KR100669685B1 - Phosphor paste composition including antioxidant for PDP and process for preparing the fluorescent film using the same - Google Patents

Abstract

The present invention relates to a phosphor paste composition for a plasma display device comprising an antioxidant and a method for producing a fluorescent film using the same, wherein the antioxidant is used, for example, by using a phenolic antioxidant and / or a phosphite antioxidant. It is done.

The fluorescent film obtained by using the phosphor paste composition for plasma display elements using such an antioxidant improves the predetermined coordinates before and after the color coordinate change and efficiency.

Description

Phosphor paste composition including antioxidant for PDP and process for preparing the fluorescent film using the same}

The present invention relates to a phosphor paste composition for a plasma display device (PDP) containing an antioxidant and a method of manufacturing a phosphor film using the same.

PDPs are self-illuminating on a similar principle to fluorescent lamps, so even in large screens, the screen brightness is uniform, the contrast is relatively high, and the viewing angle is more than 160 degrees. In addition to the advantages of large size, the PDP is composed of top and bottom glass, and even if the driver circuit portion is installed, the thickness is less than 10cm, and also has the advantage that it is considerably lighter than other display elements, attracting attention as the next generation display.

The gray scale is determined according to the energy of the electron beam that the cathode ray tube (CRT) is incident on the surface of the phosphor, whereas the PDP is adjusted by the number of discharges to display the gray scale. That is, the display of the PDP is made only by the on and off of the discharge, and the on state of the discharge is possible only when the voltage is above a certain voltage.

In the case of the PDP phosphor, the surface of the phosphor is exposed to discharge and ultraviolet ultraviolet (VUV) under discharge conditions, so that light emission and lifetime characteristics such as luminance decrease over time. In particular, the phosphor for PDP has a problem that is easily degraded in the panel manufacturing process. In other words, the phosphor is made of a paste in the current PDP process, printed and then subjected to a sintering process, resulting in a decrease in the efficiency of the phosphor and a change in color coordinates. These results have several causes, but oxidation of the activator during the firing process is one of the main reasons.

In order to overcome such a process deterioration phenomenon, Japanese Patent Application Laid-Open No. Hei 10-125240 discloses the formation of a coating layer in the form of a uniform film on the surface of the phosphor to improve the lifetime and luminous efficiency.

However, the method disclosed in the above publication can be expected to improve the lifespan and efficiency, but the improvement of the color coordinate change is insufficient and there is a need for it.

Accordingly, a technical problem of the present invention is to provide a phosphor paste composition for plasma display devices in which color coordinate change rates and efficiencies are improved simultaneously before and after firing by using an antioxidant for plastics used to prevent oxidative deterioration of plastics during a phosphor manufacturing process. It is.

Another object of the present invention is to provide a method for producing a fluorescent film using the composition.

The present invention provides a phosphor paste composition for a plasma display device comprising an antioxidant in order to achieve the above technical problem.

The phosphor paste composition includes 10 parts by weight of a solvent for a phosphor paste, 0.01 to 5 parts by weight of an antioxidant, and 1 to 30 parts by weight of a phosphor.

As antioxidant used for the said phosphor paste composition, it is preferable to use a phenolic antioxidant, a phosphite antioxidant, or a mixture thereof.

The phenolic antioxidants used in the present invention are, for example, tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3- (3 ', 5'-di -t-butyl-4'-hydroxyphenyl) propionate, 3,5-bis (1,1-dimethylethyl) 4-hydroxy-benzenepropanoic acid, 2,2'-thiodiethylene bis [3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2'-ethylidenebis [4,6-di-t-butylphenol], 1,3,5-tri (3 , 5-di-t-butyl-4-hydroxybenzyl) isoisocyanurate, 2,2'-methylenebis (6-t-butyl-4-methylphenol), 4,4'-butylidenebis ( 2-t-butyl-5-methylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,5-di-t-amylhydroquinone, 1,1,3-tri (2 '-Methyl-4'-hydroxy-5'-t-butylphenyl) butane, polymeric phenol with steric hindrance, triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl ) Propionate], N, N'-hexamethylene bis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionamide], 4,4'-thiobis (2-t-butyl-5-methylphenol), 2,2'-thiobis (6-t-butyl-4-methylphenol), 2,2 ' Methylenebis [4-methyl-6- (1-methylcyclohexyl) phenol] or 1,2-bis (3,5-di-t-butyl-4-hydroxyhydrocinnamil) hydrazine, and the like. Preference is given to tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane of formula (1)

The phosphite-based antioxidants used in the present invention are, for example, tri (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-dicumylphenyl) pentaerythritol diphosphite, tri (4-n-nonylphenyl) phosphite or tetrakis (2,4-di-tert-butyl-phenyl) 4,4'-biphenyl Lene-diphosphite and the like, and tri (2,4-di-butylphenyl) phosphite of the following general formula (2) is particularly preferable.

Antioxidant used in the phosphor paste composition serves to improve the luminous efficiency and color coordinate change of the phosphor by inhibiting the oxidation of the activator generated during the firing process of the phosphor paste, 10 parts by weight of the solvent for the phosphor paste It is preferable to use 0.0001 to 5 parts by weight, and the effect is insignificant if the amount of the antioxidant used is less than 0.0001 parts by weight, and if it exceeds 5 parts by weight, smoke is generated and contamination or side reaction occurs due to impurities.

The solvent for the phosphor paste used in the above-mentioned phosphor paste composition is not particularly limited as long as it is usually used for the manufacture of the phosphor, but butyl carbitol acetate is particularly preferable.

The phosphor used in the phosphor phosphor paste composition for a plasma display device comprising the antioxidant of the present invention can be any of red, green or blue phosphors, and green and blue phosphors which cause a decrease in efficiency and change of color coordinates during the firing process are particularly preferred. .

Method for producing a PDP fluorescent film of the present invention using the phosphor paste composition:

(A) adding a solvent for the phosphor paste and an antioxidant to dissolve to form a solution;

(B) adding a phosphor to the solution and stirring to form a phosphor paste;

(C) printing the phosphor paste on the panel with the same thickness and then drying it;

(D) calcining the phosphor paste after drying is completed.

As a condition of the drying step of step (C) of the manufacturing method, if the phosphor paste printed on the panel is sufficiently dried, there is no particular limitation, but it is performed over about 0.1 to 3 hours at a temperature of about 50 to 150 ° C. desirable.

The conditions of the firing step of step (D) in the manufacturing method is not particularly limited as long as it is a normal firing conditions, it is preferably carried out over 0.5 to 3 hours at a temperature of 400 to 500 ℃.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1

10 parts by weight of butyl carbitol acetate and 0.1 parts by weight of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane were dissolved, and blue phosphor (BaMaAl ₁₀ O ₁₇ : Eu) was dissolved. The mixture was stirred to obtain a phosphor paste. It was printed on an ITO glass substrate with the same thickness, dried at 100 ° C. for 20 minutes, and then calcined at 480 ° C. for 1 hour.

Example 2

Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) Methanol was prepared in the same manner as in Example 1 except that the amount used was 1 part by weight.

Example 3

Except that 0.1 parts by weight of tri (2,4-di-butylphenyl) phosphite was used instead of 0.1 parts by weight of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane. It prepared in the same manner as in Example 1.

Example 4

Except that 1 part by weight of tri (2,4-di-butylphenyl) phosphite was used instead of 0.1 part by weight of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane. It prepared in the same manner as in Example 1.

Example 5

Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) instead of 0.1 parts by weight of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane It was prepared in the same manner as in Example 1 except for using 0.01 part by weight of a mixture of methane and tri (2,4-di-butylphenyl) phosphite.

The mixture of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tri (2,4-di-butylphenyl) phosphite each had a weight ratio of 1: 3.

Example 6

Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) instead of 0.1 parts by weight of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane It was prepared in the same manner as in Example 1 except that 1 part by weight of a mixture of methane and tri (2,4-di-butylphenyl) phosphite were used.

The mixture of tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane and tri (2,4-di-butylphenyl) phosphite each had a weight ratio of 1: 3.

Comparative example

Tetrakisethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane was used in the same manner as in Example 1 except that the antioxidant was not used.

Experimental Example

After separating the phosphor on the panel obtained in Examples 1 to 8 and Comparative Examples, the luminescence properties of the excitation light at 147 nm were measured using a self-made VUV PL measuring apparatus.

The results are shown in Table 1 below.

Color coordinate change rate and luminous efficiency division Before firing After firing Relative value compared to the comparative example after firing y color coordinate Luminous efficiency y color coordinate Luminous efficiency y color coordinate Luminous efficiency Example 1 0.064 100 0.087 72.2 98.2% 98.6% Example 2 0.086 71.0 97.5% 97.0% Example 3 0.086 76.8 97.3% 105% Example 4 0.076 74.8 85.8% 102% Example 5 0.080 83.8 90.4% 115% Example 6 0.079 87.7 89.6% 120% Comparative example 0.088 73.2 100% 100%

As can be seen in the above experimental example, according to the method for producing a PDP phosphor using the antioxidant of the present invention, the color coordinate change rate before and after firing was excellent by about 15% at maximum due to the addition of the antioxidant, and in terms of efficiency, about 20% at maximum. It can be seen that the degree is improved. In particular, it can be seen that Examples 5 to 6 using the mixture of the antioxidants are particularly excellent in terms of color coordinate change rate and efficiency before and after firing.

Claims (16)

10 parts by weight of a solvent for a phosphor paste, 0.01 to 5 parts by weight of an antioxidant, and 1 to 30 parts by weight of a phosphor; Phosphor paste composition characterized in that the antioxidant is a mixture of the compound of formula (1) and the compound of formula (2). <Formula 1>

<Formula 2>

delete delete delete delete delete delete The composition according to claim 1, wherein the solvent for the phosphor paste is butyl carbitol acetate. (A) adding a solvent for the phosphor paste and an antioxidant to dissolve to form a solution; (B) adding a phosphor to the solution and stirring to form a phosphor paste; (C) printing the phosphor paste on the panel with the same thickness and then drying it; (D) firing the phosphor paste after drying is completed; The antioxidant is a method of producing a fluorescent film, characterized in that the mixture of the compound of formula (1) and compound of formula (2). <Formula 1>

<Formula 2>

delete delete delete delete delete delete The production method according to claim 9, wherein the solvent for the phosphor paste is butyl carbitol acetate.