KR101392115B1 - A black coating composition - Google Patents

Abstract

There is provided a black coating composition comprising a black material, a high-durability insulating metal oxide particle, a polymerizable compound, and a polymerization initiator.

Description

[0001] A BLACK COATING COMPOSITION [0002]

More particularly, the present invention relates to a black coating composition having high resistance, high heat resistance, chemical resistance, and high film hardness when applied to a substrate to form a film, and having durability even in a high temperature process .

Currently, the flat panel display market has grown to such a degree that it can not support the demand. At the center of the market is a plasma display panel (PDP), a liquid crystal display device (LCD), an organic light emitting display (OLED) There are displays. In particular, LCD is a major product in the flat panel display market and consists of color filters, thin film transistors and liquid crystals. A color filter used in a color liquid crystal display device, an image pickup device, or the like is generally formed by uniformly applying a coating composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is patterned by spin coating, The coating film formed by heating and drying is exposed and developed, and if necessary, further heating and curing is repeated for each color to form pixels of each color. Here, the black matrix to be patterned is usually formed by using a black photosensitive resin composition, and may be formed by using a black thermosetting resin composition according to a modification of the coating method.

The black coating composition is an essential material for a flat panel display panel material such as a color filter, a liquid crystal display (LCD), an organic light emitting display (OLED), a plasma display panel (PDP) In recent years, attempts have been made to introduce a black column spacer which can serve as a column spacer capable of supporting a TFT-array layer and a color filter layer through a black matrix. In this case, a uniform optical density Optical density (OD) as well as excellent electrical insulation. However, if only carbon black is used for forming black column spacers, as in a conventional black matrix, the optical density is satisfactory but the electrical insulation is poor. In addition, the black matrix materials using inorganic compounds all have low insulating properties, and thus fail to satisfy the properties required in the black column spacers. In addition, in a panel in which a black matrix is formed on a TFT surface or a color filter is formed on a panel, electric insulation is required to have a high insulation property or low dielectric property in order to directly affect the liquid crystal. In addition, the use of the black coating composition is being applied not only to the interior of the color filter but also to the outside of the display.

In recent years, various manufacturing methods such as LCD, OLED, PDP, touch panel display and the like have been variously applied, so that silicon oxide processing, ITO sputtering or other sputtering process may be applied after the coating process of the black coating composition. In this case, especially, in the case of the sputtering process, the temperature also progresses to a temperature of 350 ° C or higher, and electrical properties such as insulation and dielectric constant of the black coating composition after the high temperature process can be greatly changed from the values before the process.

According to an aspect of the present invention, there is provided a black coating composition comprising a black material, an insulating metal oxide particle, a polymerizable compound, and a polymerization initiator.

According to another aspect of the present invention, there is provided a process for producing a black material, which comprises a black material, a high-durability insulating metal oxide particle, a binder resin, a polymerizable compound, a polymerization initiator and a solvent, 1 to 60 parts by weight of the high-durability insulating metal oxide particles and 1 to 70 parts by weight of the high-durability insulating metal oxide particles, wherein the high-durability insulating metal oxide particles are silica or alumina particles having an average particle diameter of 60 to 150 nm, By weight of the black coating composition.

According to another aspect of the present invention, there is provided a black coating composition comprising a black material, a high-durability insulating metal oxide particle, a thermosetting resin composition, and a solvent.

According to another aspect of the present invention, there is provided a black coating film formed by applying and polymerizing the above-mentioned black coating composition.

According to still another aspect of the present invention, there is provided an image display apparatus including the black coating film.

1 is a conceptual diagram for explaining whether or not a conductive path is formed depending on the size of high-durability insulating metal oxide particles.

Hereinafter, the present invention will be described in detail.

The black coating composition according to the present invention comprises a black material (A1), a high-durability insulating metal oxide particle (A2), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E). Optionally, the black coating composition further comprises a binder resin (B) necessary for development, or may further comprise a solvent (E) for controlling the coating properties or for dissolving the polymerization initiator. Also, although not particularly limited, the black coating composition may optionally further comprise an additive (F).

Hereinafter, each component contained in the black coating composition of the present invention will be described in more detail.

The black material (A1)

The black material (A1) is not limited to a particular material as long as it is a light-shielding pigment. Specific examples thereof include inorganic pigments such as metal oxides, complex oxides, metal sulfides and metal carbonates such as carbon black, titanium black, iron, copper, manganese, cobalt, chromium, nickel, zinc, calcium and silver.

Particularly in carbon black, known carbon blacks such as furnace black, thermal black, channel black and lamp black can be used, and carbon black coated with a resin can be used. In particular, carbon black coated with a resin may be more preferable because it has lower conductivity than carbon black not coated.

Specific examples of the carbon black include MA-8 (manufactured by Mitsubishi Chemical), but the present invention is not limited thereto.

The carbon black resin composition may further include an additive such as a dispersant.

The dispersant plays a role of controlling aggregation between carbon blacks. The dispersant may include a hydrophilic group and a hydrophobic group capable of controlling aggregation between carbon blacks. The surface of the carbon black constituting the carbon black resin composition may be treated with a dispersant beforehand.

The dispersant may be a urethane-based dispersant, an acrylic-based dispersant, or an epoxy-based dispersant, but is not limited thereto.

Examples of the urethane dispersant include those selected from the group consisting of disperbyk 2150 (BYK chemie), disperbyk 164 (BYK chemie), disperbyk 163 (BYK chemie), and combinations thereof.

An example of the acrylic dispersant is disperbyk 2070 (manufactured by BYK Chemie).

Highly durable insulating metal oxide particles (A2)

As the high-durability insulating metal oxide particles (A2), inorganic metal oxide particles such as silica, alumina, titania, and zirconia can be applied. The high-durability insulating metal oxide particles (A2) can be used either singly or in combination of two or more of the above-mentioned inorganic metal oxide particles, and can be uniformly mixed with the black material (A1) while providing excellent durability and electrical insulation .

The durable insulation may be silica (SiO ₂₎ or alumina (Al ₂ O ₃₎ particles and preferred examples of the metal oxide particles (A2). The silica or alumina particles used may be substantially spherical, less than 1 micrometer sized particles dispersed in an aqueous or other solvent medium.

The high-durability insulating metal oxide particles (A2) used in the present invention may have an average particle diameter of 50 nm or more in consideration of electrical characteristics. Also, in consideration of the roughness of the coating surface, the average particle diameter of the highly durable insulating metal oxide particles (A2) may be 150 nm or less. The average particle diameter of the highly durable insulating metal oxide particles (A2) may preferably be 60 to 150 nm, more preferably 60 to 120 nm, still more preferably 70 to 120 nm. The high-durability insulating metal oxide particles (A2) of the present invention can improve the insulating property and prevent aggregation between the black materials due to the heat of the black material (for example, carbon black) used together and to prevent the rise of the conductivity and the rise in the relative dielectric constant Because it is used for the purpose, the size is preferably 50 nm or more. In other words, the average particle diameter of the insulating metal oxide particles (A2) must be 50 nm or more to prevent percolation of the carbon black particles.

1 is a conceptual diagram for explaining whether or not a conductive path is formed depending on the size of high-durability insulating metal oxide particles. Referring to Fig. 1, when the average particle diameter is less than 50 nm, the high-durability insulating metal oxide particles A2 are filled with void spaces between the black materials A1, as shown in Fig. 1 (a) The conductive path can be formed as indicated by the dotted line in the drawing, which makes it impossible to obtain an effective high resistance and a low relative dielectric constant. On the other hand, as shown in FIG. 1 (b), when the average particle size has large average particle diameters such as the above range, effective high resistance and low relative dielectric constant can be obtained. However, if it exceeds the above range, a high resistance and a low relative dielectric constant can be obtained, but since the roughness of the coating surface is raised, it is possible to cause a bad surface property, which is also visible to the naked eye. The average particle size can be determined using a transmission electron microscope.

In addition, the silica or alumina particles generally have a surface area of greater than about 100 m 2 / gram. For maximum improvement of the shear value, the particles preferably have a narrow particle size distribution, i.e. the polydispersity may be 2.0 or less, preferably 1.5 or less. If desired, smaller amounts of larger particles may be added, but such additions may not contribute to shear value increases.

Specific examples of the silica include, but are not limited to, nano-silica in which a solvent of a nano-silica sol product (SS-SOL 3080, SS-SOL 100;

In the case of using the highly durable insulating metal oxide particles (A2), the shape of the particles is not limited. The highly durable insulating metal oxide particles can be surface treated with a silane coupling agent or the like. In this case, compatibility with the binder resin and adhesion properties can be improved.

When the sum of solid contents of the black material (A1) and the high-durability insulating metal oxide particles (A2) is 100 parts by weight in order to ensure more excellent durability, electrical insulation and uniform optical density, (A1) is contained in an amount of 5 to 95 parts by weight based on 100 parts by weight of the solid content, and the high-durable insulating metal oxide particles (A2) is contained in an amount of 5 to 95 parts by weight .

The black material (A1) may be contained in an amount of 1 to 60 parts by weight based on 100 parts by weight of the solid content in the black coating composition. When the content of the black material (A1) is less than 1 part by weight, the optical density is not sufficient. When the content of the black material (A1) is more than 60 parts by weight, the optical density is sufficient but pattern formation may be difficult.

The high-durability insulating metal oxide particles (A2) may be contained in an amount of 1 to 70 parts by weight based on 100 parts by weight of the solid content in the black coating composition. If the content of the high-durability insulating metal oxide particles (A2) is less than 1 part by weight, the insulating property and the durability are not sufficient. If the content is more than 70 parts by weight, sufficient insulating property and durability are sufficient. However, pattern formation is difficult or sufficient optical density I can not.

The binder resin (B)

As the binder resin (B), those generally used in the art can be applied, and in particular, the binder resin (B) is preferably a copolymer of a compound having an unsaturated carboxyl group and other monomer copolymerizable therewith.

The compound having an unsaturated carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized and can be used singly or in combination of two or more kinds.

Examples of the compound having an unsaturated carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of the dicarboxylic acid; mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both ends such as? -carboxypolycaprolactone mono (meth) acrylate, monomethyl (meth) acrylate, monomethyl maleic acid, Mono-2 - ((meth) acryloyloxy) ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate or mixtures thereof. Among the above-exemplified compounds having an unsaturated carboxyl group, acrylic acid and methacrylic acid are preferable because of their excellent copolymerization reactivity and solubility in a developing solution.

The other monomer capable of copolymerizing with the carboxyl group-containing monomer is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene,? -Methylstyrene and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinylcyanide compounds such as acrylonitrile, methacrylonitrile and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, Unsaturated oxetanecarboxylate compounds, and the like.

In addition, the binder resin may use a cadene resin commonly used in the art.

The cardade resin is a mixture of 3,3-bis (4-hydroxyphenyl) -2-benzofuran-1 (3H) (3H) -one, 3,3-bis (4-hydroxy-2,5-dimethylphenyl) (3H) -one, 3,3-bis (4-hydroxy-5-isopropyl-2-methylphenyl) -2-benzofuran- , 3,3-bis (3,5-dibromo-4-hydroxyphenyl) -2-benzofuran-l (3H) (4-hydroxyphenyl) -10-anthrone, 1,2-bis (4-carboxyphenyl) carboran, 1, Bis (4'-carboxyphenyl) phthalide, 9,10-bis- (4-carboxyphenyl) (4-aminophenyl) -anthracene, anthrone dianiline, and aniline phthalein. Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane and bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis Bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxyphenyl) (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, (4-hydroxyphenyl) propane, bis (4-hydroxy-3-chlorophenyl) Bis (4-hydroxyphenyl) ether and bis (4-hydroxy-3,5-diclophenyl) ether, 9,9- Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9- (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9- (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) Or at least one of the monomers.

The binder resin (B) may be contained in an amount of 5 to 60 parts by weight, preferably 10 to 40 parts by weight, based on 100 parts by weight of the solid content in the black coating composition. If the binder resin (B) is within the above content range on the basis of the above-mentioned criteria, it is possible to form a pattern, and resolution and retention rate are improved.

The polymerizable compound (C)

The polymerizable compound (C) is a compound capable of polymerizing under the action of a polymerization initiator described below by energy such as heat or light, and examples thereof include monofunctional monomers, bifunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Of these, multifunctional monomers having two or more functional groups are preferably used.

The polymerizable compound (C) may be used in an amount of 5 to 80 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the total of the binder resin (B) and the polymerizable compound (C) . When the polymerizable compound (C) is in the range of 5 to 80 parts by weight on the basis of the above-mentioned criteria, it is preferable since pattern characteristics become good.

The polymerization initiator (D)

The polymerization initiator (D) is not limited, but it is preferable to use at least one compound selected from the group consisting of triazine-based compounds, acetophenone-based compounds, nonimidazole-based compounds and oxime compounds.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one oligomers and the like.

The acetophenone compound may be a compound represented by the following general formula (1).

≪ Formula 1 >

Wherein R ₁ to R ₄ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms, a benzyl group which may be substituted with an alkyl group having a carbon number of 1 to 12 Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl- 2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 2-amino (4-morpholinophenyl) propan-1-one, 2-methyl- 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one 2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino .

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, the phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by an alkoxy group, and the like. Of these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 5,5'-tetraphenylbiimidazole can be preferably used.

Examples of the oxime compounds include compounds represented by the following formulas (2) to (4).

(2)

(3)

≪ Formula 4 >

In addition to the above-mentioned polymerization initiator, other polymerization initiators commonly used in this field may be further used in combination with such a degree that the effect of the present invention is not impaired. Examples of other polymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, anthracene-based compounds, and polyfunctional thiol compounds. These may be used alone or in combination of two or more.

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

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

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

Examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis- -Mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid Methyl, titanocene compounds and the like can be mentioned as other polymerization initiators.

According to the present invention, the polymerization initiator (D) may be used in combination with the polymerization initiator (D-1). When the polymerization initiator (D) is used in combination with the polymerization initiator (D-1), the black coating composition containing the black initiator (D-1) is more preferable because productivity is improved when the black matrix or black column spacer is formed using the same.

As the polymerization initiator (D-1), at least one compound selected from the group consisting of an amine compound and a carboxylic acid compound can be preferably used.

Specific examples of the amine compound in the polymerization initiator (D-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, (2-ethylhexyl) benzoic acid, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone And aromatic amine compounds such as 4,4'-bis (diethylamino) benzophenone. As the amine compound, an aromatic amine compound is preferably used. Specific examples of the carboxylic acid compound in the polymerization initiator (D-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenyl Aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the polymerization initiator (D) is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the binder resin (B) and the polymerizable compound (C) based on the solid content. The content of the polymerization initiator (D-1) is 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the total of the binder resin (B) and the polymerizable compound (C) Buddha. When the content of the polymerization initiator (D) is in the above range on the basis of the above criteria, the black coating composition is highly sensitized, and the strength of the pixel portion formed by using the composition and the smoothness on the surface of the pixel portion are favorable Do. When the amount of the polymerization initiator (D-1) used is within the above range on the basis of the above criteria, the sensitivity of the black coating composition is higher and the pattern characteristic is improved.

Solvent (E)

The solvent (E) is not particularly limited and various organic solvents conventionally used in the art can be used.

Specific examples of the solvent (E) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, Alkylene glycol alkyl ether acetates such as monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate, alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate,

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, Alcohols such as glycol and glycerin, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

Among the above-mentioned solvents, an organic solvent having a boiling point of 100 to 200 ° C in the solvent is preferably used from the viewpoint of coatability and drying property, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid Ethyl and 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, 3-methoxy Methyl propionate and the like.

These solvents (E) may be used alone or in combination of two or more.

The content of the solvent (E) is 20 to 90 parts by weight, preferably 60 to 85 parts by weight based on 100 parts by weight of the entire black coating composition containing the same. When the content of the above-mentioned solvent (E) is in the range of 20 to 90 parts by weight based on the above-mentioned criteria, it can be coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater It is preferable because the coating property becomes good.

Additive (F)

The black coating composition of the present invention may optionally contain additives (F) such as other polymer compounds, curing agents, pigment dispersants, adhesion promoters, antioxidants, ultraviolet absorbers,

Specific examples of the other polymer compound specifically include thermosetting resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane .

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

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, and triglycidyl isocyanurate.

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

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the curing aid compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, acid generators, and the like.

The carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of commercially available epoxy resin curing agents include trade name (ADEKA HARDONA EH-700) (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (Manufactured by Shin-Etsu Chemical Co., Ltd.).

The curing agent and the curing auxiliary compound exemplified above may be used alone or in combination of two or more.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, and amphoteric surfactants. These may be used alone or in combination of two or more.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac (Manufactured by Dainippon Ink & Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon (manufactured by Asahi Glass Co., Ltd.) (Manufactured by Lubrisol), EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto), and Disperbyk-series (manufactured by BYK-chemie).

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

The adhesion promoter may be used alone or in combination of two or more. It is preferable to use 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the solid content of the black coating composition.

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

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate.

The black coating composition of the present invention can be produced, for example, by the following method.

The black material A1 is mixed with the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the black material becomes about 0.15 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (B) may be blended. The obtained dispersion of the black material (A1) is mixed with the remainder of the solvent (E) at a certain ratio using a stirrer or the like. After adding the insulating particles (A2), the remainder of the binder resin (B), the polymerizable compound (C) and the polymerization initiator (D) and, if necessary, the additive (F) And further added to a predetermined concentration to obtain a desired black coating composition.

According to one embodiment, the black coating composition may comprise a black material, a high-durability insulating metal oxide particle, a thermosetting resin composition, and a solvent. The thermosetting resin composition may include a thermosetting resin, a curing agent, and a curing catalyst. The thermosetting resin may be at least one selected from the group consisting of an epoxy resin, a polyurethane resin, a melamine resin, a urea resin, a phenol resin, and an alkyd resin. According to one embodiment, When applied and polymerized, a black coating film may be formed on the substrate. Spin coating, or the like, and then the polymer is formed in the black coating composition by heat or light, and the solvent is removed and cured to a solid phase. The black coating film thus formed is excellent in heat resistance, low electric insulating property, and high film hardness by including inorganic oxide particles.

According to one embodiment, the black coating film may be applied to various image display devices such as LCD, OLED, PDP, and touch panel display. The black coating film may be disposed on the black matrix layer or the upper substrate, for example, to enhance the contrast ratio of a liquid crystal display (LCD). Meanwhile, the black coating film may be formed on an insulating film of a capacitive touch panel, for example.

In the image display device using the black coating film, the reflectance is reduced and the contrast ratio is increased to improve the visibility of the screen. Since the inorganic oxide particles are contained in the film, heat resistance, insulation and durability are high.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, numerals in the tables indicate parts by weight.

≪ Black material (A1) Dispersion Production Examples 1 to 4 >

80 parts by weight of the black material (A1), the dispersing agents (F1, F2) and the solvent (E1) were previously mixed in the vessel and stirred for 3 minutes using a homogenizer, The process of performing the treatment for 3 minutes was repeated three times to carry out dispersion. After the dispersion was completed, 20 parts by weight of the remaining amount of the solvent (E1) was added to prepare black material dispersions BK 1 to 4.

The black material dispersion (BK) Manufacturing example
1 (BK1) Manufacturing example
2 (BK2) Manufacturing example
3 (BK3) Manufacturing example
4 (BK4) Black material
(A1) PBK 16 16 16 16 The pigment dispersant (F1) 4 3 2 0 The pigment dispersant (F2) 0 One 2 4 Solvent (E1) 80 80 80 80 Viscosity (cp @ 20 rpm) 1.60 1.85 2.13 2.30 Particle size (nm) 118 120 126 124

≪ Detailed Description of Components Used in Table 1 >

The black material (A1)

  PBK: Carbon Black (MA-8, manufactured by Mitsubishi)

Dispersant (F1): Disperbyk-2150 (BYK chemi)

Dispersant (F2): Disperbyk-163 (BYK chemi)

Solvent (E1): Propylene glycol monomethyl ether acetate

≪ Examples 1 to 7 and Comparative Examples 1 to 5 >

Each component described in Table 2 below was mixed to obtain a black coating composition.

division
Example Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 1 Example 2 Example 3 Example 4 Example 5 Black material
The dispersion (BK) BK1
34 BK2
34 BK3
34 BK4
34 BK1
34 BK1
33.04 BK1
34 BK1
38.76 BK2
38.76 BK4
38.76 BK1
34 BK1
34 Insulating particle
(A2) Average size 70 nm 70 nm 70 nm 70 nm 70 nm 110 nm 110 nm 40 nm 160 nm input 4.76 4.76 4.76 4.76 4.76 5.72 4.76 Binder
Resin (B) Cadillac resin (WR-101, manufactured by Adeca)
4.2 (based on 100% solids) Polymerizable
The compound (C) Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
4.2 polymerization
Initiator (D) -9- ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (Irgacure OXE02; Produce)
1.0 Solvent (E) Propylene glycol monomethyl ether acetate
51.32 Additive (F1) Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd.)
0.5 Additive (F2) 3-methacryloxypropyltrimethoxysilane
0.02

≪ Insulating particles (A2) used in Table 2 >

- SS-SOL 30FH Solvent removal silica (average particle diameter 40 nm, manufactured by Eskemec)

- SS-SOL 3080 solvent-removed silica (average particle diameter 70 nm, manufactured by Eschemtech)

- SS-SOL 100 solvent-removed silica (average particle diameter 110 nm, manufactured by Eschemtech)

- SILNOS SOL Solvent Removal Silica (average particle diameter 160 nm, manufactured by ABC Nanotech)

<Experimental Example>

A 2-inch square glass substrate (# 1737, manufactured by Corning Incorporated) was sequentially washed with a neutral detergent, water and alcohol, and then dried. The black coating composition according to the above examples and comparative examples was exposed on this glass substrate at an exposure amount of 365 nm (100 mJ / cm 2), and the resultant coating was spin-coated so as to have a thickness of 3.0 탆 after the post-baking , And then pre-dried in a clean oven at 100 DEG C for 3 minutes. After cooling, the substrate coated with the black coating composition was irradiated with light (365 nm) at an exposure dose of 100 mJ / cm 2 using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio DENKI CO., LTD. Thereafter, it was baked at 220 캜 for 30 minutes.

1. Optical density measurement

The optical density of the black substrate produced by the above method was measured at a wavelength of 400 to 750 nm using OSP-200 (manufactured by Olympus Corporation). The measured results are shown in Table 3. And as an evaluation reference optical density OD of at least 4.0 at a wavelength of 550nm, and the average optical density OD _ave is preferably not less than 3.0.

2. Measurement of relative dielectric constant

An aluminum electrode was formed on the black substrate formed by the above method using an aluminum vacuum deposition equipment and a mask. At this time, the aluminum electrode was deposited in a thickness of 0.075 ± 0.025 μm on the black layer and the non-coating layer (ITO electrode) in a circular shape with a diameter of 5 mm.

The electrostatic capacity when an AC voltage of 1 to 100 kHz and 1 V was applied to the aluminum electrode on the coating layer of the deposited sample and the aluminum electrode of the non-coating layer using a capacitance meter (trade name: LCR meter 4284A, Agilnet) And the relative dielectric constant was calculated from the value, and is shown in Table 3. It is preferable that the relative dielectric constant is less than 5.0 as an evaluation standard.

division
Example Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 1 Example 2 Example 3 Example 4 Example 5 OD 4.1 4.2 4.3 4.3 4.1 4.1 4.1 4.7 4.5 4.7 4.1 4.2 OD _ave 3.1 3.0 3.4 3.3 3.3 3.0 3.1 3.6 3.5 3.5 3.0 3.2 Relative dielectric constant 4.2 4.2 4.6 4.6 4.6 3.8 4.6 27 31 30 8.1 4.5

As shown in Table 3, according to the embodiments using the black coating composition including the carbon black as the color material and the silica as the high-durability insulating metal oxide particle, a black coating film having a uniform optical density and excellent electrical insulation was obtained . However, in the case of Comparative Examples 1-3 in which the high-durability insulating metal oxide particles were not combined, it was confirmed that the relative dielectric constant characteristics were poor compared to Examples 1 to 7 in which both the black material and the high-durability insulating metal oxide particles were used in combination .

Particularly, in the case of Example 1 and Comparative Example 4, the same black material carbon black was applied, but it can be seen that the difference in the relative dielectric constant occurs when the size of the average particle diameter of the applied silica is different. That is, in Comparative Example 4, due to the small average particle diameter, it was not able to effectively lower the value of the relative dielectric constant, i.e., less than 5.0. This proves that when the average particle diameter of silica is small, it does not effectively inhibit percolation of carbon black. In the case of Comparative Example 5, although the relative dielectric constant characteristics were good, the roughness of the surface was bad enough to be visible to the naked eye during coating, which was unsuitable for coating materials.

3. Evaluation of heat resistance

The black substrate prepared by the above method was measured with a Mitsubishi Chemical Surface Resistance Meter (model name: Hiresta-UP, MCP-HT450). Thereafter, the substrate subjected to the heat treatment at 300 캜 for 30 minutes and the substrate subjected to the heat treatment at 400 캜 for 30 minutes were again measured for the secondary resistance by the same measuring system. The evaluation was made according to the following evaluation criteria based on the change in the primary resistance value and the secondary resistance value, and the results are shown in Table 4.

division Example Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 1 Example 2 Example 3 Example 4 Example 5
Heat-resistant property 300 ° C
Heat resistance O O O O O O O X X X X O 400 ° C
Heat resistance O O O O O O O X X X X O Pencil hardness 5H 5H 5H 5H 5H 5H 5H 3H 3H 3H 4H 4H

?: Primary resistance value / Secondary resistance value <10 ⁴ ?

?: 10 ⁴ ? Cm 2 <primary resistance value / secondary resistance value <10 ⁶ ?

X: primary resistance value / secondary resistance value > 10 &lt; ⁶ &gt;

As can be seen from the above results, it can be seen that in the embodiments in which the high-durability insulating inorganic oxide particles are mixed, the change in the resistance value is smaller than that in the comparative examples in which the high-durability insulating inorganic oxide particles are not mixed. From this, not only the black substrate can have a low dielectric property due to the inorganic oxide particles, but also the electric resistance value can be stably maintained even at the additional high temperature thermal process. As in the measurement of the relative dielectric constant, in Comparative Example 4, when the high temperature was applied, the small average particle diameter of the insulating particles did not effectively prevent the percolation of the carbon black, which resulted in failure to maintain an effective resistance value . From the pencil hardness measurement results, it can be seen that the embodiments have a higher film hardness than the comparative examples.

According to the present invention, a black coating film having excellent electrical insulation as well as a black coating composition having a high and uniform optical density can be produced. The black coating film has low dielectric constant, high resistance, high heat resistance, chemical resistance, and high film hardness, and can continuously maintain electrical characteristics and properties for a post-process, especially a high temperature process. When the black coating film is applied to an image display apparatus, the reflectance is decreased and the contrast ratio is increased, so that the visibility of the screen can be improved.

Claims (16)

A black material, a high-durability insulating metal oxide particle, a polymerizable compound and a polymerization initiator,
Wherein the high-durability insulating metal oxide particles have an average particle diameter of 60 to 150 nm and a polydispersity of 2.0 or less. delete delete The method according to claim 1,
Wherein the high-durability insulating metal oxide particles are surface-treated with a silane coupling agent. The method according to claim 1,
Wherein the highly durable insulating metal oxide particles are at least one selected from the group consisting of silica, alumina, titania, and zirconia. The method according to claim 1,
Wherein the black material comprises at least one inorganic pigment selected from the group consisting of carbon black, titanium black, metal oxides, complex oxides, metal sulfides and metal carbonates. The method according to claim 1,
The black material is 5 to 95 parts by weight based on 100 parts by weight of the sum of the solid content of the black material and the high durable insulating metal oxide particles and the high durable insulating metal oxide particles are 5 to 95 parts by weight, Wherein the solid content of the high-durability insulating metal oxide particles is 5 to 95 parts by weight of the total composition. delete delete delete delete delete delete delete delete delete

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