MXPA97008368A - Improved phosphorus complex that has high brillan - Google Patents

Abstract

An improved red, green or blue phosphorus complex produced by adhering a chromium compound to red, green or blue phosphorus using a polymer binder or an inorganic binder, or without a binder, has a high brilliance without changing the characteristics of the phosphor

Description

IMPROVED PHOSPHORUS COMPLEX WHICH HAS HIGH BRILLIANCE DESCRIPTION OF THE INVENTION The present invention relates to an improved phosphorus complex and, more specifically, to an improved phosphorus complex having high brightness which includes conventional phosphorus and a material which adheres over conventional phosphorus, and is able to facilitate the transfer of electrons. Generally, visible rays are emitted by almost all materials when materials are heated to high temperatures. However, some materials emit visible rays at room temperature when electron beams or ultraviolet light are irradiated to the material. Generally, this phenomenon is called "luminescence" and the material that causes this phenomenon is called phosphorus. To this day, the phosphors which are used in a Braun tube are prepared by mixing an activator with a host material and then calcined at 700 ° C to 1300 ° C for more than 30 minutes. The host material includes a compound of calcium oxide, strontium, barium, beryllium, magnesium, zinc, cardio and the like, sulfur compounds thereof, selenium compounds thereof, fluoride compounds thereof, silicon compounds of the same, phosphate compounds thereof, arsenate compounds thereof, tungstanate compounds (tungstate) thereof. In addition, manganese, magnesium, copper, bismuth, antimony, lead, titanium and various rare earth elements are used as activators. In calcination, a flux can also be used which is a compound that has good solubility for phosphorus to increase the particle size of the phosphorus. Phosphorus of the conventional zinc sulfide (ZnS) type comprises zinc and cardio, which belong to the class Ilb of the Periodic Table, and sulfur, selenium (Se), tellurium (Te) which belong to class VIb of the Periodic Table as the host material. Copper, silver and gold are used as activators, which belong to Class Ib of the Periodic Table and aluminum and chlorine are used as co-activators. Examples of phosphorus of type ZnS are ZnS: Cu, Au, Al (green phosphorus) and ZnS: Ag, Cl (blue phosphorus) Phosphorus of the ZnS type has been used mainly as phosphorus for cathode ray tubes since phosphorus can illuminate several visible rays by changing the host material or the activator. ZnS type phosphors for cathode ray tubes are one of the most efficient phosphors. However, this has the disadvantage that the Vd (dead voltage) at which the luminescence begins is high and brightness saturation phenomena occur. The saturation of brightness means that no additional increase in brightness occurs. Additionally, phosphorus of the rare earth type is actively studied as red phosphorus, and YV04: Eu is practically used as a red phosphorus. The host material thereof comprises YV04, Y202S, La202S and Gd202S and the like. On the other hand, the elements of rare earths include europium (Eu), terbium (Tb), samarium (Sm), cerium (Ce), praseodium (Pr) are mainly used as activators. The characteristic of phosphorus is that its energy efficiency is lower than that of the ZnS type group, but saturation of brilliance does not occur. The phosphors which light the red color, between the previous phosphorus, are Y203: Eu3 + and Y (V, P) 04: Eu3 +. Recently, the Y202S: Eu3 + has been developed as red phosphorus of the rare earth type. Therefore, matches can be classified into white, red, green, yellow and blue matches by their colors. To this day, the three colors of red, green and blue phosphors (R. G. B.) are mainly used. Recently, green phosphorus has been actively developed, and the example of it is (ZnCd) S: Cu, Al, ZnS: Cu, Al, ZnS: Cu, Al, Au, Zn2Si04: Mn, Zn2Si04: Mn, As, ZnO , and (ZnCd): S: Cu, Al, and the like.

To this day, the demand for color display devices ("CDT") has increased according to the development of multimedia, therefore a phosphorus that has greater brightness than the current phosphorus is required. The improvement of phosphorus brightness is essential to improve the quality and increased accuracy of Braun tubes. Recently, a phosphorus sensitizer has been added in order to increase the brightness of red phosphorus. In order to increase the brightness of green phosphorus, Bi, Tb and Sb and the like have been added to the phosphorus. Additionally, in order to increase the brightness of blue phosphorus, a material has been added to phosphor which is capable of facilitating the transfer of hollow electron pairs, or a sensitizer. The coactivator of which the luminance wavelength of the spectrum corresponds to the wavelength of the absorption spectrum of an activator is used as the sensitizer. However, the above methods have disadvantages in that they are complicated and difficult since a conventional process for preparing a phosphorus in the condition thereof, must be further changed using sensitizers or Bi, Tb and Se and the like. Additionally, the brilliance of the matches is not increased as expected by the previous methods.

In order to solve the aforementioned disadvantages of conventional phosphorus, the present invention provides an improved phosphorus complex having high brightness without deteriorating phosphorus characteristics. The present invention also provides an improved phosphorus complex having high brilliance which can be easily prepared without changing a conventional process of preparing phosphorus. In order to achieve the above objects, the present invention provides an improved phosphorus complex having high brightness comprising phosphorus and; a material which adheres on a phosphor surface and which is capable of facilitating the transfer of electrons. In the present invention, the material which is capable of facilitating electron transfer is preferably the water-insoluble chromium compound, and most preferably the chromium compound selected from the group consisting of chromium phosphate, chromium hydroxide and chromium fluoride. The preferred amount of the chromium compound to be adhered on the phosphorus is 0.00001 to 5.0 wt% phosphorus. If the phosphorus is red phosphorus, the most preferred amount of the chromium compounds to be adhered on the phosphorus is 0.00001 to 1.0% by weight of the phosphorus, and if the phosphorus is green or blue, the most preferred amount of the chromium compound has to be adhered onto phosphorus is 0.00001 to 5.0% by weight of the phosphorus. The preferred diameter of the chromium compound is 10 nm to 1 μm. The phosphorus may be selected from the group consisting of red phosphorus comprising Y202S: Eu or Y203: Eu, green phosphorus comprising ZnS: Cu, Al or ZnS: Cu, Al, Au and blue phosphorus comprising ZnS: Ag or ZnS : Ag, Cl. The improved phosphorus complex having high brightness of this invention can be prepared by adhering a material which is capable of facilitating the transfer of electrons over phosphorus, using a binder, or precipitating the material on phosphorus. In the above method of preparing an improved phosphorus complex, the preferred binder is selected from the group consisting of a polymer binder and an inorganic binder. More preferably, the polymer binder is a compound selected from the group consisting of gelatin, a mixture of gelatin and gum arabic, casein and polymethyl methacrylate (PMMA), and an inorganic binder is a compound selected from the group consisting of potassium silicate , zinc hydroxide and magnesium phosphate. Additionally, in the above method of preparation, to the improved phosphorus complex, a hardening agent can be used to firmly adhere the material which is capable of facilitating the transfer of electrons over phosphorus. The preferred curing agent is glutaraldehyde. Additional objects, advantages and novel features of the invention will be indicated in part in the description which follows, and in part will become apparent to those skilled in the art after examination of the following or can be learned by the practice of the invention. invention. The object and advantages of the invention can be realized and achieved by means of the particular instrumentalities and combinations indicated in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing a structure of an improved phosphorus complex according to the present invention; Figure 2 is a graph showing the luminescence spectra of conventional red phosphorus on which the chromium and red phosphorus compounds adhere on which chromium compounds adhere according to one embodiment of the present invention; Figure 3 is a graph showing the luminescence spectra of conventional green phosphorus on which chromium compounds do not adhere and green phosphorus on which chromium compounds adhere according to another embodiment of the present invention; Figure 4 is a graph showing the luminescence spectra of conventional blue phosphorus on which the chromium and blue phosphorus compounds do not adhere on which chromium compounds adhere according to another embodiment of the present invention; In the following detailed description, only the preferred embodiment of the invention has been shown and described, simply by way of illustration of the best mode contemplated in carrying out the invention. As will be realized, the invention is capable of modification in various obvious aspects, all without departing from the scope of the invention. Therefore, the drawing and the description are taken into account as an illustration in their nature, and not as restrictive. The present invention is illustrated with reference to Figure 1. As shown in Figure 1, the improved phosphorus complex of the present invention can be prepared by adhering a material which is capable of facilitating the transfer of electrons onto the surface of a match. For example, the chromium compound is adhered on the surface of a phosphorus using a polymer binder or an inorganic polymer, or precipitated on the surface of the phosphorus. In addition to the above method, the improved phosphorus complex of the present invention can be prepared by any conventional method which can adhere the chromium compound to the phosphorus. The material which adheres on the surface of the phosphorus and which is capable of facilitating the transfer of electrons easily transfers the electrons to the phosphorus by receiving a beam of high-voltage electrons on the surface of the phosphorus, thereby increasing the brightness of the phosphorus increasing the amount of phosphorus to be illuminated. A final phosphorus product or a phosphor which is not coated with silicon dioxide (SiO2) or a pigment, such as a phosphorus of the present invention can be used. The present invention is further explained in detail with reference to the following example which is within the scope of this invention. [Example 1] 0.01 parts by weight of chromium phosphate are added to 0.2 parts by weight of gum arabic and stirred, and then 100 parts by weight of Y202S: Eu are added thereto and stirred. After this, 0.2 parts by weight of gelatin is added to the product and mixed. 10% by weight of acetic acid is added to the mixed product to adjust the pH of the mixed product to a pH of 4 in order to adhere the gelatin and the Cr compound to the phosphorus. After adding ice to the resulting product to adjust the temperature of the resulting product to 4 ° C, s add the gelatin and glutaraldehyde thereto to polymerize the gum arabic with the gelatin and wash it with pure water. After this, the obtained phosphorus is filtered and dried in an oven at 100 ° C for one day to produce the red phosphorus. [Examples 2-8] Red phosphorus is produced by the same procedure described in Example 1 by changing the amount of chromium phosphate as shown in Table 1 below. [Example 9] 0.03 parts by weight of chromium phosphate are added to 0.2 parts by weight of gum arabic and stirred, and 100 parts by weight of Y203: Eu are added thereto and stirred. After this, 0.2 parts by weight of the gelatin are added to the product and mixed. 10% by weight of acetic acid is added to the mixed product to adjust the pH of the mixed product to a pH of 4 in order to adhere the gelatin and the Cr compound to the phosphorus. After adding ice to the resulting product to adjust the temperature of the resulting product to 4 ° C, gelatin and glutaraldehyde are adhered to it to polymerize gum arabic with gelatin, and washed with pure water. After this, the obtained phosphorus is filtered and dried in an oven at 100 ° C for one day to produce the red phosphorus. [Example 10] After stirring 0.03 parts by weight of chromium phosphate, 100 parts by weight of Y202S: Eu are added and stirred for 30 minutes. After the same, 0.5 parts by weight of ZnSO4 is added to the product and stirred for 30 minutes. NH40H is added to the resulting product to adjust the pH of the resulting product to a pH of 7 in order to form zinc hydroxide as a binder, and the obtained phosphorus is dried at about 100 ° C in an oven for one day to produce phosphorus Red. [Comparative Example 1] Red phosphorus is prepared by the same procedure as in Example 1, except that chromium phosphate is not used. The relative brightness and color coordinates of the phosphorus produced by the preceding examples 1 to 10 and comparative example 1 is determined and the results thereof are shown in Table 1 below. The relative brightness is determined by applying voltage lOkVs to the detachable CRT on which the phosphor is coated from Examples 1 to 10 and Comparative Example 1. The phosphor screen is prepared by a precipitation method using barium acetate and potassium silicate .

[Table 1] [Example 11] 0.01 parts by weight of chromium phosphate are added to 0.05 parts by weight of gum arabic and agitated, and then 100 parts by weight of ZnS: Cu, Al is added thereto and stirred. After this, 0.5 parts by weight of gelatin is added to the product and mixed. 10% by weight of acetic acid is then added to the mixed product to adjust the pH of the mixed product to a pH of 4 in order to adhere the gelatin and the Cr compound to the phosphorus. After adding ice to the resulting product to adjust the temperature of the resulting product to 4 ° C, glutaraldehyde is added to the product to polymerize gum arabic with the gelatin and washed with pure water. After this, the obtained phosphorus is dried at approximately 100 ° C in an oven for one day to produce green phosphorus. [Examples 12-18] Green phosphorus is prepared by the same procedure described in Example 11 by changing the amount of chromium compound as shown in Table 2 below. [Example 19] Green phosphorus is prepared by the same procedure described in Example 11 except that ZnS: Cu, Al, Au is used as phosphorus and the amount of the chromium compound to be added is changed as shown in the Table 2 below. [Example 20] 0.1 parts by weight of ZnS04 are added to 0. 05 parts by weight of chromium phosphate, add 100 parts by weight of ZnS: Cu, Al, Au to it, and stir the product. After this, NH4OH is added to the resulting product to adjust the pH of the resulting product to a pH of 9 in order to adhere the Cr compound to the phosphorus. The obtained phosphorus is dried at approximately 100 ° C for one day to produce green phosphorus. [Example 21] 0.05 parts by weight of water-soluble chromium sulfate are dissolved in distilled water, and 100 parts by weight of ZnS: Cu, Al are added thereto and stirred. After this, an excess of ammonium hydroxide is added thereto to form a precipitate of the chromium compound on the surface of the phosphorus. The obtained phosphorus is filtered and dried at approximately 100 ° C for one day to produce green phosphorus. [Comparative Example 2] Green phosphorus is prepared by the same procedure as in Example 11, except that the chromium compound is not used. [Comparative Example 3] Green phosphorus is prepared by the same procedure as in Comparative Example 2, except that ZnS: Cu, Al, Au is used as phosphorus. The relative brightness and color coordinates of the phosphorus prepared by examples 11 to 21 above and comparative examples 2 to 3 are determined, respectively, and the results thereof are shown in Table 2 below. The relative brightness is determined by applying voltage lOkVs to the detachable CRT on which the phosphor is coated from Examples 11 to 21 and Comparative Examples 2 to 3. The phosphor screen is prepared by a precipitation method using barium acetate and sodium silicate. potassium. [Table 2] [Example 22] 0.02 parts by weight of chromium phosphate are added to 0.13 parts by weight of gum arabic and stirred, and then 100 parts by weight of ZnS: Ag is added thereto and stirred. After this, 0.13 parts by weight of gelatin is added to the product and mixed. 10% by weight of acetic acid is added to the mixture to adjust the pH to 3.4 to adhere the gelatin and the chromium phosphate to the phosphorus. After adding ice to the phosphorus to adjust the phosphorus temperature to 4 ° C, 1 ml of glutaraldehyde is added to it to polymerize gum arabic and gelatin and washed with pure water. The product is dried at a temperature of 100 ° C in an oven for a day or more to produce the blue phosphorus having high brightness. [Examples 23-27] Blue phosphorus having high brightness is prepared by the same procedure described in Example 22 by changing the amount of the chromium compound as shown in Table 2 below. [Example 28] 0.03 parts by weight of chromium phosphate is stirred and then 100 parts by weight of ZnS: Ag is stirred for 30 minutes. After that, 0.5 parts by weight of ZnSO4 is added thereto and stirred for 30 minutes. After adding NH4OH to the resulting product to adjust the pH 7, the resulting phosphorus is dried in an oven at about r ° 0 ° C for a day or more to produce the blue phosphorus. [Example 29] 0.05 parts by weight of soluble chromium sulfate are dissolved in water, in distilled water, and 100 parts by weight of ZnS: Ag are added thereto and stirred. After this, an excess of ammonium hydroxide is added thereto to precipitate the chromium compound on the phosphor surface. The obtained phosphorus is filtered and dried at approximately 100 ° C for more than one day to produce blue phosphorus. [Comparative Example 4] The blue phosphorus is prepared by the same procedure described in Example 22, except that the chromium compound is not added to the phosphorus. The relative brightness and color coordinates of the matches produced by the above examples 22 to 29 and the comparative example 4 are determined and the results thereof are shown in Table 3 below. The relative brightness is determined by applying lOkVs to a detachable CRT on which the phosphor of examples 22 to 29 and comparative example 4 is coated. The phosphor screen is prepared to determine the brightness by a precipitation method using barium acetate and potassium silicate.

[Table 3] As shown in Tables 1 to 3, the phosphor brightness, according to the present invention, is increased to 10% without any change of color coordinates. Additionally, as shown in Figures 2 a 4, luminescence spectra of standard phosphors are shown and the phosphorus in which 0.03 parts by weight of the Cr compound is adhered, the phosphorus spectrum height of this invention is incredibly increased. Therefore, it has been shown that the Cr compound can increase the efficiency of cathodoluminescence. Therefore, the adhesion of the Cr compound to phosphorus can increase the brightness of phosphorus without greatly changing the property of phosphorus. As shown in Tables 1 to 3 and Figures 2 to 4, when the chromium compound is adhered to phosphorus, the brightness of phosphorus can be increased without changing the phosphorus property. In this description, only the preferred embodiment of the invention has been shown and described, but, as mentioned above, it is understood that the invention allows the use of various combinations and environments and allows changes or modifications within the scope of the concepts of inventiveness as they are expressed in the present.

Claims (9)

1. CLAIMS 1. An improved phosphorus complex having high brightness, characterized in that it comprises: phosphorus; and a material which adheres to the surface of phosphorus and easily allows the transfer of electrons.
2. 2. The improved phosphorus complex, according to claim 1, characterized in that the material which is capable of facilitating electron transfer comprises chromium compounds.
3. 3. The improved phosphorus complex according to claim 2, characterized in that the material which is capable of facilitating electron transfer comprises a water-insoluble chromium compound.
4. 4. The improved phosphorus complex according to claim 2, characterized in that the chromium compound is selected from the group consisting of chromium phosphate, chromium hydroxide and chromium fluoride. 5. The improved phosphorus complex, according to claim 1, characterized in that the amount of the chromium compound is 0.00001 to
5. 5.0% by weight of the phosphorus.
6. 6. The improved phosphorus complex according to claim 2, characterized in that a diameter of the chromium compound is within the range of 10 nm to 1 μm.
7. 7. The improved phosphorus complex, according to claim 1, characterized in that the phosphorus is red phosphorus comprising Y202S: Eu or Y203: Eu.
8. 8. The improved phosphorus complex according to claim 1, characterized in that the phosphorus is green phosphorus comprising ZnS: Cu, Al or ZnS: Cu, Al, Au.
9. 9. The improved phosphorus complex according to claim 1, characterized in that the phosphorus is blue phosphorus comprising ZnS: Ag or ZnS: Ag, Cl.