KR100794178B1 - Ink for forming non-frit black matrix for plasma display panel - Google Patents

Abstract

The present invention relates to an organosol ink for forming a metal oxide pattern, and more particularly, to an ink for forming a black matrix (BM) without frit on a front substrate of a plasma display panel (PDP). The present invention relates to an organosol ink for forming a metal oxide pattern comprising a ring or linear or branched saturated or unsaturated carboxylic acid metal having 2 to 21 carbon atoms and having 1 to 3 carboxyl groups, and an organic solvent balance.

The complete solution-free frit-free cobalt organosol ink according to the present invention substantially reduces material loss and is non-contact by replacing the existing multi-step complex photolithography process with an inkjet process that can be replaced by one process. It is not limited by the size of the board which is gradually increasing in size, and can simplify the process and dramatically shorten the process time to maximize productivity.

Black Matrix, Cobalt Oxide, Frit, Ink Jet

Description

Ink for forming non-frit black matrix for plasma display panel on the front substrate of plasma display panel

1 is a schematic cross-sectional view showing the structure of a PDP

2 is a flowchart illustrating an adhesion mechanism in which cobalt is chemically bonded to an ITO surface.

Figure 3 is a (a) cross-sectional SEM (b) 1000 magnification SEM photograph of the cobalt oxide film (prepared in Example 1), (c) EDX data, (d) transmittance measurement results, (e) XRD data

FIG. 4 shows (a) cross-sectional SEM, (b) 1000-magnification SEM, (c) 5000-magnification SEM, and (d) 10000 of a cobalt oxide film (prepared in Example 2) where the surface is dense and flattened by addition of triethanolamine Magnification SEM, (e) reflectance, (e) transmittance

FIG. 5 shows (a) cross-sectional SEM, (b) 1000-magnification SEM, (c) 5000-magnification SEM, and (d) 10000 of cobalt oxide film (prepared in Example 3) where polyethyleneglycol was added and the surface was dense and flattened. Magnification SEM, (e) reflectance, (e) transmittance

FIG. 6 shows (a) cross-sectional SEM, (b) 1000-magnification SEM, (c) 5000-magnification SEM, (d) 10000-magnification SEM, and (e) of a polypyrrolidone-added cobalt oxide film (prepared in Example 4) Reflectance, (e) transmittance

turn Applicant Country Applicant (Inventor) Name of invention Public number Characteristics of the technology One) Japan Sun Ink Manufacturing Co., Ltd. (Hujiwara Nobuya) Manufacturing Method of Plasma Display Panel Patent Publication 2004-63247 Method and composition for preparing black matrix for PDP with composition of frit + cobalt oxide + binder + photocuring polymer + photocuring agent 2) Korea LG Electronics Co., Ltd. (Songmugang) Plasma display panel Patent Publication 2001-0059008 Black matrix composed of ruthenium oxide and lead oxide carbon 3) Korea Samsung SDI Corporation (Lee Jun Bae) Black matrix and its manufacturing method Patent Publication 2003-0029291 Black matrix of an alloy composed of SiO and at least two metals selected from the group consisting of Fe, Co, Ti and V by vacuum deposition. 4) Korea LG Electronics Co., Ltd. Plasma display panel Patent Publication 2003-0037489 As a black powder, at least one of cobalt (Co) oxide, chromium (Cr) oxide, manganese (Mn) oxide, copper (Cu) oxide, iron (Fe) oxide, and carbon (C) oxide, , Black matrix comprising at least one of PbO-B2O3-Bi2O3, ZnO-SiO2-Al2O3 and PbO-B2O3-CaO-SiO2 as frit glass

The present invention relates to an organosol ink for forming a metal oxide pattern, and more particularly, to an ink for forming a black matrix (BM) without frit on a front substrate of a plasma display panel (PDP). It is about.

It is sometimes necessary to form a metal oxide pattern on a substrate used for an electronic device. For example, the black matrix of the plasma display panel is printed by screen printing using black paste on the lower end of the bus electrode in order to improve the contrast of the screen. In this case, the black paste used was a composition containing a black composite oxide in the form of a copper oxide or chromium oxide or iron oxide or an oxide mixed with them. As shown in the structure of the PDP of FIG. 1, an insulating paste is required in a PDP that generates a discharge between electrodes on the same substrate and implements a screen when the black matrix becomes conductive, since the discharge is inhibited.

In general, black matrices of plasma display panels form a paste of black metal oxide together with a glass frit and form a pattern by lithography after film formation.

Japanese Patent Application Publication No. 2004-63247, filed by Japan Solar Ink Manufacturing Co., Ltd., discloses the results of research using cobalt oxide as black inorganic fine particles. In the disclosed patent, cobalt oxide and organic binder having a particle size of 0.05-5 microns, a photopolymerizable monomer, a photopolymerization initiator, and a particle size of 5 microns or less having a softening point of 400-600 ° C. to form a black matrix by a conventional photolithography process. A certain amount of glass powder, conductive powder, and silica powder were added to improve adhesion between the substrate and the black matrix. However, this technique is a limiting factor in the application of printing because the glass frit component must be included to improve adhesion to the glass substrate. In addition, after film formation, the pattern is developed by lithography and then etched to produce such a subtractive method. However, the subtractive method is a general pattern forming technique applied to a semiconductor or a display. As the additives can achieve precise patterns, they can shorten the process and prevent the waste of materials to obtain economical efficiency, which is very advantageous in terms of environmental and manufacturing cost savings.

An object of the present invention is to provide an ink for black matrices capable of forming a black matrix pattern having good physical properties without frits by a conventional printing method.

It is also an object of the present invention to provide an ink for black matrix for forming a black matrix pattern by an ink jet printing method.

Organo for forming a metal oxide pattern without frits on a glass substrate comprising a ring or linear or branched saturated or unsaturated hydrocarbon carboxylic acid metal having 2 to 21 carbon atoms and having 1 to 3 carboxyl groups and a residual amount of organic solvent according to the present invention. Sol ink is provided. The carboxylic acid metal is preferably fatty acid cobalt and the metal oxide pattern is preferably a black matrix. Hydrogen in the carboxylic acid metal may be substituted with 1 to 15 fluorine, preferably 1 to 9 fluorine.

The fatty acid cobalt is preferably defined by the following formula (1).

(CF3) n (CH2) m (CH) l (COO-) x Coy

N = 0-3 are preferably 1, l = 0-3 are preferably 0, m = 0-15, x = 1-3, and y = x / 2.

The fatty acid cobalt in the organo sol ink is preferably 0.01 to 90 wt.%, Most preferably 1 to 50 wt.%. The organic solvent is a lower aliphatic alcohol, a lower aliphatic ketone, or a heterocyclic organic solvent or a mixture thereof. For example, acetone, methanol, ethanol, normal propanol, isopropanol, normal butanol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, perfuryl alcohol, methyl ethyl ketone, diacetone alcohol, THF, pyrrolidone, Polypyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-1,2-imidazolidinone or mixtures thereof. Heterocyclic organic solvents and lower aliphatic ketones should be used in the range of 0.1 to 5 wt.% To increase dispersion stability. The organic solvent may further comprise 0.1 to 5 wt.% Of a polyhydric alcohol, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, or glycerol for controlling the drying rate.

In addition, the present invention provides a method of forming a black matrix pattern without frit by forming a pattern on a front substrate of a plasma display panel with the organo sol ink and then firing in an oxidizing atmosphere. The organo sol ink of the present invention is formed on a substrate by contact or non-contact, then dried and burned in an oxidizing atmosphere to decompose organic matter and form a metal oxide pattern. In particular, fatty acid cobalt is used to form black cobalt oxide to form a black matrix on a substrate. Although the present invention is not limited thereto, FIG. 2 proposes an explanation of an adhesion mechanism in which cobalt is chemically bonded to the ITO surface.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

1 mole of cobalt acetate is added to water and stirred for 30 minutes to dissolve completely. In a separate vessel, dilute 2 moles of trifluoroacetic acid in water and stir for 30 minutes. Add the trifluoroacetic acid solution to the solution of cobalt acetate and stir for 30 minutes. All experiments are conducted at room temperature. The resulting mixed solution is mounted on a rotary distillation apparatus to completely remove organic materials that have not reacted with water, and then cobalt trifluoroacetate is prepared. 10 g of the resulting cobalt trifluoroacetate is dissolved in 5 g of methanol, followed by complete solution by addition of 5 g of normal-propanol. Use a low boiling point solvent or high boiling point solvent to adjust the viscosity to 8 ~ 15 cP with ink jetting, and use a surfactant such as Aerosol OT or Triton to adjust the contact angle with the substrate to 20 ~ 45 °. Adjust by addition.

Lines were formed on the glass substrate by the inkjet method. The equipment used for the experiment was manufactured by Litrex corporation, the head meniscus pressure was set to -20mm, the experimental condition was applied 119.5V applied voltage at the frequency of 1.2kHz, and the piezo operating time was 9.8us. Set to. Printing speed is 20mm / sec.

After drying at 200 ° C., the firing process was heated up at a rate of 5 ° C./min from room temperature to 575 ° C., then maintained at 575 ° C. for 30 minutes, and then cooled slowly to room temperature to terminate the reaction, and the firing pattern was tested. Fig. 3 shows the results of measurement with the spectrophotometer model name (CM-2600d), which is released for measurement by Minolta of Japan. 3 are (a) cross-sectional SEM (b) 1000 magnification SEM photographs, (c) EDX data, (d) transmittance measurement results, and (e) XRD data of a cobalt oxide film, respectively. X-rays of the components in the box on the left of (c) are shown on the right EDX graph. In the graph on the right, the materials analyzed in the square are oxygen, cobalt and silica, and silica is the peak that appears when glass is used as a substrate, and the remaining cobalt and oxygen means that the film is completely made of cobalt oxide. (d) is the result of measuring the transmittance in the visible region by UV, (e) proves that the film produced by the X-ray diffractometer analysis result is cobalt oxide.

Example 2

10 g of cobalt trifluoroacetate is dissolved in 5 g of methanol, followed by complete solution by addition of 5 g of normal-propanol. In order to achieve flatness and densification of the film, 0.015 g of triethanolamine is added. A low boiling point solvent or a high boiling point solvent may be used to adjust the viscosity to 8 to 15 cP, and a surfactant such as aerosol OT or triton may be adjusted to adjust the contact angle with the substrate to 20 to 45 ° to enable ink jetting. Line formation and firing were the same as in Example 1. The measured results are shown in Figure 4 in (a) cross-sectional SEM, (b) 1000-magnification SEM, (c) 5000-magnification SEM, (d) 10000-magnification SEM, (e) reflectance of the cobalt oxide film (prepared in Example 2). , (e) transmittance.

 Example 3

10 g of cobalt trifluoroacetate is dissolved in 5 g of methanol, followed by complete solution by addition of 5 g of normal-propanol. In order to achieve flatness and densification of the film, 0.015 g of polyethylene glycol is added. A low boiling point solvent or a high boiling point solvent may be used to adjust the viscosity to 8 to 15 cP, and a surfactant such as aerosol OT or triton may be adjusted to adjust the contact angle with the substrate to 20 to 45 ° to enable ink jetting. Line formation and firing were the same as in Example 1. The measurement results are shown in Figure 5 in (a) cross-sectional SEM, (b) 1000-magnification SEM, (c) 5000-magnification SEM, (d) 10000-magnification SEM, (e) reflectance of the cobalt oxide film (prepared in Example 3). , (e) transmittance.

Example 4

10 g of cobalt trifluoroacetate is dissolved in 5 g of methanol, and then 5 g of normal-propanol is added to complete solution. 0.015 g of polypyrrolidone is added to achieve flatness and densification of the film. A low boiling point solvent or a high boiling point solvent may be used to adjust the viscosity to 8 to 15 cP, and a surfactant such as aerosol OT or triton may be adjusted to adjust the contact angle with the substrate to 20 to 45 ° to enable ink jetting. Line formation and firing were the same as in Example 1. The measured results are shown in Figure 6 in (a) cross-sectional SEM, (b) 1000-magnification SEM, (c) 5000-magnification SEM, (d) 10000-magnification SEM, (e) reflectance of the cobalt oxide film (prepared in Example 4). , (e) transmittance.

The present invention makes it possible to produce a frit-free cobalt organo sol ink in complete solution. The full solution frit-free cobalt organosol ink according to the present invention substantially reduces material losses by replacing the existing multi-step complex photolithography process with an inkjet process that can be replaced by one process. -demand, DOD), non-contact type is not limited by the size of the substrate is gradually larger, the process can be maximized by dramatically shortening the direct write process time.

Claims (15)

An organo sol ink for forming a metal oxide pattern without frit on a glass substrate comprising a ring, a linear or branched, saturated or unsaturated hydrocarbon carboxylic acid metal having 2 to 21 carbon atoms and a carboxyl group having 1 to 3 carbon atoms and an organic solvent balance. The organo sol ink according to claim 1, wherein hydrogen of the carboxylic acid metal is substituted with 1 to 15 fluorine. The organosol ink according to claim 2, wherein the carboxylic acid metal is fatty acid cobalt, hydrogen of the fatty acid cobalt is substituted with 1 to 9 fluorine, the metal oxide pattern is a black matrix, and the black sol is formed on a plasma display panel without frit. . The organosol ink according to claim 1, wherein the fatty acid cobalt is defined by the following formula (1). (CF3) n (CH2) m (CH) l (COO-) x Coy (Where n = 0-3, m = 0-15, l = 0-3, x = 1-3, y = x / 2) The organosol ink according to claim 4, wherein n = 1 in the formula (1). The organo sol ink of claim 3, wherein the fatty acid cobalt comprises 0.01 to 90 wt.% And an organic solvent balance. 7. An organo sol ink according to claim 6 wherein the fatty acid cobalt is 1-50 wt.%. The organo sol ink according to claim 7, wherein the organic solvent is a lower aliphatic alcohol, a lower aliphatic ketone, or a heterocyclic organic solvent. The method of claim 8, wherein the organic solvent is acetone, methanol, ethanol, normal propanol, isopropanol, normal butanol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol, perfuryl alcohol, methyl ethyl ketone, diacetone alcohol, An organosol ink which is an organic solvent selected from the group consisting of THF, pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-1,2-imidazolidinone and mixtures thereof. delete delete 10. The organo sol ink according to claim 9, wherein said organo sol ink is used for forming the black matrix of the plasma display panel by ink jet printing. 10. The organo sol ink of claim 9, wherein said organo sol ink is used for black matrix formation of a plasma display panel by offset printing. 14. A method of forming a black matrix pattern without frit by forming a pattern on a front substrate of a plasma display panel using the organosol ink of any one of claims 1 to 9, 12 and 13. Way. delete

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