KR20110116810A - Surface-coated metal oxide black pigment and photoresist composition comprising thereof for black matrix - Google Patents

Abstract

The present invention relates to a metal oxide black pigment surface-treated with an organic phosphonic acid, a pigment dispersion prepared therefrom and a photoresist composition and a black matrix to which the photoresist composition is applied. Metal oxide black pigment surface-treated with organic phosphonic acid can be used as a black matrix material that requires high resistance and low dielectric constant due to further improved dispersion stability and electrical properties.

Description

Surface-coated metal oxide black pigment and photoresist composition comprising conjugate for black matrix}

The present invention relates to a metal oxide black pigment surface-treated with organic phosphonic acid to have excellent dispersion stability and electrical insulation properties, and a pigment dispersion and a photoresist composition for a black matrix.

LCD (liquid crystal display) is a transparent portion and an opaque portion by inserting a liquid crystal material at intervals of 1 to 10 ㎛ on a transparent substrate of glass on which the transparent electrode is installed, by applying a voltage between the electrodes to align the liquid crystal in a certain direction To form. On the other hand, the LCD of the natural color is applied to the three primary color layer of red, blue and green color on the transparent glass substrate, and adjust the voltage to control the light transmission of the liquid crystal, as a result of the three primary color filter of red, blue and green color The color is displayed by controlling the amount of light transmitted through the screen.

As a method of forming the trichromatic colored layer, there are a method of forming a trichromatic colored layer on a substrate provided with a black matrix that divides each of the colored layers in advance, and first forming a trichromatic colored layer and then installing a black matrix. . The role of the black matrix is to separate the three primary colors to prevent color mixing, and to block light to the liquid crystal driving electrode or TFT (TFT) installed on the substrate. The black matrix can be made by applying chromium or carbon black as a light shielding agent. When chromium is applied, the light shielding performance, environmental resistance, and chemical resistance is excellent, but the production cost is high due to complex processes and high equipment costs, and there are environmentally harmful problems. Due to these problems, recently, the black matrix using carbon black has been actively studied and put into practice. However, the black matrix to which carbon black is applied also has a disadvantage of preventing cross talk between adjacent electrode layers only by providing an insulating layer on the black matrix.

On the other hand, the color filter substrate can be produced by a method such as dyeing, printing, pigment dispersion, electrodeposition, etc., mainly produced by the pigment dispersion method. The pigment dispersion method is a method of manufacturing a color filter by coating a photoresist composition containing a light-shielding material, exposing a pattern of a form to be formed, and then repeating the process of removing and curing non-exposed areas for each color. The pigment dispersion method is used in the manufacture of the black matrix because it has the advantage of improving the heat resistance and durability, which is the most important property of the color filter, and maintaining the thickness of the film uniformly.

In recent years, as the demand for LCD devices and color filter makers has increased the demand for light and thin display devices, carbon black and titanium black are being actively studied for lighter and thinner display materials. To improve the properties of resistance, conductivity, light shielding performance, optical density, etc., the surface structure of organic black millbase and the application of new materials are being studied.

Disclosure of Invention An object of the present invention is to provide a metal oxide black pigment and a black resist photoresist composition including the same, which are excellent in dispersion stability and light shielding performance and have high electric resistance to prevent crosstalk between electrode layers in a color filter substrate. To provide.

In order to achieve the above object, the present invention provides a metal oxide black pigment surface-treated with an organic phosphonic acid. Through surface treatment with organic phosphonic acid, dispersion stability and light shielding performance may be improved, and insulation may be improved while increasing electrical resistance, thereby preventing crosstalk between electrode layers.

Although there is no particular limitation on the metal oxide, the metal oxide is preferably a fourth, fifth or sixth cycle of the metal oxide or a mixture thereof, and more preferably copper, iron, manganese and palladium. , Oxides of metals such as nickel, cobalt, and the like, most preferably CuMn ₂ O ₄ , Cu _X Mn _{3 - X} O ₄ (0 <x <3), Cu _{X +1} Mn _{2 -X} O ₄ (0 <x <2), Cu (II) O, Fe ₃ O ₄ , Fe ₂ O ₃ , MnO, Mn ₂ O ₃ and Mn ₃ O ₄ is a metal including at least one or more oxide selected from. Commercially available metal oxide black pigments include, for example, Black Oxide (KOLORJET); Black # 3510 and # 3550 (Dainichi Seika Color); Iron Oxide Black 330, 5330 and 722 from Yuxing; SC444 Spinel black Pbk26 from Sinopia; Pigment 24-3061Pk and Pigment 24-3060 (Ferro); Bayferrox 318, 318M (DF) and 328 (LANXESS); Black 3702, 3250, 6350 and 3300 from Asahi Kasei; Calisha Con Black Oxide and Conjet Black Oxide (CIBA); AB 820 (KAWANURA Chemical); Black 20C920, 20C980, 30C933, 30C965, 376A, 430, 444, 10C909A, 10P922 and 411A (Shepherd); And 42-302A, 303A, 303B, 307A, 313A, 42-710A and 701B (TOMATEC).

In order to disperse | distribute a metal oxide black pigment to a dispersion liquid in order to surface-treat with an organic phosphonic acid, it is preferable that a dispersion particle size is 10 micrometers or less. If the dispersion particle size is larger than 10 μm, the uniformity of the surface treatment is lowered and the overall surface treatment efficiency and efficacy are lowered. As a dispersion, water or ethanol aqueous solution is suitable. Dispersion for surface treatment of the metal oxide black pigment of the present invention is preferably dispersed using an ultrasonic disperser.

The organic phosphonic acid used for the surface treatment of the metal oxide black pigment is preferably phosphonoacetic acid (PAA), dihydroxyphosphynylacetic acid, 4-phosphonoaminobenzoic acid (4 -phosphonoamino benzoic acid), 2-phosphonooxypropanoic acid, phosphonobenzene acetic acid, 2-carboxyethyl phosphonic acid (ECPA), 3- 3-aminopropyl phosphonic acid (APPA), 4-aminophenyl phosphonic acid (APA), 2,4-diphosphono-1,2-butanedicarboxylic acid (2, 4-diphosphono-1,2-butanedicarboxylic acid, 4-carboxyphenyl phosphonic acid (CPPA), 4-phosphonoxy benzoic acid, 3-phosphonopropioic acid (3-phosphonopropionic acid), 2-phosphonoxybenzoic acid (3-phosphonoxyben zoic acid) and mixtures thereof.

The metal oxide black pigment surface-treated with organic phosphonic acid is dispersed using ultrasonic waves to disperse the metal oxide black pigment in water or ethanol aqueous solution to have a particle size of 10 μm or less, and the organic phosphonic acid is used at a temperature of 50 ° C. to 80 ° C. After surface treatment for 30 minutes or more, the mixture is washed with water / ethanol solution 5 times or more and dried in a vacuum.

After the surface treatment, the organic phosphonic acid content in the pigment is preferably 0.1 to 10% by weight based on the total amount of the metal oxide black pigment and the organic phosphonic acid. If it is less than 0.1% by weight, excellent dispersion properties, dispersion stability, and electrical insulation may not be obtained than the untreated metal oxide black pigment, and if it exceeds 10% by weight, light shielding performance may be degraded, and dispersion property and dispersion stability may be degraded. .

The metal oxide black pigment surface-treated with the organic phosphonic acid is used for the preparation of the surface-treated metal oxide black pigment dispersion comprising a dispersant and a dispersing medium having an electron donor group. In the metal oxide black pigment dispersions surface-treated with such organic phosphonic acids, the content of the surface-treated metal oxide black pigments is usually 10 to 40% by weight based on the total weight of the pigment dispersion. If it is less than 10% by weight, it is not possible to obtain coloring and shielding power, and when it exceeds 40% by weight, the dispersion viscosity is too high, so that it is not easy to handle the dispersion, and in particular, the adhesion of the formed black matrix to the substrate may be reduced.

Dispersants with electron donating groups exhibit excellent dispersing effects on metal oxide black pigments surface treated with organic phosphonic acids, reducing the viscosity of the metal oxide black pigment dispersions surface treated with organic phosphonic acids and By maximizing the inherent excellent properties (insulation properties, coloring power, shielding power) of the pigment of the surface-treated metal oxide, it is possible to provide a photoresist composition for a black matrix having a high light shielding effect.

Dispersants with electron donating groups are those which are soluble in the dispersion medium and the content is 1 to 10% by weight based on the total weight of the pigment dispersion. If less than 1% by weight, the dispersibility of the surface-treated metal oxide black pigment may be lowered, and when used in more than 10% by weight, developability and dispersion stability of the photoresist composition may be lowered.

For dispersants having an electron donor group, an “electron donor group” means a substituent that tends to provide electrons in the molecule. A dispersing agent having an electron donor is preferably _{-NH 2, -OH, -OCH 3,} -OCOCH 3, -N (CH 3) 2, -NHCOCH 3 , and C ₁ -C molecule the electron donor selected from the ₁₀ group It is a compound which has one or more in a inside.

Oily dispersants having electron donor groups are selected from the group consisting of polycarboxylic acid esters such as polyurethanes and polyacrylates, unsaturated polyamides, amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids and polysiloxanes. Can be.

Aqueous dispersants with electron donating groups are water soluble, such as (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone One or more selected from the group consisting of resins (water soluble high molecular compounds), anionic, nonionic and amphoteric surfactants. Anionic surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ester sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalein sulfonate, sodium alkyldiphenyl ether Disulfonate, monoethanol amine lauryl sulfonate, triethanolamine lauryl sulfate, ammonium lauryl sulfonate, mono ethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanol of styrene-acrylic acid copolymer One or more may be selected from the group consisting of amines and polyoxyethylene alkyl ether phosphates. Nonionic surfactants are a group consisting of polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyne ether phosphate, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate One or more may be selected from. The amphoteric surfactant may be an alkyl betaine such as betaine alkyldimethylaminoacetate, an alkylimidazoline or mixtures thereof.

Commercially available dispersants with amine groups as electron donating groups include Disperbyk 2000, 2001, 130, 161, 162, 163, 164, 165, 166 and 182 (by BYK Chemie); EFKA 4025, 4300, 4330, 4340, 4047, 4046, 4008, 4009, 4010, 4020, 4050, 4055, 4061 and 4080 (CIBA); Or Solsperse 13240, 13940, 24000GR, 28000, 20000, 12000, 27000, 76400 and 76500 (Lubrizol).

The polymerizable dispersant having an electron donating group preferably has a network structure. This structure is a factor for improving the surface adhesion to the metal oxide black pigment.

The dispersion medium is preferably 55 to 85% by weight relative to the total weight of the pigment dispersion, the pigment dispersion stability is lower when the content of the dispersion medium is less than 55% by weight, and the solid content of the pigment dispersion is less when the dispersion medium is more than 85% by weight. Optical shielding performance cannot be realized. Typically, a cellulose acetate solvent or a hydrocarbon compound having an ether or ester bond is used. For example, cellulose acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxy ethyl acetate, 3-ethoxyethyl propionate and propylene glycol monomethyl ether propionate One or more may be selected from the group consisting of: In general, the propylene glycol monomethyl ether is preferably 65% by weight or more and 80% by weight or less with respect to the total weight of the pigment dispersion, and different solvents may be used depending on the type of dispersant.

The dispersion of the metal oxide black pigment surface-treated with an organic phosphonic acid is performed using a paint shaker, a sand mill, a ball mill, a roll mill, or the like. In general, the pigment dispersion of a uniform composition can be obtained by dispersing for 30 minutes to 24 hours at 10 to 50 ℃. In terms of stability of the dispersion, the average dispersion particle size of the surface-treated metal oxide black pigment in the dispersion is preferably 10 nm or more, and the average dispersion particle size of the surface-treated metal oxide black pigment in terms of shielding power, dispersion stability, and coloring power is 500. It is preferable that it is nm or less.

The metal oxide black pigment dispersion surface-treated with the organic phosphonic acid is used for the preparation of the photoresist composition for the black matrix. The photoresist composition for the black matrix may be prepared by mixing the pigment dispersion, the photoresist resin solution, and the solvent.

In the photoresist composition for a black matrix of the present invention, the metal oxide black pigment dispersion surface-treated with an organic phosphonic acid is preferably 30 wt% to 50 wt% with respect to the total weight of the photoresist composition. If it is less than 30% by weight, the optical density may be low, and when it exceeds 50% by weight, the adhesion may be lowered. The photoresist resin solution is preferably 30 to 50% by weight based on the total weight of the photoresist composition. If it is less than 30% by weight, the adhesion may be lowered, and if it exceeds 50% by weight, the optical density may be lowered.

The photoresist resin solution includes a photopolymerizable monomer, a prepolymer, a photopolymerization initiator, a solvent, and other optional components. The photopolymerization initiator, the photopolymerizable monomer, the prepolymer and the solvent in the photoresist resin solution may be appropriately selected according to the pattern purpose of the photoresist. The photopolymerizable monomer is preferably 5% to 20% by weight based on the total weight of the photoresist resin solution. If it is less than 5% by weight, the adhesion may be lowered. If it exceeds 20% by weight, the optical density is lowered. The photopolymerizable monomer is at least one ethylenic compound having at least one addition polymerizable ethylenically unsaturated double bond in which polymerization is induced by radicals, and typically, at least one acrylate monomer having at least one functional group can be used. The prepolymer serves as a binder resin, the content of which is preferably 10% to 30% by weight relative to the total weight of the photoresist resin solution. If it is less than 10 weight%, adhesive force will fall, and if it exceeds 30 weight%, a viscosity will rise and it will be difficult to coat a coating film with a uniform thickness. As the prepolymer, one or more prepolymers typically selected from polyester acrylates, alkyd acrylates and polyol acrylates can be used. The photopolymerizable initiator generates radicals and the content thereof is preferably 0.05 wt% to 5 wt% with respect to the total weight of the photoresist resin solution. If it is less than 0.05 wt%, the photocurability may be lowered, thereby lowering the adhesion. If it is more than 5 wt%, the storage stability may be deteriorated. As the photopolymerizable initiator, one or more photopolymerizable initiators typically selected from carbonyl compounds, sulfur compounds, azo compounds and organic peroxides can be used. The solvent contained in the photoresist resin solution is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone , 3-heptanone, 2-hydroxyethyl propionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl- Group consisting of 3-ethoxypropionate, butyl acetate, amylpermate, isoamyl acetate, isobutyl acetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate and γ-butyrolacetate One or more solvents, wherein the content is based on the total weight of the photoresist resin solution To 50% by weight to 70% by weight. If the content is less than 50% by weight, the storage stability may be deteriorated. If the content is more than 70% by weight, the photoresist resin solution enters a lot when the photoresist is manufactured. It becomes difficult to obtain a uniform coating film of constant thickness. Other optional components include benzyltrimethylammonium chloride, quaternary amines such as diethylhydroxysaamine, organic acids such as oxalic acid and copper compounds such as methyl ether, t-butylpyrocatechol, organic phosphine, phosphite and copper naphthenate May be used and they may be added in the preparation of the pigment dispersion.

The solvent used in the photoresist composition of the present invention is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2- Heptanone, 3-heptanone, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, With ethyl-3-ethoxypropionate, butyl acetate, amylpermate, isoamyl acetate, isobutyl acetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate and γ-butyrol acetate At least one solvent selected from the group consisting of: the content is based on the total weight of the photoresist composition That the more than 10% by weight to 30% by weight is preferred. If it is less than 10% by weight, the storage stability may be lowered, and when it exceeds 30% by weight, it is difficult to obtain a uniform coating film having a predetermined thickness when the photoresist solution is coated on the substrate while the solid content is lowered. The photoresist composition may be used in the form of a coating liquid by a suitable solvent, and a spinner, a wire bar, a flow coating machine, a die coating machine, etc. may be used as the coating device. Image exposure is performed by placing a negative matrix pattern mask on the photopolymerizable layer and irradiating ultraviolet rays through the pattern mask, and an alkali developer is used as a developer, and an inorganic alkali agent such as potassium hydroxide is mainly used.

The viscosity of the photoresist composition for the black matrix is preferably 1 to 100 cP, considering that the thickness of the coating film should be adjusted to be uniform.

The black matrix formed by the present invention is particularly suitable as a black matrix for color filters, having an optical density of 1.2 or more per micrometer and a high electrical resistance.

The black matrix is formed by applying a photoresist composition comprising a surface treated metal oxide black pigment and then performing heat drying, exposure, development, and heat curing. In addition, the color filter applies a photoresist composition in which red, blue, and green colors are dispersed on the surface of the black matrix, and sequentially performs heat drying, exposure, development, and heat curing to form pixel images of each color. It is manufactured by.

Metal oxide black pigment surface-treated with organic phosphonic acid can be used as a black matrix material that requires high resistance and low dielectric constant due to further improved dispersion stability and electrical properties.

The present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

<Production of Surface-treated Metal Oxide Pigments- Example  1>

In order to control the particle size of the initial metal oxide pigment (Black 30C933, Shepherd color), 100g of metal oxide pigment was dispersed in 1000cc of water, and then made into an aqueous dispersion of a metal oxide pigment having an average particle size of 10 μm through sonication. Then 1 g of phosphonoacetic acid is completely dissolved in 100 g of water / ethanol 1: 1 solution. The phosphonoacetic acid solution is added to the metal oxide pigment aqueous dispersion with stirring. At this time, the temperature of the solution is maintained at 50 ℃ to 80 ℃ and stirred for 1 hour to the surface treatment. Subsequently, the surface-treated metal oxide pigment is washed five times or more with a water / ethanol 1: 1 solution, and vacuum dried under a nitrogen atmosphere.

<Production of Surface-treated Metal Oxide Pigments- Example  2>

In order to control the particle size of the initial metal oxide pigment (Black 30C933, Shepherd color), 100g of metal oxide pigment was dispersed in 1000cc of water, and then made into an aqueous dispersion of a metal oxide pigment having an average particle size of 10 μm through sonication. Then 1.5 g of 3-phosphonopropionic acid is completely dissolved in 100 g of water / ethanol 1: 1 solution. The 3-phosphonopropionic acid solution is added to the metal oxide pigment aqueous dispersion with stirring. At this time, the temperature of the solution is maintained at 50 ℃ to 80 ℃ and stirred for 1 hour to the surface treatment. Subsequently, the surface-treated metal oxide pigment is washed five times or more with a water / ethanol 1: 1 solution, and vacuum dried under a nitrogen atmosphere.

<Production of Surface-treated Metal Oxide Pigments- Example  3>

In order to control the particle size of the initial metal oxide pigment (Black 30C933, Shepherd color), 100g of metal oxide pigment was dispersed in 1000cc of water, and then made into an aqueous dispersion of a metal oxide pigment having an average particle size of 10 μm through sonication. Then, 3 g of 2-phosphonoxybenzoic acid is completely dissolved in 100 g of water / ethanol 1: 1 solution. The 2-phosphonoxybenzoic acid solution is added to the aqueous metal oxide pigment aqueous dispersion with stirring. At this time, the temperature of the solution is maintained at 50 ℃ to 80 ℃ and stirred for 1 hour to the surface treatment. Subsequently, the surface-treated metal oxide pigment is washed five times or more with a water / ethanol 1: 1 solution, and vacuum dried under a nitrogen atmosphere.

< Surface treatment  Metal Oxide Pigment Manufacturer- Comparative example  1>

The metal oxide pigment of Comparative Example 1 (Black 30C933, Shepherd color) was prepared in the same manner except that the surface was not treated with organic phosphonic acid in the above examples.

Table 1 below shows the characteristics of the metal oxide pigment surface treated with organic phosphonic acid. The surface-treated metal oxide pigments are distinguished from the untreated metal oxide pigments of the comparative examples in terms of volume resistivity. In the case of surface-treated metal oxide pigments, the movement of electrons is suppressed by the presence of the organic phosphonic acid coating layer, resulting in a marked increase in volume resistivity. The amount of surface-treated organic phosphonic acid can be known through TGA (Thermal Gravity Analysis) analysis. The amount of surface-treated organic phosphonic acid can be determined by increasing the temperature to 300 ° C. in TGA and measuring the weight change.

Table 1. Comparison of Characteristics of Surface Treated Metal Oxide Pigments

1) wt%, organic phosphonic acid / (metal oxide pigment + organic phosphonic acid)

2) Metal Oxide Pigment Aqueous Solution

3) Volume resistivity of carbon black

<For Black Matrix Photoresist  Composition Preparation- Example  4>

Using the metal oxide pigment prepared in Example 1, a photoresist composition for forming a black matrix was prepared in the following manner.

First, 8 wt% of a 20 wt% metal oxide pigment surface-treated with an organic phosphonic acid and a dispersant solsperse 24000 with an electron donor were added to 72 wt% of propylene glycol monomethyl ether acetate, followed by Netzsch nano It disperse | distributed in the minicer which is a dispersing machine, and obtained the metal oxide pigment dispersion liquid surface-treated with the organic phosphonic acid of the uniform composition with favorable dispersion stability.

On the other hand, 23% by weight of epoxy acrylate as a prepolymer, 3% by weight of lauryl acrylate, 3% by weight of methyl methacrylate, 3% by weight of 2-hydroxyethyl acrylate and 1% by weight of methacrylic acid as a photopolymerizable monomer And 65% by weight of propylene glycol monomethyl ether acetate as a solvent, 2% by weight of 2-methyl- (4- (methylthiophenyl) -2-monopolyno-1-propanone as a photoinitiator was added to the photoresist resin. The solution was prepared.

40 wt% of the surface-treated metal oxide pigment dispersion, 40 wt% of the photoresist resin solution, and 20 wt% of propylene glycol monomethyl ether acetate were mixed and dispersed to prepare a photoresist composition for a black matrix. The photoresist composition was applied to a glass plate and a metal plate with a spin coater, dried at 80 ° C. for 2 minutes, and then heat-treated at 220 ° C. for 30 minutes to form a film having a thickness of about 1 μm on each plate.

<For Black Matrix Photoresist  Composition Preparation- Example  5>

A photoresist composition was prepared in the same composition and method as in Example 4 except that the metal oxide pigment (Black 30C933, Shepherd color) manufactured by Example 2 was used to form a black matrix film.

<For Black Matrix Photoresist  Composition Preparation- Example  6>

A photoresist composition was prepared in the same composition and method as in Example 4, except that the metal oxide pigment (Black 30C933, Shepherd color) manufactured by Example 3 was used to form a black matrix film.

<For Black Matrix Photoresist  Composition Preparation- Comparative example  2>

Comparative Example 2 was a photoresist composition was prepared in the same composition and method as in Example 4 except for using the surface treatment of the metal oxide pigment (Black 30C933, Shepherd color) of Comparative Example 1 to form a black matrix film.

The optical density was measured by interpolating the optical density at 1 μm by measuring the OD for each thickness based on the thickness of 1 μm, and the adhesion was measured by performing a cross-cut tape test. In the cross-cut tape test, 11 lines of width and length are drawn at 1mm intervals to make 100 squares. The storage stability was stored at 45 ° C. and the dates of viscosity and dispersion particle size were within 5%. In addition to the above optical density, the surface resistance was further measured by the physical properties of the film. The results are shown in Table 2.

Table 2. Characteristics of Coating Film

1) Optical Density = -log (T% / 100)

 T%: 550nm light transmittance

 Example) 0.1% transmittance: optical density (OD) = 3

2) Adhesion: Residual Square / Full Cross-cut Square

As shown in Table 2, storage stability of the metal oxide pigment was improved, optical density was increased, and surface electrical resistance was also increased.

Claims (20)

Metal oxide black pigment surface treated with organic phosphonic acid. The organic phosphonic acid of claim 1, wherein the organic phosphonic acid is phosphonoacetic acid (PAA), dihydroxyphosphynylacetic acid, 4-phosphonoamino benzoic acid, 2- 2-phosphonooxypropanoic acid, phosphonobenzene acetic acid, 2-carboxylethyl phosphonic acid (ECPA), 3-aminopropylphosphonic acid (3- aminopropyl phosphonic acid (APPA), 4-aminophenyl phosphonic acid (APA), 2,4-diphosphono-1,2-butanedicarboxylic acid (2,4-diphosphono-1,2- butanedicarboxylic acid, 4-carboxyphenyl phosphonic acid (CPPA), 4-phosphonoxy benzoic acid, 3-phosphonopropionic acid, 2 -Phosphonoxybenzoic acid (3-phosphonoxybenzoic acid) and mixtures thereof Pigment according to claim. The pigment according to claim 1, wherein the organic phosphonic acid content in the pigment after the surface treatment is 0.1 to 10% by weight based on the total amount of the metal oxide pigment and the organic phosphonic acid. The pigment according to claim 1, wherein the metal oxide is a fourth, fifth or sixth cycle of the metal oxide or a mixture thereof on the periodic table. The method of claim 1 wherein the metal oxide is CuMn ₂ O ₄ , Cu _X Mn _{3 - X} O ₄ (0 <x <3), Cu _{X +1} Mn _{2 -X} O ₄ (0 <x <2), Cu (II) O, Fe ₃ O ₄ , Fe ₂ O ₃ , MnO, Mn ₂ O ₃ And at least one metal oxide selected from Mn ₃ O ₄ . A metal oxide black pigment surface treated with 10 to 40% by weight of the organic phosphonic acid according to claim 1, based on the total weight of the pigment dispersion; Dispersants having from 1 to 10% by weight electron donating groups; And 55 to 85% by weight of a dispersion medium. 7. The pigment dispersion according to claim 6, wherein the average dispersion particle size of the metal oxide black pigment surface-treated with the organic phosphonic acid is 10 nm to 50 nm. The method of claim 6 wherein the dispersing agent having an electron donor is _{-NH 2, -OH, -OCH 3,} -OCOCH 3, -N (CH 3) 2, -NHCOCH 3 And a compound having at least one electron donating group in the molecule selected from a C ₁ -C ₁₀ alkyl group. The dispersant according to claim 6, wherein the dispersing agent having an electron donating group is a polycarboxylic acid ester, an unsaturated polyamide, an amine salt of polycarboxylic acid, an ammonium salt of polycarboxylic acid, an alkylamine salt of polycarboxylic acid, a polysiloxane, a (meth) acrylic acid-styrene copolymer, (Meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, sodium lauryl sulfate, polyoxyethylene alkyl ester sulfate, sodium dodecylbenzene sulfonate, Alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalein sulfonate, sodium alkyldiphenylether disulfonate, monoethanol amine lauryl sulfonate, triethanolamine lauryl sulfate, ammonium la Uryl sulfonate, mono ethanolamine stearate, sodium stearate, sodium Lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyne ether phosphate, Pigment dispersion, characterized in that at least one selected from the group consisting of polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, alkyl betaine and alkylimidazoline. 7. The pigment dispersion according to claim 6, wherein the dispersion medium is a cellulose acetate solvent or a hydrocarbon compound having an ether or ester bond. The method of claim 6 wherein the dispersion medium is cellulose acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methoxypropyl acetate, 2-methoxy ethyl acetate, 3-ethoxyethyl propionate and propylene glycol mono Pigment dispersion, characterized in that at least one selected from the group consisting of methyl ether propionate. 30% to 50% by weight of the pigment dispersion according to claim 6, based on the total weight of the photoresist composition; 30 wt% to 50 wt% photoresist resin solution; And 10 wt% to 30 wt% of a solvent. 13. The method according to claim 12, wherein the photoresist resin solution comprises 5 wt% to 20 wt% of a photopolymerizable monomer, based on the total weight of the photoresist resin solution; 10 wt% to 30 wt% prepolymer; 0.05 wt% to 5 wt% photopolymerization initiator; And 50 wt% to 70 wt% of a solvent. The photoresist composition of claim 13, wherein the photopolymerizable monomer is at least one ethylenic compound having at least one ethylenically unsaturated double bond. The photoresist composition of claim 13, wherein the photopolymerizable monomer is at least one acrylate having at least one functional group. The photoresist composition of claim 13, wherein the prepolymer is one or more prepolymers selected from polyester acrylates, alkyd acrylates and polyol acrylates. The photoresist composition of claim 13 wherein the photopolymerization initiator is at least one photopolymerization initiator selected from carbonyl compounds, sulfur compounds, azo compounds and organic peroxides. The solvent of claim 13, wherein the solvent included in the photoresist resin solution is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexa. Paddy, 2-heptanone, 3-heptanone, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl-3-ethoxy Propionate, ethyl-3-ethoxypropionate, butyl acetate, amylpermate, isoamyl acetate, isobutyl acetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate and γ- Photoresist bath, characterized in that at least one solvent selected from the group consisting of butyrol acetate Relic. 13. The solvent of claim 12 wherein the solvent is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxyethylpropionate, 3-methyl-3-methoxybutylpropionate, ethyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3 From the group consisting of ethoxypropionate, butyl acetate, amylpermate, isoamyl acetate, isobutyl acetate, butylpropionate, isopropylbutyrate, ethylbutyrate, butylbutyrate, ethylpyruvate and γ-butyrolacetate At least one solvent selected. 20. The black matrix to which the photoresist composition of claim 12 is applied.