KR102361595B1 - Black photosensitive resin composition, and black matrix and column spacer for liquid crystal display manufactured thereby - Google Patents

Abstract

The present invention relates to a black photosensitive resin composition and a black matrix and column spacer for a liquid crystal display prepared therefrom, and more particularly, to a black photosensitive resin composition comprising an alkali-soluble resin and a photopolymerizable compound in a certain content ratio range, and the same It relates to a black matrix and a column spacer for a liquid crystal display manufactured from
The black photosensitive resin composition having the above composition not only secures physical properties such as optical density, insulation, light-shielding property, and elastic recovery rate required for both the black matrix and the column spacer, but also has excellent adhesion to improve the durability and reliability of the liquid crystal display device. have.

Description

Black photosensitive resin composition and black matrix and column spacer for liquid crystal display prepared therefrom

The present invention relates to a black photosensitive resin composition usable for both a black matrix and a column spacer having excellent light-shielding properties, elastic recovery rate, solvent resistance, reliability, and high adhesion properties, and a black matrix and column spacer for a liquid crystal display manufactured thereby. will be.

The display industry has undergone a rapid change from a cathode-ray tube (CRT) to a flat panel display represented by a plasma display panel (PDP), an organic light-emitting diode (OLED), and a liquid-crystal display (LCD). In particular, LCD is a major product in the flat panel display market and consists of an upper plate equipped with a color filter, a lower plate equipped with a thin film transistor (TFT), and a liquid crystal injected therebetween.

The color filter is a key component that expresses color in LCD and has been adopted for a wide range of uses such as notebook PCs, monitors, and portable terminals along with the spread of flat panel displays. These color filters implement various colors on the screen through patterns of red (R), green (G), and blue (B) on the substrate, and between each of the red (R), green (G), and blue (B) patterns. A black matrix that prevents light leakage between pixels, an overcoat (OC) that improves flatness by correcting the step difference between each pixel, and a column spacer that maintains the cell-gap between the two substrates ( CS (column spacer).

In the production of curli filters, a photosensitive resin composition containing a colorant corresponding to each color of red (R), green (G), and blue (B) is uniformly coated by spin coating on a substrate on which a black matrix is patterned. After that, the coating film formed by heating and drying is exposed and developed, and operation of further heating and curing if necessary is repeated for each color to form pixels of each color. In this case, the black matrix BM is positioned at the boundary between the colored layers of each color to prevent color mixing of different colors in each pixel or to hide the electrode pattern, and is mainly formed of a black photosensitive resin composition. In addition, the overcoat OC and the column spacer CS are also formed using the photosensitive resin composition.

Accordingly, the importance of the photosensitive resin composition is increasing as the use of LCDs is advanced and diversified, and the demand for excellent mechanical properties and rapid response to light to improve productivity and durability is increasing.

In addition to this, it is recently required that one material used inside the display simultaneously perform various roles. Typically, as a black matrix-integrated column spacer, not only the uniform optical density (OD) required in the black matrix, but also excellent electrical insulation is required. In addition, very high reliability is required, and the dissolution properties of the used colorant to the organic solvent must be controlled.

However, when only carbon black is used to form a black matrix-integrated column spacer like a general black matrix, optical density is satisfied but electrical insulation is poor. In addition, all black matrix materials using inorganic compounds did not satisfy the physical properties required for the black matrix integrated column spacer due to low insulating properties.

In addition, in a panel in which a black matrix is formed on the TFT surface or formed on top of a color filter, high insulation or low dielectric properties are required because electrical insulation directly affects the liquid crystal. As such, although the composition of the photosensitive composition for forming the black matrix and the column spacer is similar, in the case of the column spacer, it is not easy to apply one composition to both due to the difference in required physical properties, such as not using a colorant. not.

For example, Korean Patent Laid-Open No. 2012-0033893 discloses a binder resin, a polyfunctional monomer, a photopolymerization initiator or a photosensitizer, and a solvent, and a black pigment such as aniline black, perylene black, or metal oxide is added as a colorant thereto. technology is mentioned.

In addition, Korean Patent Publication No. 2013-0081019 discloses that a copolymer having a specific polymerization unit is added to the photosensitive resin composition consisting of an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator and a solvent, and this copolymer increases the degree of crosslinking. A method for improving storage stability and chemical resistance when forming a black matrix and black column spacer by having a reactive functional group is described.

These patents provide a resin composition that can be used as both a black matrix and a column space through various combinations of compounds used as colorants or addition of a copolymer having a reactive group. There is only an improvement in the effect, and the effect is not sufficient.

Meanwhile, Korean Patent Laid-Open No. 2009-0107718 limits the addition ratio of the binder polymer and the polymerizable compound having an ethylenically unsaturated bond in the ink composition for a curli filter, but this is to improve color characteristics when forming a color filter. It is independent of the proposed surface roughness improvement.

Korean Patent Publication No. 2012-0033893 Korean Patent Publication No. 2013-0081019 Korean Patent Publication No. 2009-0107718

Accordingly, the present applicant has conducted various studies to prepare a photosensitive resin composition that can be used as both by simultaneously satisfying the physical properties of the black matrix and the column spacer of the liquid crystal display. It has been confirmed that the black matrix and column spacer can improve the reliability and durability of the liquid crystal display by satisfying the optical density, light blocking properties, electrical insulation, elastic recovery rate, and chemical resistance required by the black matrix and column spacer, and at the same time having excellent adhesion. Thus, the present invention was completed.

Accordingly, it is an object of the present invention to provide a black photosensitive resin composition comprising an alkali-soluble resin and a photopolymerizable compound in a certain ratio so as to be used for forming a black matrix and a column spacer.

In addition, another object of the present invention is to provide a use of the black photosensitive resin composition for producing a black matrix.

In addition, another object of the present invention is to provide a use of the black photosensitive resin composition to prepare a column spacer.

In addition, another object of the present invention is to provide a use in which the black photosensitive resin composition can be used for manufacturing a black matrix-integrated column spacer.

In order to achieve the above object, the present invention comprises a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,

It provides a black photosensitive resin composition comprising 5 to 70 parts by weight of a photopolymerizable compound based on 100 parts by weight of the alkali-soluble resin to form a coating film having a root mean square roughness (R _q ) value of 350 to 900 Å.

In addition, the present invention features a black matrix for a liquid crystal display prepared from the black photosensitive resin composition.

In addition, the present invention is characterized in that the column spacer for a liquid crystal display made of the black photosensitive resin composition.

In addition, the present invention features a black matrix-integrated column spacer for a liquid crystal display prepared from the black photosensitive resin composition.

The black photosensitive resin composition according to the present invention not only secures physical properties such as optical density, insulation, light-shielding property, and elastic recovery rate required for both the black matrix and the column spacer, but also has excellent adhesion to improve the durability and reliability of the liquid crystal display device. can

The present invention provides a black photosensitive resin composition that can be used as a black matrix, a column spacer, or a black matrix-integrated column spacer in a liquid crystal display device.

In general, the smaller the amount of the photopolymerizable compound in the black photosensitive resin composition, the better the surface roughness, but when the amount of the photopolymerizable compound is too small, other required physical properties such as elastic recovery rate may be reduced. Therefore, it is necessary to properly control the content of each component to achieve an optimal balance between the required physical properties.

The present invention provides a black photosensitive resin composition in which an alkali-soluble resin and a photopolymerizable compound are adjusted in a specific content ratio, and the surface roughness and elastic recovery rate of the coating film formed by using the alkali-soluble resin and the photopolymerizable compound in a certain ratio are improved. can Therefore, the black photosensitive resin composition not only secures physical properties such as optical density, electrical insulation, light shielding, heat resistance, solvent resistance, etc. required for both the black matrix and the column spacer, but also has improved surface roughness and elastic recovery to improve adhesion. Therefore, it is possible to secure the advantages of improving the light leakage phenomenon that occurs when the conventional surface roughness is poor, the decrease in shielding properties due to this, and the difficulty in driving the liquid crystal display device.

The black photosensitive resin composition according to the present invention contains an alkali-soluble resin and a photopolymerizable compound in a certain content ratio, and in addition, a colorant, a photoinitiator and a solvent.

Hereinafter, each composition will be described.

The alkali-soluble resin in the present invention has reactivity and alkali solubility under the action of light or heat, acts as a dispersion medium for solid content including colorants, and functions as a binder resin, which is alkaline used in the development step of coating film production using the resin composition Any binder resin soluble in the developer can be used.

Alkali-soluble resin according to the present invention is used by selecting one having an acid value of 50 to 200 (KOH mg / g). The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer and is involved in solubility. If the acid value of the alkali-soluble resin is less than the above range, it is difficult to secure a sufficient development speed. Conversely, if the acid value exceeds the above range, the adhesion with the substrate is reduced, so that a short circuit of the pattern is likely to occur, and the storage stability of the entire composition is lowered to increase the viscosity. a problem arises

In addition, the alkali-soluble resin may consider limitation of molecular weight and molecular weight distribution (Mw/Mn) in order to improve surface hardness for use as a color filter. Preferably, the weight average molecular weight is 3,000 to 30,000 Da, preferably 5,000 to 20,000 Da, and the molecular weight distribution is in the range of 1.5 to 6.0, preferably 1.8 to 4.0. The alkali-soluble resin having the molecular weight and molecular weight distribution within the above ranges is excellent in the solubility of the non-exposed part in the developer as well as the aforementioned improved hardness and high residual film rate, and can improve resolution.

The alkali-soluble resin includes one selected from the group consisting of a polymer of a carboxyl group-containing unsaturated monomer, a copolymer with a monomer having an unsaturated bond copolymerizable therewith, and combinations thereof.

In this case, the carboxyl group-containing unsaturated monomer may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid. Specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be its mono(2-methacryloyloxyalkyl) ester, for example, succinic acid mono(2-acryloyloxyethyl), succinic acid mono(2-methacryloyloxyethyl) ), mono(2-acryloyloxyethyl phthalate), mono(2-methacryloyloxyethyl) phthalate, etc. are mentioned. The unsaturated polyhydric carboxylic acid may be a mono(meth)acrylate of the dicarboxy polymer at both terminals, and examples thereof include ω -carboxypolycaprolactone monoacrylate and ω -carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively.

In addition, the monomer copolymerizable with the carboxyl group-containing unsaturated monomer is an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, an unsaturated From the group consisting of ether compounds, vinyl cyanide compounds, unsaturated imide compounds, aliphatic conjugated diene compounds, macromonomers having monoacryloyl or monomethacryloyl groups at the ends of molecular chains, bulky monomers, and combinations thereof Only 1 selected type is possible.

More specifically, the copolymerizable monomer is styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p- Methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethylether, p-vinylbenzylmethylether, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidyl aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Oxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acryl Rate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylic Rate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl Acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3- unsaturated carboxylic acid esters such as phenoxypropyl methacrylate, glycerol monoacrylate, and glycerol monomethacrylate; 2-Aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl groups such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate acid aminoalkyl ester compounds; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate, a vinyl propionate, a vinyl butyrate, and a vinyl benzoate; unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, and N-2-hydroxyethylmethacrylamide; unsaturated imide compounds such as maleimide, benzylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; and a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. macromonomers having; Bulky monomers such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, and a monomer having a rosin skeleton capable of lowering the relative dielectric constant can be used.

The content of the alkali-soluble resin is 5 to 50% by weight, preferably 5 to 40% by weight within 100% by weight of the total black photosensitive resin composition. This content is a range selected by considering solubility in a developer and pattern formation in various ways. When used within the above range, solubility in a developer is sufficient to form a pattern, and the film of the pixel portion of the exposed part during development The reduction is prevented and the omission property of the non-pixel portion is improved.

The photopolymerizable compound is not particularly limited as long as it is a substance that polymerizes and cures by receiving light irradiation such as ultraviolet rays, and is a compound that can be polymerized by the action of a photoinitiator. The photopolymerizable compound is a component for enhancing the strength of the pattern, and may be a monofunctional monomer, a bifunctional monomer, or a trifunctional or more polyfunctional monomer.

Specific examples of the monofunctional monomer include acrylate, methacrylate, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like. Commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), or Viscot 158 (Osaka Yuki Chemical High School). can

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) acrylate, Bis(acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc. are mentioned. Commercially available products include Aronix M-210, M-1100, 1200 (Toagosei), KAYARAD HDDA. (Nippon Kayaku), Biscott 260 (Osaka Yuki Chemical High School), AH-600, AT-600 or UA-306H (Kyoeisha Chemical).

Specific examples of the trifunctional or more multifunctional photopolymerizable compound include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate , pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, thipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylate Tiddipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are available. Commercially available products include Aronix M-309, TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD. DPHA-40H (Nippon Kayaku Co., Ltd.) and the like.

Among the photopolymerizable compounds exemplified above, trifunctional or higher (meth)acrylic acid esters and urethane (meth)acrylates are particularly preferable in that they have excellent polymerizability and can improve strength.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The content of the photopolymerizable compound may be included in an amount of 0.1 to 40% by weight, preferably 1 to 20% by weight within 100% by weight of the total black photosensitive resin composition. This content range is a range selected in various ways in consideration of the tendency for the strength or smoothness of the column spacer or the black matrix integrated column spacer to become good. If the content is less than the above range, the strength and smoothness are insufficient, and conversely, the range If it exceeds, a problem occurs that patterning is not easy due to high strength, so it is appropriately used within the above range.

The black photosensitive resin composition according to the present invention contains 5 to 70 parts by weight of the photopolymerizable compound, preferably 10 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. This content ratio range serves to control the surface roughness and elastic recovery rate of the pattern generated after irradiation with light. On the contrary, when the content ratio is exceeded, there is a problem in that durability is lowered due to excessive surface roughness.

Specifically, the black photosensitive resin composition includes an alkali-soluble resin and a photopolymerizable compound in the above content ratio to form a coating film having a root mean square roughness (R _q ) value of 350 to 900 Å.

In general, the roughness parameter, which is a statistical value indicating the degree of surface roughness, is R _a , R _q , R _z , R _max expressed as a value.

R _a is It represents the arithmetic mean roughness, and specifically, the absolute value of the height that changes within the measurement area is measured from the surface, which is the average line, and arithmetic averaged. Also called arithmetic average, center line average.

R _q is a parameter that has _a similar meaning to R a , but R _a is an arithmetic average and is calculated using the general average method, but R _q is called root mean square roughness. Measured from the line-in surface and expressed as the root mean square.

R _max means the maximum peak to vally roughness height. It is taken as much as the reference length from the roughness section curve, and is parallel to the center line of the section curve and refers to the distance between two parallel lines that are in contact with the highest mountain and the deepest valley.

R _z is a 10-point average roughness (ten point height), as much as the reference length is taken from the roughness section curve, an arbitrary straight line (reference line) parallel to the mean line of the section curve is drawn, and the average value of the distance from the baseline of the five highest mountains and It is expressed as the difference from the average of the distances from the baseline of the five lowest valleys.

In particular, the present invention considers the R _q value among the roughness parameters described above, which indicates the local state of the surface of the coating film formed through the R _q value, and the root mean square roughness of the coating film formed of the black photosensitive resin composition (R _q ) By having a value in the range of 350 to 900 Å, the effect of improving adhesion may be exhibited. If it is less than 350 Å in the range of the R _q value, the content of the colorant constituting the black photosensitive resin composition should be very low. However, it is difficult to provide light blocking properties to the black matrix, the column spacer, or the black matrix-integrated column spacer. Conversely, when the R _q value exceeds 900 Å, the surface unevenness is severe, making it difficult to apply to a liquid crystal display device.

In addition, the arithmetic mean roughness (R _a ) of the coating film formed of the black photosensitive resin composition of the present invention has a value in the range of 250 to 650 Å. If the _Ra value is out of the above range, the surface of the coating film may become too smooth or too rough, thereby inhibiting the desired effect of improving adhesion.

In addition, the black photosensitive resin composition can be applied on a substrate, dried and cured to obtain a coating film, and at this time, by including 5 to 70 parts by weight of a photopolymerizable compound with respect to 100 parts by weight of the alkali-soluble resin, the elastic recovery rate is 85 to 95% coating film can be obtained. The elastic recovery rate can be measured by checking the amount of change recovered after pressing the pattern formed on the substrate at a constant speed using a hardness meter.

The colorant constituting the black photosensitive resin composition of the present invention may serve to provide light-blocking properties to prevent light leakage to the black matrix and to prevent malfunction of devices due to externally generated light in the column spacer.

The colorant is not particularly limited in the present invention as long as it has light-shielding properties in visible light, and all known colorants such as organic pigments, dyes and black pigments may be used, and these may be used alone or in combination of two or more.

As an example, the organic pigment is a compound classified as a pigment in the color index (CI; published by The Society of Dyers and Colorists), specifically, the following color index (CI) Names can be given.

C.I. Pigment Yellow No. 1, C.I. Pigment Yellow No. 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 55, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow No. 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment Yellow No. 128, C.I. Pigment Yellow No. 137, C.I. Pigment Yellow No. 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow No. 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow No. 153, C.I. Pigment Yellow No. 154, C.I. Pigment Yellow No. 155, C.I. Pigment Yellow No. 166, C.I. Pigment Yellow No. 168, C.I. Pigment Yellow No. 173, C.I. Pigment Yellow No. 180, C.I. Pigment Yellow No. 211;

C.I. Pigment Orange No. 5, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 14, C.I. Pigment Orange No. 24, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 34, C.I. Pigment Orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment Orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment Orange No. 43, C.I. Pigment Orange No. 46, C.I. Pigment Orange No. 49, C.I. Pigment Orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment Orange No. 64, C.I. Pigment Orange No. 65, C.I. Pigment Orange No. 68, C.I. Pigment Orange No. 70, C.I. Pigment Orange No. 71, C.I. Pigment Orange No. 72, C.I. Pigment Orange No. 73, C.I. Pigment Orange No. 74;

C.I. Pigment Red No. 1, C.I. Pigment Red No. 2, C.I. Pigment Red No. 5, C.I. Pigment Red No. 9, C.I. Pigment Red No. 17, C.I. Pigment Red No. 31, C.I. Pigment Red No. 32, C.I. Pigment Red No. 41, C.I. Pigment Red No. 97, C.I. Pigment Red No. 105, C.I. Pigment Red No. 122, C.I. Pigment Red No. 123, C.I. Pigment Red No. 144, C.I. Pigment Red No. 149, C.I. Pigment Red No. 166, C.I. Pigment Red No. 168, C.I. Pigment Red No. 170, C.I. Pigment Red No. 171, C.I. Pigment Red No. 175, C.I. Pigment Red No. 176, C.I. Pigment Red No. 177, C.I. Pigment Red No. 178, C.I. Pigment Red No. 179, C.I. Pigment Red No. 180, C.I. Pigment Red No. 185, C.I. Pigment Red No. 192, C.I. Pigment Red No. 194, C.I. Pigment Red No. 202, C.I. Pigment Red No. 206, C.I. Pigment Red No. 207, C.I. Pigment Red No. 208, C.I. Pigment Red No. 209, C.I. Pigment Red No. 214, C.I. Pigment Red No. 215, C.I. Pigment Red No. 216, C.I. Pigment Red No. 220, C.I. Pigment Red No. 221, C.I. Pigment Red No. 224, C.I. Pigment Red No. 242, C.I. Pigment Red No. 243, C.I. Pigment Red No. 254, C.I. Pigment Red No. 255, C.I. Pigment Red No. 262, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I. Pigment Red No. 272;

C.I. Pigment Blue No. 15, C.I. Pigment Blue No. 15:3, C.I. Pigment Blue No. 15:4, C.I. Pigment Blue No. 15:6, C.I. Pigment Blue No. 16, C.I. Pigment Blue No. 60, C.I. Pigment Blue No. 80;

C.I. Pigment Purple No. 1, C.I. Pigment Purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38;

C.I. Pigment Green No. 7, C.I. Pigment Green No. 36, C.I. Pigment Green No. 58;

C.I. Pigment Brown No. 23, C.I. Pigment Brown No. 25;

C.I. Pigment Black No. 1, C.I. Pigment Black No. 7.

In some cases, these organic pigments are treated with rosin, surface treatment using a pigment derivative into which acidic or basic groups are introduced, surface graft treatment using a polymer compound, etc., fine particle treatment using sulfuric acid, or using an organic solvent or water. It may be that washing treatment or the like has been performed.

In addition, pigments used in printing inks, inkjets, etc., and water-soluble azo, insoluble azo, phthalocyanine, quinacritone, isoindolinone, isoindoline, perylene, perinone, dioxyzine, anthraquinone, dianone Traquinonyl, anthrapyrimidine, ananthrone, indanthrone, pravanthrone, pyranthrone pigments, etc. can be used.

The black pigment may be aniline black, perylene black, titanium black, or carbon black, and may be used without particular limitation as long as it has light-shielding properties.

Available carbon blacks include CHBK-17 from Mikuni Saxo Co.; Donghae Carbon Co., Ltd. SYSTO 5HIISAF-HS, SYSTO KH, SYSTO 3HHAF-HS, SYSTO NH, SYSTO 3M, SYSTO 300HAF-LS, SYSTO 116HMMAF-HS, SYSTO 116MAF, SYSTO FMFEF- HS, cisto SOFEF, cisto VGPF, cisto SVHSRF-HS, and cisto SSRF; Diagram Black II, Diagram Black N339, Diagram Black SH, Diagram Black H, Diagram LH, Diagram HA, Diagram SF, Diagram N550M, Diagram M, Diagram E, Diagram G, Diagram R, Diagram N760M, Diagram of Mitsubishi Chemical Corporation LR, #2700, #2600, #2400, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45, #45L, #25, # CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL30B, and OIL31B; PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIAL BLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101; RAVEN-1100ULTRA, RAVEN-1080ULTRA, RAVEN-1060ULTRA, RAVEN-1040, RAVEN-1035, RAVEN-1020, RAVEN-1000, RAVEN-890H, RAVEN-890, RAVEN-880ULTRA, RAVEN-860ULTRA, RAVEN-850, RAVEN-820, RAVEN-790ULTRA, RAVEN-780ULTRA, RAVEN-760ULTRA, RAVEN-520, RAVEN-500, RAVEN-460, RAVEN-450, RAVEN-430ULTRA, RAVEN-420, RAVEN-410, RAVEN- 2500ULTRA, RAVEN-2000, RAVEN-1500, RAVEN-1255, RAVEN-1250, RAVEN-1200, RAVEN-1190ULTRA, and RAVEN-1170 etc. are mentioned.

The carbon black is not particularly limited as long as it is a light-shielding pigment, and known carbon black may be used. Examples of the carbon black as the black pigment include channel black, furnace black, thermal black, lamp black, and the like.

In addition, carbon black coated with resin may be used as the carbon black as the black pigment. Since the resin-coated carbon black has lower conductivity than the resin-coated carbon black, excellent electrical insulation properties can be imparted when forming a black matrix or black column spacer.

Dyes include, for example, C.I. Solvent Yellow No. 2, C.I. Solvent Yellow No. 14, C.I. Solvent Yellow No. 16, C.I. Solvent Yellow No. 33, C.I. Solvent Yellow No. 34, C.I. Solvent Yellow No. 44, C.I. Solvent Yellow No. 56, C.I. Solvent Yellow No. 82, C.I. Solvent Yellow No. 93, C.I. Solvent Yellow No. 94, C.I. Solvent Yellow No. 98, C.I. Solvent Yellow No. 116, C.I. Solvent Yellow No. 135; C.I. Solvent Orange No. 1, C.I. Solvent Orange No. 3, C.I. Solvent Orange No. 7, C.I. Solvent Orange No. 63; C.I. Solvent Red No. 1, C.I. Solvent Red No. 2, C.I. Solvent Red No. 3, C.I. Solvent Red No. 8, C.I. Solvent Red No. 18, C.I. Solvent Red No. 23, C.I. Solvent Red No. 24, C.I. Solvent Red No. 27, C.I. Solvent Red No. 35, C.I. Solvent Red No. 43, C.I. Solvent Red No. 45, C.I. Solvent Red No. 48, C.I. Solvent Red No. 49, C.I. Solvent Red No. 91:1, C.I. Solvent Red No. 119, C.I. Solvent Red No. 135, C.I. Solvent Red No. 140, C.I. Solvent Red No. 196, C.I. Solvent Red No. 197; C.I. Solvent Purple No. 8, C.I. Solvent Purple No. 9, C.I. Solvent Purple No. 13, C.I. Solvent Purple No. 26, C.I. Solvent Purple No.28, C.I. Solvent Purple No. 31, C.I. Solvent Purple No. 59; C.I. Solvent Blue No. 4, C.I. Solvent Blue No. 5, C.I. Solvent Blue No. 25, C.I. Solvent Blue No. 35, C.I. Solvent Blue No. 36, C.I. Solvent Blue No. 38, C.I. Solvent Blue No. 70; C.I. Solvent Green No. 3, C.I. Solvent Green No. 5, C.I. Solvent Green No. 7 etc. are mentioned.

The colorant is included in an amount of 1 to 50% by weight, preferably 5 to 40% by weight in 100% by weight of the total black photosensitive resin composition. If it is used in less than the above content, the optical density is lowered. Conversely, when used in excess of the above range, the relative dielectric constant becomes too high, which may cause a problem in driving when the liquid crystal display device is introduced.

The colorant in the present invention may be used together with a dispersing agent and a dispersing aid if desired.

As said dispersing agent, although suitable dispersing agents, such as cationic, anionic, and nonionic, can be used, for example, A polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, etc. are mentioned. Such dispersants are commercially available, for example, as acrylic copolymers, DisperBYK-2000, DisperBYK-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK), Solsperse 5000 (manufactured by Lubrizol) ), as polyurethane, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-165, DisperBYK-167, DisperBYK-170, DisperBYK-182 (above, manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol) ), Solsperse 24000 (manufactured by Lubrizol) as polyethyleneimine, and Ajisper PB821, Ajisper PB822, and Ajisper PB880 (manufactured by Ajinomoto Fine Techno, Ltd.) as polyester.

As said dispersing auxiliary agent, a pigment derivative is mentioned, for example, Specifically, copper phthalocyanine, diketopyrrolopyrrole, the sulfonic acid derivative of quinophthalone, etc. are mentioned.

These dispersants can be used individually or in mixture of 2 or more types. The content of the dispersant is usually 100 parts by weight or less, preferably 1 to 70 parts by weight, and more preferably 10 to 50 parts by weight based on 100 parts by weight of the colorant. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

The photopolymerization initiator in the present invention is a compound for initiating polymerization of the photopolymerizable compound, and is not particularly limited in the present invention, but acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, and anthracene-based compounds , anthraquinone-based, and biimidazole-based compounds may be used, and these may be used alone or in combination of two or more.

The acetophenone compound is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy) Phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl- oligomers of 2-dimethylamino-1-(4-morpholinophenyl)butan-1-one and 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propan-1-one are possible and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one among them is preferably used.

Benzophenone-based compounds include benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis(dimethyl amino)benzophenone, 4,4'-bis (diethyl amino) benzophenone and the like are possible.

As a triazine-based compound, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxy styryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxy naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloro methyl) -s-triazine, 2- (p-triyl) -4,6-bis (trichloro methyl) -s-triazine, 2- Biphenyl-4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho 1-yl)-4,6- Bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2,4-trichloro methyl ( piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxy styryl)-6-triazine, and the like are possible.

The thioxanthone-based compound may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of the oxime-based compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and commercial products such as OXE-01 and OXE-02 from Ciba are representative.

As the benzoin-based compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like can be used.

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

Examples of the anthraquinone-based compound include 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benzanthraquinone, and 2,3-diphenyl anthraquinone.

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, the phenyl group at the 4,4',5,5' position is replaced by a carboalkoxy group Substituted imidazole compounds and the like are possible.

The photopolymerization initiator may be used in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight within 100% by weight of the total black photosensitive resin composition. This content range is in consideration of the photopolymerization rate of the photopolymerizable compound and the physical properties of the finally obtained coating film. If the content is less than the above range, the polymerization rate is low and the overall process time may be prolonged. Since the physical properties of the coating film may be rather deteriorated over time, it is appropriately used within the above range.

The photopolymerization initiator may be used in combination with a photopolymerization initiator adjuvant. When a photopolymerization initiation aid is used together with the photoinitiator, the black photosensitive resin composition containing them becomes more sensitive, and productivity is improved when using the photopolymerization initiator to form a column spacer for maintaining a cell gap, so it is preferable.

The photopolymerization initiation adjuvant may be used to increase polymerization efficiency, and may include an amine-based compound, an alkoxyanthracene-based compound, and a thioxanthone-based compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- Dimethylaminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name, Michler's ketone), 4,4'-bis(diethylamino)benzophenone , 4,4'-bis(ethylmethylamino)benzophenone etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

Further, examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-die Toxanthracene etc. are mentioned.

As the thioxanthone-based compound, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone etc. are mentioned.

The photopolymerization initiation adjuvant may be directly manufactured or commercially available, and for example, the EAB-F series (Hodogaya Chemical Industry Co., Ltd.) may be used.

Such a photopolymerization initiation adjuvant is generally 10 moles or less per 1 mole of the photopolymerization initiator, and preferably used within the range of 0.01 to 5 moles. When the photopolymerization initiation auxiliary agent is used within the above range, the effect of improving the productivity can be expected by increasing the polymerization efficiency.

As the solvent in the present invention, any solvent capable of dissolving or dispersing the above-mentioned composition is used, and the present invention is not particularly limited. Representative examples include alkylene glycol monoalkyl ethers, alkylene glycol alkyl ether acetates, aromatic hydrocarbons, ketones, lower and higher alcohols, and cyclic esters. More specifically, as the solvent, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; Alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate Ryu; 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, ethylene glycol, and glycerin; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; Cyclic esters, such as ( gamma )-butyrolactone, etc. are mentioned.

Among the above solvents, organic solvents having a boiling point of 100 to 200°C in the above solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxypropionic acid and esters such as ethyl and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate ethyl, 3-methyl and methyl toxypropionate. These solvents can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent is not particularly limited, but may be the remainder to satisfy 100% by weight of the black photosensitive resin composition, and may be included, for example, in an amount of 20 to 85% by weight, and when included within the range, applicability will be good. can

In addition, the black photosensitive resin composition of the present invention may further include one or more additives selected from adhesion promoters, surfactants, dispersants, antioxidants, ultraviolet absorbers, thermal polymerization inhibitors, and leveling agents.

The adhesion promoter includes methacryl such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyldimethoxysilane, methacryloyloxypropyltriethoxysilane, and methacryloyloxypropyldimethoxysilane. At least one selected from the group consisting of loyl silane coupling agents may be used, and as the alkyl trimethoxy silane, at least one selected from the group consisting of octyltrimethoxy silane, dodecyltrimethoxy silane, and octadecyltrimethoxy silane species can be used.

As the surfactant, MCF 350SF, F-475, F-488, F-552 (manufactured by DIC), etc. may be used, but the present invention is not limited thereto, and the range may be further expanded in some cases.

As the dispersing agent and leveling agent, all of those generally used in the art may be used.

As the antioxidant, 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-g,t-butylphenol, etc. may be used, and as the ultraviolet absorber, 2-(3- t-Butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole, alkoxy benzophenone, and the like can be used. The thermal polymerization inhibitor includes hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis(3-methyl-6- t-butylphenol), 2,2-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptoimidazole, etc. can be used.

In addition, the black photosensitive resin composition of the present invention may further include one or more secondary additives selected from a carbon black dispersion, a functional resin binder, a monomer, a radiation-sensitive compound, and other additives.

The preparation of the black photosensitive resin composition as described above is not particularly limited in the present invention, and a known method for preparing the photosensitive resin composition is followed.

For example, after adding the colorant to the solvent, the remaining composition and other additives may be added and obtained through stirring. In this case, the colorant may be dissolved or dispersed in a solvent or alkali-soluble resin, and when the additive is in the form of a solution, it may be added in advance to the solvent together with the colorant.

The black photosensitive resin composition thus prepared can be preferably used as a black matrix, column spacer, or black matrix-integrated column spacer of a display device, preferably a liquid crystal display device.

As a column spacer for maintaining a cell gap, the black photosensitive resin composition according to the present invention includes an alkali-soluble resin and a photopolymerizable compound in a certain content ratio to form a coating film having an R _q value in a specific range, thereby improving adhesion and increasing reliability. have. In addition, the black photosensitive resin composition of the present invention is less deformed by external pressure, has flexibility and a high elastic recovery rate, and can prevent damage from light due to its excellent light-shielding properties.

In addition, the black photosensitive resin composition according to the present invention has high optical density (OD), light blocking properties and electrical insulation required for the black matrix, and thus can satisfy the physical properties required for both the black matrix and the column spacer, and as a result, the black matrix It is also preferably applicable as an integral column spacer.

The black matrix integrated spacer does not form a black matrix and a column spacer, respectively, but can serve as both a black matrix and a column spacer in one pattern, and the black photosensitive resin composition according to the present invention can be used.

The introduction of the black matrix may be patterned through a photolithography method after coating to form a pattern. The photolithography method is not particularly limited in the present invention, and any known method using the photosensitive resin composition is applicable.

For example, the patterned black matrix is

a) applying a black photosensitive composition to the substrate surface;

b) drying the solvent by precure (pre-bake);

c) applying a photomask on the obtained film and irradiating actinic light to cure the exposed portion;

d) performing a developing process for dissolving the unexposed part using an aqueous alkali solution; and

e) It can be obtained by performing drying and post-baking.

The substrate is a glass substrate or a polymer plate is used. As a glass substrate, especially soda-lime glass, barium-strontium containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be used preferably. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide or polysulfone.

In this case, a wet coating method using a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater), or an inkjet coating device is possible to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate, etc. The heating temperature and heating time in the prebaking are appropriately selected according to the solvent to be used, and are performed at a temperature of, for example, 80 to 150°C for 1 to 30 minutes.

Moreover, exposure performed after a prebaking is performed by an exposure machine, and only the part corresponding to a pattern is exposed by exposing through a photomask. In this case, the irradiated light may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

Alkali development after exposure A desired pattern is formed by this development for the purpose of removing the resist of the non-removable part of the unexposed part. As a developing solution suitable for this alkali development, for example, a carbonate of an alkali metal or alkaline earth metal An aqueous solution or the like can be used. In particular, using an aqueous alkali solution containing less than 1 to 3 wt% of carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, etc., using a developer or ultrasonic cleaner within a temperature of 10 to 50 ° C, preferably 20 to 40 ° C. to do it

The post-baking is performed to increase adhesion between the patterned color conversion layer and the substrate, and is performed through heat treatment at 80 to 220° C. for 10 to 120 minutes. Post-bake As with pre-bake, it is performed using an oven, a hot plate, or the like.

The black matrix obtained through this method is formed to have a sufficient size, several to several thousand micrometers, preferably 0.1 to 100 μm, more preferably 1 to 50 μm, to maintain high photosensitivity and enable excellent fine pattern formation. do.

These black matrix, column spacers, or black matrix-integrated column spacers not only secure physical properties such as optical density, elastic recovery rate, electrical insulation, and light blocking properties required for all of them, but also have excellent adhesion, heat resistance, and solvent resistance to ensure liquid crystal display The reliability of the device can be improved.

Hereinafter, preferred examples are presented to help the understanding of the present invention, but the following examples are merely illustrative of the present invention, and it will be apparent to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention, It goes without saying that such variations and modifications fall within the scope of the appended claims. In addition, "%" and "part" which show content below are based on mass unless otherwise indicated.

production example 1. Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux cooling tube, a dropping funnel and a nitrogen introduction tube was prepared. As a monomer dropping lot, a mixture 40 of 3,4-epoxytricyclodecan-8-yl (meth)acrylate and 3,4-epoxytricyclodecan-9-yl (meth)acrylate in a molar ratio of 50:50 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added to prepare for stirring. As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanthiol and 24 parts by weight of PGMEA were added to prepare stirring.

Thereafter, 395 parts by weight of PGMEA was added to the flask, the atmosphere in the flask was exchanged from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring.

Then, the monomer and the chain transfer agent were started dripping from the dropping lot. The dropping was carried out for 2 hours while maintaining 90° C., and after 1 hour, the temperature was raised to 110° C. and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH/g.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

For the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin, the GPC method was used under the following conditions, and the ratio of the weight average molecular weight and the number average molecular weight obtained at this time was calculated as the molecular weight distribution (Mw). /Mn).

Device: HLC-8120GPC (manufactured by Toso Co., Ltd.)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

production example 2. on the side chain an epoxy group, a carboxyl group, and polymeric Preparation of Resins Containing Unsaturated Bonds

130 g of methoxybutyl acetate and 110 g of methoxybutanol were put into a 1 liter separation flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel and nitrogen inlet tube, and after raising the temperature to 80° C., ω-carboxy-poly Caprolactone monoacrylate (Aronix M5300: manufactured by Toagosei Co., Ltd.) 202 g, 3,4-epoxytricyclodecan-9-yl acrylate and 3,4-epoxytricyclodecan-8-yl acrylate A mixture of 50:50 (molar ratio) 148 g and 30 g of azobisdimethylvaleronitrile in 380 g of methoxybutyl acetate was added dropwise over 5 hours, and further aged for 3 hours to obtain a copolymer having a carboxyl group.

The reaction was carried out under a nitrogen stream. The obtained copolymer had a solid content of 35.5 wt%, an acid value of 108 KOHmg/g, and a weight average molecular weight (Mw) of 12100 and a dispersion degree of 1.98 as a result of GPC.

Thereafter, 38 g of glycidyl methacrylate, 7 g of 1,8-diazabicycloundecene-7 (DBU) and 3 g of metoquinone are added to the obtained copolymer, and reacted at 75° C. for 10 hours, followed by light and/or heat. A curable resin solution was obtained. The reaction was carried out under a mixed air stream containing 7% by weight of oxygen and 93% by weight of nitrogen.

Example 1 to 6 and Comparative Examples 1 to 3

After adding PGMEA as a solvent to the mixer, a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator were added thereto, and uniformly mixed through stirring to prepare a black photosensitive resin composition. At this time, the composition follows the composition of Table 1, and the content ratio of the alkali-soluble resin and the photopolymerizable compound is as shown in Table 2 below.

A 5×5 cm glass substrate (Corning, #1737) was washed with a neutral detergent and water and dried. The obtained black photosensitive resin composition was applied on the glass substrate by spin coating, then placed on a heating plate and dried at a temperature of 80 to 120° C. for 1 to 2 minutes to remove the solvent.

Then, ultraviolet rays were irradiated on the thin film. At this time, the ultraviolet light source was irradiated with light at an exposure dose (365 nm) of 40 to 150 mJ/cm 2 in an atmospheric atmosphere using an ultra-high pressure mercury lamp (trade name: USH-250D) manufactured by Ushio Denki Co., Ltd. to form a pattern.

The thin film irradiated with ultraviolet light was developed by immersion in a KOH aqueous solution developing solution having a pH of 10.5 for 2 minutes.

The glass substrate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 to 250° C. for 10 to 30 minutes to prepare a pattern. The thickness of the film prepared above was formed to be 3.5㎛.

Composition (wt%) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 coloring agent A-1 ¹⁾ 0.72 0.72 0.72 0.72 0.72 0.72 0.72 0.72 0.15 A-2 ²⁾ 4.42 4.42 4.42 4.42 4.42 4.42 4.42 4.42 4.42 A-3 ³⁾ 3.66 3.66 3.66 3.66 3.66 3.66 3.66 3.66 3.66 Alkali-soluble resin B-1 ⁴⁾ 6.26 7.3 8.34 9.39 9.91 - 5.74 10.43 5.94 B-2 ¹⁰⁾ - - - - - 9.39 - - - photopolymerizable compound KAYARAD DPHA ^{5 )} 4.17 3.13 2.09 1.04 0.52 1.04 4.69 - 5.06 photopolymerization initiator Irgacure OXE-02 ⁶⁾ 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 0.47 additive DisperBYK-163 ⁷⁾ 2.19 2.19 2.19 2.19 2.19 2.19 2.19 2.19 2.19 Solsperse 5000 ⁸⁾ 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 0.11 solvent PGMEA ^{9 )} 78 78 78 78 78 78 78 78 78 1) CI Pigment Red No. 194
2) CI Pigment Blue No. 15:6
3) Carbon Black PBk7 (MA8, Mitsubishi Chemical Co., Ltd.)
4) the resin prepared in Preparation Example 1
5) Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
6) Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) (Ciba Specialty Chemical company)
7) Polyurethane pigment dispersant (manufactured by BYK)
8) Acrylic pigment dispersant (manufactured by Lubrizol)
9) Propylene glycol monomethyl ether acetate
10) the resin prepared in Preparation Example 2

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Alkali-soluble resin: photopolymerizable compound 100:67 100:43 100:25 100:11 100:5 100:11 100:81 - 100:85

Experimental example 1. Surface roughness evaluation

For the patterns obtained in Examples 1 to 6 and Comparative Examples 1 to 3, using Dektak 6M (Veeco), R _a and R _q values were measured, and surface roughness was evaluated through this. As for the measurement method, the measurement scan range of Dektak was set to 500 μm, and the measurement range point of the result value was set to 50 μm and 450 μm, respectively, within the entire scan range. The measurement point is the front part of the fabricated board. The obtained results are shown in Table 3 below.

Experimental example 2. Adhesion evaluation

Using TQC's Cross Cut Adhesion Test CC1000 on the patterns prepared in Examples 1 to 6 and Comparative Examples 1 to 3, 11 lines were drawn horizontally and vertically at intervals of 1 mm on the surface to obtain a total of 100 grids. Cutting was carried out so that The adhesion of the cut surface was evaluated using TQC's tape. At this time, the adhesion was evaluated based on the following criteria, and the results obtained are shown in Table 3 below.

<Standard>

○: Maintain more than 90 patterns

△: 60 to 89 patterns are maintained

X: keep 9 to 59 patterns

Experimental example 3. color power evaluation

The coloring power was evaluated for the patterns prepared in Examples 1 to 6 and Comparative Examples 1 to 3 using a 301 densitometer manufactured by X-Rite. At this time, the coloring power was evaluated based on the following criteria, and the results obtained are shown in Table 3 below.

<Standard>

○: 2.0 or higher

△: 1.0 or more and less than 2.0

X: less than 1.0

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 R _q (Å) 822 630 534 426 887 472 2359 1354 320 R _a (Å) 560 410 350 270 620 283 1760 835 183 adhesion ○ ○ ○ ○ ○ ○ X X ○ color power ○ ○ ○ ○ ○ ○ ○ ○ X

Referring to Table 3, in the case of Examples 1 to 6 prepared with a composition containing an alkali-soluble resin and a photopolymerizable compound in a certain amount according to the present invention, the R _q value of the formed film is in the range of 350 to 900 Å. did In addition, it was confirmed that the R _a value of the formed film falls within the range of 250 to 650 Å.

However, in the case of Comparative Example 1 containing the photopolymerizable compound in an excess of the content ratio and Comparative Example 2 not containing the photopolymerizable compound at all, the R _q value showed a value of 1000 Å or more, and it was confirmed that the adhesion was poor compared to the Example. In the case of Comparative Example 3, the content of the colorant was low and the adhesion was excellent, but the coloration power was poor.

Experimental example 4. modulus of elasticity evaluation

Using a Fisher durometer (Fischerscope H100C, Helmut-Fisher) on the patterns prepared in Examples 1 to 6 and Comparative Examples 1 to 3, the amount of displacement recovered after pressing at a rate of 3.3mN/sec to 50mN To confirm, the elastic modulus was calculated, and the results obtained are shown in Table 4 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 modulus of elasticity
(%) 88% 91% 94% 92% 91% 95% 54% 61% 49%

Referring to Table 4, in the case of Examples 1 to 6 prepared with the composition containing the alkali-soluble resin and the photopolymerizable compound in a predetermined amount according to the present invention, it was confirmed that the elastic modulus is 85% or more.

However, in Comparative Examples 1 and 3 including the photopolymerizable compound in an excess of the content ratio, and Comparative Example 2 not including the photopolymerizable compound at all, it can be seen that the modulus of elasticity is not good at an average of 59%.

The black photosensitive resin composition according to the present invention can be preferably used as a black matrix, a column spacer, or a black matrix-integrated column spacer of a liquid crystal display device.

Claims (10)

It contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent,
The colorant includes at least one of CI Pigment Red No. 194 and CI Pigment Blue No. 15:6,
A black photosensitive resin composition comprising 5 to 70 parts by weight of a photopolymerizable compound with respect to 100 parts by weight of the alkali-soluble resin to form a coating film having a root mean square roughness (R _q ) value of 350 to 900 Å. According to claim 1,
A black photosensitive resin composition comprising 10 to 50 parts by weight of a photopolymerizable compound based on 100 parts by weight of the alkali-soluble resin. According to claim 1,
The alkali-soluble resin is a black photosensitive resin composition comprising an epoxy group, a carboxyl group and a polymerizable unsaturated bond in the side chain. According to claim 1,
The coating film is a black photosensitive resin composition, characterized in that the arithmetic mean roughness (R _a ) value of 250 to 650 Å. According to claim 1,
The black photosensitive resin composition is present in 100% by weight of the total composition.
A black photosensitive resin composition comprising 1 to 50% by weight of a colorant, 5 to 50% by weight of an alkali-soluble resin, 0.1 to 40% by weight of a photopolymerizable compound, 0.01 to 10% by weight of a photoinitiator, and the remainder of the solvent. A coating film obtained by coating, drying and curing the black photosensitive resin composition according to any one of claims 1 to 5 on a substrate. 7. The method of claim 6,
The coating film, characterized in that the elastic recovery rate of the coating film is 85 to 95%. A black matrix for a liquid crystal display comprising the coating film of claim 6 . A column spacer for a liquid crystal display, comprising the coating film of claim 6. A black matrix-integrated column spacer for a liquid crystal display comprising the coating film of claim 6 .