-shielding layer made using the same, and a display device including the light-shielding layer.

The black photosensitive resin composition is an indispensable material for the production of display elements such as color filters, liquid crystal display materials, organic light emitting devices (EL) and display panel materials. For example, a color filter such as a color liquid crystal display requires a light-shielding layer at a boundary portion between coloring layers such as red, green, and blue in order to enhance display contrast and coloring effect, The light-shielding layer is mainly formed of a black photosensitive resin composition.

Particularly, the development direction of recent liquid crystal display displays is set to high luminance and high color reproduction rate. In order to achieve the above properties, there is an attempt to achieve a high luminance and high color reproduction rate by reducing the reflectance of light coming outdoors. The method that is mainly developed for reducing the reflectance of the display is a method of applying an anti-reflection (AR) film and an anti-glare (AG) film, which are anti-reflection films of polarizing films.

However, such a method is now confined to limitations, and efforts to reduce the reflectance by other methods are continuing.

One embodiment is to provide a black photosensitive resin composition capable of controlling the reflectance.

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

Another embodiment is to provide a display device including the light-shielding layer.

One embodiment includes (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a pigment dispersion comprising carbon black; (E) an inorganic material; And (F) a solvent, wherein the inorganic material is contained in an amount of 10% by weight or less based on the total amount of the black photosensitive resin composition.

The inorganic material may be contained in an amount of 1 wt% to 10 wt% based on the total amount of the black photosensitive resin composition.

The inorganic material may have an average particle diameter of 50 nm to 150 nm.

The inorganic material may include TiO _2, BaSO _3, ZrO _2, or a combination thereof.

The carbon black may have a primary particle size of 50 nm to 100 nm.

The carbon black may have an oil absorption of 50 ml / 100 g to 90 ml / 100 g.

The binder resin may be a cadmium-based binder resin.

The weight average molecular weight of the cationic binder resin may be 1,000 to 50,000 g / mol.

The black photosensitive resin composition preferably contains 0.5 to 20% by weight of the binder resin (A) relative to the total amount of the black photosensitive resin composition; 1 to 20% by weight of the photopolymerizable monomer (B); 0.1 to 10% by weight of the photopolymerization initiator (C); 1 to 20% by weight of the pigment dispersion (D); 1 to 10% by weight of the inorganic material (E); And (F) 40 wt% to 90 wt% of the solvent.

The black 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 black photosensitive resin composition.

Another embodiment provides a display device including the light-shielding layer.

The display device may be a liquid crystal display device (LCD).

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

When the light-shielding layer is produced using the black photosensitive resin composition according to one embodiment, the reflectance can be reduced, and high luminance and high color reproduction of the display device using the same can be realized.

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, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.

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, A C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl 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 C20 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.

In the present specification, "*" refers to the same or different atom or moiety connected to the formula.

The black photosensitive resin composition according to one embodiment comprises (A) a binder resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a pigment dispersion comprising carbon black; (E) an inorganic material; And (F) a solvent, wherein the inorganic material is contained in an amount of 10% by weight or less based on the total amount of the black photosensitive resin composition.

The reflectance can be reduced when the light-shielding layer (black matrix) is manufactured by using the black photosensitive resin composition containing a certain amount of the inorganic material, and the brightness and color reproduction ratio of the display device such as the liquid crystal display device including the light shielding layer (black matrix) can be greatly improved.

Each component will be described in detail below.

(A) Binder resin

The binder resin may be a carcass binder resin, an acrylic binder resin, a polyimide binder resin, a polyurethane binder resin, or a combination thereof.

Among the above-mentioned kinds of binder resins, the cadmium-based binder resin or a mixture of the cadmium-based binder resin and the acrylic-based binder resin may be used. When these binder resins are used, the heat resistance and chemical resistance of the black photosensitive resin composition can be improved.

The weight average molecular weight of the cationic binder resin may be from 1,000 g / mol to 50,000 g / mol, and specifically from 3,000 g / mol to 35,000 g / mol. When the weight average molecular weight of the cationic binder resin is within the above range, excellent patterning property and developability can be obtained in the production of the light-shielding layer.

The cadmium binder resin may be a compound containing a repeating unit represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₂₄ to R ₂₇ each independently may be a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,

R ₂₈ and R ₂₉ are each independently a hydrogen atom or CH ₂ OR _a (R _a is a vinyl group, an acrylic group or a methacryl group)

R ₃₀ may be a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acryl group, or a methacryl group,

Z ₁ is a single bond, O, CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different and are a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group , Or a compound represented by any one of the following formulas (2) to (12)

Z ₂ can be an acid anhydride residue or an acid dianhydride residue.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In Formula 6,

R _f is a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH = CH ₂ , or a phenyl group.

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The cationic binder resin can be specifically obtained by reacting a compound represented by the following formula (13) with a tetracarboxylic acid dianhydride.

[Chemical Formula 13]

The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 2, 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylether tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3 , 6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetra Carboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, and the like, but are not limited thereto.

The acrylic binder resin may contain a first ethylenic unsaturated monomer 　 And a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin comprising at least one acrylic repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, 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 an amount of 5 to 50% by weight based on the total amount of the acrylic binder resin, specifically 10 to 40% by weight.

The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.

Specific examples of the acrylic binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used alone or in combination of two or more.

The weight average molecular weight of the acrylic binder resin may be from 3,000 g / mol to 150,000 g / mol, and may be specifically from 5,000 g / mol to 50,000 g / mol, more specifically from 20,000 g / mol to 30,000 g / mol. 　 When the weight average molecular weight of the acrylic binder resin is within the above range, the black photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion to a substrate when the light-shielding layer is produced.

The acid value of the acrylic binder resin may be from 15 mgKOH / g to 60 mgKOH / g, and specifically from 20 mgKOH / g 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.

When the cadmium-based binder resin and the acrylic-based binder resin are used in combination, the acrylic-based binder resin may be contained in an amount of more than 0 wt% to 20 wt% or less based on 100 wt% of the binder resin. Developability is improved when the acrylic binder resin is contained within the above-mentioned range, but if it is out of the range, the process margin may be lowered.

The binder resin preferably has a ratio of the total amount of the black photosensitive resin composition 　 0.5% to 20% by weight, and more specifically, 1% to 10% by weight. When the binder resin is contained within the above range, the viscosity is appropriately maintained, and the patterning property, the processability, and the developing property are excellent when the light-shielding layer is produced.

(B) Photopolymerization  Monomer

The photopolymerizable monomer may be a monomer or oligomer generally used in a photosensitive resin composition, and a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol Diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, bisphenol A epoxy acrylate , Ethylene glycol monomethyl ether acrylate, trimethylolpropane triacrylate, trisacryloyloxyethyl phosphate, and the like.

A commercially available product of the photopolymerizable monomer is exemplified 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 monomer may be contained in an amount of 1% by weight to 20% by weight based on the total amount of the black photosensitive resin composition, specifically 5% by weight to 15% by weight. When the photopolymerizable monomer is contained within the above range, the compatibility with the binder resin is improved, and the patterned property in the production of the light shielding layer and the sensitivity in the presence of oxygen are excellent, and a smooth surface film can be obtained.

(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 compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 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) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (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- -9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Can be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- -1-one, 1- (4-phenylsulfanylphenyl) -butane-1,2-dione-2-oxime- 1-one oxime-O-acetate, 1- (4-phenylsulfanylphenyl) -butan-1-one oxime -O-acetate, and the like can be used.

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

The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.

Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .

The photopolymerization initiator may be contained in an amount of 0.1% by weight to 10% by weight based on the total amount of the black photosensitive resin composition, and may be contained in an amount of 0.1% by weight to 3% by weight. When the photopolymerization initiator is contained within the above range, the sensitivity of the radical is good, the pattern surface invasion by the development can be minimized, and fume generation due to unreacted initiator can be prevented.

(D) Pigment dispersion

The pigment dispersion contains carbon black.

The carbon black is generally classified according to the primary particle size and the structure. The classification according to the primary particle size is classified according to the size of the primary particle diameter of the carbon black, and the classification according to the above structure depends on the structure of the carbon black And is associated with the secondary particle size of the carbon black. Here, the 'primary particle diameter' of carbon black means the diameter of the carbon black particles measured using a transmission electron microscope (TEM) or an X-ray diffractometer (XRD), and the 'secondary particle diameter' The primary particles can be expressed as the oil absorption, as the size of the secondary particles connected in multiple directions like a chain. That is, the carbon black having a small secondary particle diameter has a small oil absorption amount, but the carbon black having a large secondary particle diameter has a large oil absorption. Therefore, classification of the carbon black according to the structure is classified according to the amount of oil absorption. Even if the primary diameters of the carbon black are the same, the oil absorption can vary depending on the secondary particle size.

The term "oil absorption amount" means the amount of oil necessary to add oil to the carbon black to obtain a kneaded state having a certain degree of fluidity. Usually expressed in ml of oil for 100 g of pigment.

The carbon black in the pigment dispersion may have a primary particle diameter of 50 nm to 100 nm or an oil absorption of 50 ml / 100 g to 90 ml / 100 g.

Even when the primary particle size of the carbon black is out of the range of 50 nm to 100 nm, when the oil absorption amount is within the range of 50 ml / 100 g to 90 ml / 100 g or when the oil absorption amount of the carbon black is out of the range of 50 ml / 100 g to 90 ml / Even if the primary particle diameter is within the range of 50 nm to 100 nm, it may have a reflectance reducing effect. Specifically, the reflectance can be controlled to 10% or less. When the reflectance is controlled within the above range, the display device including the black matrix manufactured using the composition according to one embodiment can achieve high brightness and high color gamut. Further, the carbon black has a primary particle diameter within the above range, so that the stability in the pigment dispersion can be further improved.

The carbon black may be used as a pigment, and the pigment may be used in a black photosensitive resin composition in the form of a pigment dispersion by mixing together a dispersant, a solvent and the like. Specifically, the pigment dispersion can be obtained by mixing the carbon black, the dispersant, and the solvent.

The carbon black is not particularly limited, and examples thereof include graphitized carbon, furnace black, acetylene black, and ketjen black.

The dispersant may help to uniformly disperse the carbon black in the solvent.

Examples of the dispersing agent include a nonionic compound, an anionic compound, a cationic compound, or a combination thereof. Specific examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts , An alcohol alkylene oxide adduct, a sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine.

DISPERBYK-161, DISPERBYK-160, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160, DISPERBYK-130, DISPERBYK- -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 PB711 and PB821 from Ajinomoto.

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

The solvent is the same as the type of the solvent described below.

The pigment dispersion may be contained in an amount of 1% by weight to 20% by weight based on the total amount of the black photosensitive resin composition, specifically 1% by weight to 10% 　 % ≪ / RTI > by weight. When the pigment dispersion is contained within the above range, it is possible to manufacture a light-shielding layer having excellent insulating property and excellent adhesion strength while maintaining a constant optical density.

(E) Inorganic material

The black photosensitive resin composition according to an embodiment includes an inorganic material, and the inorganic material is contained in an amount of 10% by weight or less based on the total amount of the black photosensitive resin composition.

For example, the inorganic material may be included in an amount of 1% by weight to 10% by weight based on the total amount of the black photosensitive resin composition. If the inorganic material is contained in an amount of less than 1% by weight or more than 10% by weight based on the total amount of the black photosensitive resin composition, the reflectance may rather increase, which may be undesirable.

The inorganic material may have an average particle diameter of 50 nm to 150 nm. When the inorganic material is included in the above range, the reflectance is reduced.

The inorganic material may include TiO _2, BaSO _3, ZrO _2, or a combination thereof. For example, the inorganic material may be a BaSO ₃ or ZrO ₂ (zirconia). When the kind of the inorganic material is limited as described above, it is possible to achieve a reflectance reduction effect superior to other inorganic materials.

(F) Solvent

The solvent may be a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment dispersion, or a material having compatibility with the inorganic material but not reacting with the binder resin.

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- ; 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 Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, Ethyl benzoate, 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.

Considering the miscibility and reactivity of the solvent, ketones such as cyclohexanone are preferred; 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 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 about 40% by weight to 90% by weight, for example, 50% by weight to 90% by weight, based on the total amount of the black photosensitive resin composition. When the solvent is contained within the above range, the black photosensitive resin composition has an appropriate viscosity, so that the coating properties are excellent when the light-shielding layer is prepared.

(G) 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; Silane coupling agents; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof, and the like.

Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.

Examples of the fluorine-based surfactant, BM Chemie Corporation ^{BM-1000 ®, BM-1100} ® , and the like; Mecha Pack F 142D ^® , Copper F 172 ^® , Copper F 173 ^® , Copper F 183 ^® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ^®, the same FC-170C ^®, copper FC-430 ^®, the same FC-431 ^®, and the like; Asahi Grass Co., Inc. Saffron S-112 ^®, the same S-113 ^®, the same S-131 ^®, the same S-141 ^®, the same S-145 ^®, and the like; 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 desired properties.

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

(1) Coating and Film Formation Step

The above-mentioned black photosensitive resin composition is coated on a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method or applicator method to a desired thickness, for example, a thickness of 0.9 to 4.0 m And then the solvent is removed by heating at a temperature of 70 to 100 DEG C for 1 to 10 minutes to form a coating film.

(2) Exposure step

In order to form a black matrix pattern necessary for the obtained coating film, a mask of a predetermined type is interposed, and active lines of 200 nm to 500 nm are irradiated.

As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.

The exposure dose varies depending on the kind of each component of the above-mentioned black photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high-pressure mercury lamp is used, the exposure dose is 500 mJ / cm ² (By a 365 nm sensor).

(3) Development step

Following the above exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution as a developing solution, so that only the exposed portion is left to form an image pattern.

(4) Post-treatment step

The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.

By using the above-mentioned black photosensitive resin composition, it is possible to obtain a pattern excellent in high adhesion and straightness required for the light-shielding layer.

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 Black Photosensitive Resin Composition)

The following components were mixed according to the compositions shown in the following Tables 1 and 2 and then stirred for 6 hours to obtain a mixture of the components of Examples 1 to 10, Comparative Examples 1 to 5, Reference Example 1 and Reference Example 2 Thereby preparing a black photosensitive resin composition. Specifically, the content of the photopolymerization initiator was accurately measured, and after the solvent was added, the polymerization was sufficiently stirred until the initiator was completely dissolved. Thereafter, the binder resin and the photopolymerizable monomer were added sequentially, and the mixture was further stirred for about 1 hour. Thereafter, an inorganic material and other additives were added, a pigment dispersion was added, and finally the entire composition was stirred for 2 hours or more to prepare a black photosensitive resin composition.

(A) Binder resin

Cadmium binder resin (V259ME, Nippon Steel Corporation)

(B) Photopolymerization  Monomer

Diphenyl pentaerythritol hexaacrylate (DPHA, Japan Catalysts Inc.) was used.

(C) Light curing Initiator

IRGACURE OXE01 (BASF)

(D) Pigment dispersion

(D-1) A carbon black pigment dispersion having a primary particle diameter of 50 nm and an oil absorption of 45 ml / 100 g

(D-2) A carbon black pigment dispersion having a primary particle size of 30 nm and an oil absorption of 55 ml / 100 g

(D-3) A carbon black pigment dispersion having a primary particle diameter of 30 nm and an oil absorption of 40 ml / 100 g

(E) Inorganic material

(E-1) BaSO ₃ (Mikuni), average particle diameter: 85 nm

(E-2) ZrO ₂ (Mikuni), average particle diameter: 110 nm

(F) Solvent

(F-1) Propylene glycol monomethyl ether acetate (PGMEA) (Sigma-Aldrich)

(F-2) Diethylene glycol methyl ethyl ether (EDM) (Sigma-Aldrich)

(G) Other additives

γ-glycidoxypropyltrimethoxysilane (S-510, Chisso)

(Unit: wt%) Example One 2 3 4 5 6 7 8 9 10 (A) Binder resin 5.18 5.18 5.18 5.21 5.18 5.18 5.18 5.18 5.21 5.18 (B) a photopolymerizable monomer 5.18 5.18 5.18 5.21 5.18 5.18 5.18 5.18 5.21 5.18 (C) a photopolymerization initiator 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 0.19 (D) Pigment dispersion (D-1) 4.56 4.56 4.56 - - 4.56 4.56 4.56 - - (D-2) - - - 4.56 - - - - 4.56 - (D-3) - - - - 4.56 - - - - 4.56 (E) Inorganic material (E-1) One 5 10 5 5 - - - - - (E-2) - - - - - One 5 10 5 5 (F) Solvent (F-1) 67.34 63.34 58.34 63.34 63.34 67.34 63.34 58.34 63.34 63.34 (F-2) 16.2 16.2 16.2 16.2 16.2 16.2 16.2 16.2 16.2 16.2 (G) Other additives 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35 0.35

(Unit: wt%) Comparative Example Reference example One 2 3 4 5 One 2 (A) Binder resin 6.68 6.71 6.67 3.68 3.68 6.43 6.43 (B) a photopolymerizable monomer 6.68 6.71 6.67 3.68 3.68 6.43 6.43 (C) a photopolymerization initiator 0.19 0.19 0.19 0.19 0.19 0.19 0.19 (D) Pigment dispersion (D-1) 4.56 - - 4.56 4.56 4.56 4.56 (D-2) - 4.56 - - - - - (D-3) - - 4.56 - - - - (E) Inorganic material (E-1) - - - 12 - 0.5 - (E-2) - - - - 12 - 0.5 (F) Solvent (F-1) 65.34 65.28 65.36 59.34 59.34 65.34 65.34 (F-2) 16.2 16.2 16.2 16.2 16.2 16.2 16.2 (G) Other additives 0.35 0.35 0.35 0.35 0.35 0.35 0.35

Evaluation: Reflectance measurement

Each of the black photosensitive resin compositions prepared in Examples 1 to 10, Comparative Examples 1 to 5, and Reference Example 1 and Reference Example 2 was spin-coated on a glass substrate, pre-coated with a pre- bake to a thickness of about 1.3 탆. Then, after cooling for 60 seconds at room temperature, ultraviolet light of 40 mJ / cm 2 was irradiated with an ultrahigh pressure mercury lamp to induce photocuring reaction of the photosensitive part. The exposed substrate was developed in a 0.043% KOH aqueous solution at room temperature by a spray method, and then cleaned with a pure solvent for 60 seconds. After drying at room temperature, the specimens were obtained by post-bake in a convection oven at 230 ° C for 30 minutes. After the formation of the pattern sample, the reflectance of each pattern sample was measured using a MCPD (Otsuka) apparatus on the basis of a Cr substrate having a reflectance of 100% in order to measure reflectance, and the results are shown in Table 3 below .

(unit: %) reflectivity Example 1 7.01 Example 2 6.68 Example 3 6.14 Example 4 6.94 Example 5 7.35 Example 6 6.04 Example 7 5.54 Example 8 5.31 Example 9 5.58 Example 10 7.3 Comparative Example 1 8.92 Comparative Example 2 9.94 Comparative Example 3 12.01 Comparative Example 4 12.56 Comparative Example 5 12.46 Reference Example 1 7.25 Reference Example 2 7.2

It can be seen from Table 3 that the black photosensitive resin composition according to one embodiment contains 10% by weight or less of an inorganic material and thus the reflectance can be controlled. Further, when ZrO ₂ is used as an inorganic material, the effect of reducing the reflectance is greatest, and the more the primary particle size and the oil absorption amount of the carbon black are defined, the more the effect of reducing the reflectance is increased.

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) a binder resin;
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a pigment dispersion comprising carbon black;
(E) an inorganic material; And
(F) Solvent
Lt; / RTI >
Wherein the inorganic material is contained in an amount of 10% by weight or less based on the total amount of the black photosensitive resin composition.
The method according to claim 1,
Wherein the inorganic material is contained in an amount of 1 wt% to 10 wt% based on the total amount of the black photosensitive resin composition.
The method according to claim 1,
Wherein the inorganic material has an average particle diameter of 50 nm to 150 nm.
The method according to claim 1,
The inorganic material is TiO _2, BaSO _3, ZrO ₂ or a black photosensitive resin composition comprising a combination of the two.
The method according to claim 1,
Wherein the carbon black has a primary particle diameter of 50 nm to 100 nm.
The method according to claim 1,
The carbon black has an oil absorption of 50 ml / 100 g to 90 ml / 100 g.
The method according to claim 1,
Wherein the binder resin is a cadmium-based binder resin.
8. The method of claim 7,
Wherein the cationic binder resin has a weight average molecular weight of 1,000 to 50,000 g / mol.
The method according to claim 1,
The above-mentioned black photosensitive resin composition is preferably a black photosensitive resin composition,
0.5 to 20% by weight of the binder resin (A);
1 to 20% by weight of the photopolymerizable monomer (B);
0.1 to 10% by weight of the photopolymerization initiator (C);
1 to 20% by weight of the pigment dispersion (D);
1 to 10% by weight of the inorganic material (E); And
40% to 90% by weight of the solvent (F)
And the black photosensitive resin composition.
The method according to claim 1,
The black 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 black photosensitive resin composition of any one of claims 1 to 10.
A display device comprising the light-shielding layer of claim 11.
13. The method of claim 12,
Wherein the display device is a liquid crystal display device (LCD).