KR101227030B1 - Composition of alloy for phosphor raw material and method for producing thereof - Google Patents

Abstract

In the present invention, in the alloy composition for phosphor raw materials represented by the general formula M1aM2bM3c, the M1 is a divalent metal element containing at least one alkaline earth metal element, the M2 is a trivalent metal element, and the M3 is at least Si It is a tetravalent metal element containing, The range of said a is 0.5 <a <2, The range of b is 0.5 <b <2, The said range of c is 1 <c <4, The alloy composition for fluorescent material raw materials And a method for producing the same, an alloy composition for phosphor raw materials in which respective metal elements are uniformly dissolved can be produced, and an alloy containing a high content of a high melting point metal can be easily produced.

Description

Alloy composition for phosphor raw material and its manufacturing method {COMPOSITION OF ALLOY FOR PHOSPHOR RAW MATERIAL AND METHOD FOR PRODUCING THEREOF}

The present invention provides an alloy composition for phosphor raw materials represented by the general formula M1aM2bM3c, wherein M1 is a divalent metal element containing at least one alkaline earth metal element, M2 is a trivalent metal element, and M3 is at least Si. It is a tetravalent metal element to contain, The range of said a is 0.5 <a <2, The range of b is 0.5 <b <2, The range of c is 1 <c <4, The alloy composition for phosphor raw materials, and It relates to a manufacturing method thereof.

In order to emit phosphors used in fluorescent lamps, field emission displays (FEDs), plasma display panels (PDPs), cathode ray tubes (CRTs), and white light emitting diodes (LEDs), it is necessary to supply energy for exciting the phosphors to the phosphors. The phosphor is excited by an excitation source having high energy such as vacuum ultraviolet rays, ultraviolet rays, visible rays, electron beams, and emits ultraviolet rays, visible rays, and infrared rays. However, there is a problem that the phosphor is lowered in luminance when the phosphor is exposed to such an excitation source for a long time. Therefore, in recent years, many novel substances have been synthesized for ternary or higher nitrides instead of conventional phosphors such as silicate phosphors, phosphate phosphors, aluminate phosphors, borate phosphors, sulfide phosphors, and oxysulfide phosphors.

In particular, phosphors having excellent characteristics in multicomponent nitrides and oxynitrides based on silicon nitride have been developed. Patent Document 1 discloses general formula MxSiyNz: Eu where M is at least one alkaline earth metal element selected from the group consisting of Ca, Sr, and Ba, and x, y, and z are z = 2 / 3x + 4 / 3y is a number satisfied] is disclosed. These phosphors are synthesized by nitriding alkaline earth metals to synthesize nitrides of alkaline earth metals, adding silicon nitride to them, or heating them in nitrogen or argon streams using imides of alkaline earth metals and silicon as raw materials. In all, alkaline earth metal nitrides, which are sensitive to air and moisture, must be used as raw materials, and industrial production has problems.

In the manufacture of nitrides or oxynitride phosphors, it is considered preferable to use alkaline earth metal nitrides such as calcium nitride (Ca ₃ N ₂ ) and strontium nitride (Sr ₃ N ₂ ), but in general, nitrides of divalent metals are moisture It is easy to produce hydroxide by reaction with, and is unstable in a moisture containing atmosphere.

For the above reason, a new phosphor raw material and raw material manufacturing method were required. Regarding a method for producing a nitride phosphor using metal as a starting material, Patent Document 2 describes that a transition element, a rare earth element, aluminum, and an alloy thereof can be used as a raw material. However, the embodiment which actually used an alloy as a raw material is not described, and differs largely from this invention by using the combustion synthesis method which ignites to a raw material and raises it to high temperature (3000K) instantly.

Patent Document 3 describes an example in which an alloy of a tetravalent metal element, a divalent metal element, and an alkaline earth metal is produced using an arc melting method or a high frequency melting method and then used as a raw material of a nitride phosphor. However, there is a problem that it is difficult to manufacture the alloy of the target composition by volatilization of the low melting point metal by the melting point difference of each metal element. Due to the volatilized metal, more raw material metals than necessary are consumed. In addition, when the alloy is produced by the above method, there is a limit in increasing the content of silicon, which is a high melting point metal.

[Prior Art Literature]

Patent Document 1: Japanese Published Patent Application No. 2003-515665

Patent Document 2: Japanese Unexamined Patent Publication No. 2005-54182

Patent Document 3: Korea Patent Publication No. 10-2008-0097174

The present invention provides a method capable of producing an alloy composition having a desired composition by suppressing volatile components in the manufacture of an alloy for LED phosphor raw material. In addition, it is to provide an alloy raw material composition of the form in which each metal raw material is uniformly dissolved by using the above method.

However, the problem to be solved by the present invention is not limited to the above-mentioned problem, but also include other problems not mentioned, as well as all will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, one aspect of the present invention, in the alloy composition for phosphor raw material represented by the general formula M1aM2bM3c, wherein M1 is a divalent metal element containing at least one alkaline earth metal element, the M2 Is a trivalent metal element, M3 is a tetravalent metal element containing at least Si, the range of a is 0.5 <a <2, the range of b is 0.5 <b <2, and the range of c is 1 < It provides c <4, an alloy composition for phosphor raw material.

According to another aspect of the present invention, in a method of producing an alloy composition for phosphor raw material, after producing a binary primary alloy, the phosphor raw material is prepared by melting the primary alloy by a high frequency induction heating method to produce a final alloy composition. It provides a method for producing the alloy composition for.

Using the production method of the present invention, it is possible to produce an alloy composition for phosphor raw material in which the respective metal elements are uniformly dissolved. In addition, an alloy containing a high content of high melting point metal can be easily produced.

1 is a state diagram of Ca-Si, Al-Si, Ca-Si metal used in the preparation of Ca-Al-Si-based alloy.
Figure 2 is a state diagram of the Sr-Si, Al-Si, Sr-Si metal used in the production of the Sr-Al-Si-based alloy.
3 is a state diagram of Ba-Si, Al-Si, Ba-Si metal used in the production of Ba-Al-Si-based alloy.

Hereinafter, with reference to the accompanying drawings will be described in detail the contents of the present invention to be easily carried out by those skilled in the art.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

One aspect of the present invention is an alloy composition for phosphor raw materials represented by the general formula M1aM2bM3c, wherein M1 is a divalent metal element containing at least one alkaline earth metal element, and M2 is a trivalent metal element. Is a tetravalent metal element containing at least Si, wherein the range of a is 0.5 <a <2, the range of b is 0.5 <b <2, and the range of c is 1 <c <4. It provides an alloy composition.

In an exemplary embodiment, M1 is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, and M2 is 1 selected from the group consisting of Al, Ga, In, and Sc. At least one element, and M3 may be at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf, but is not limited thereto.

In the present invention, three metals are made of a binary alloy composition and three primary alloys of Ca (or Sr, Ba) / Si, Ca / Al, and Al / Si, depending on the composition. The process of making a composition was applied by the manufacturing method of the alloy composition for fluorescent material. According to this method, there is an advantage that the melting point of the alloy can be adjusted due to the mutual ratio. For example, as shown in FIG. 1, when the alloy is manufactured at a ratio of Ca: Si = 0.26: 0.74, the melting point of the Ca / Si alloy containing Si may be about 260K from 1687K to 1420K, but the temperature may be lowered.

In the same manner, in the case of other alloys, the melting temperature of the alloy can be adjusted by selecting an appropriate primary alloy production ratio from the state diagrams of FIGS. 2 and 3. In addition, in the case of Al and Ca having a low melting point, the temperature can be raised above the melting point of each alloy according to the melting temperature of the alloy containing Si, so that the melting point between the three alloys can be adjusted. By calculating the mass and and has the advantage of being able to quantitatively match the composition of the final alloy.

According to another aspect of the present invention, in the method for producing the alloy composition for phosphor raw materials, after producing a binary primary alloy, the primary alloy is melted by a high frequency induction heating method to produce a final alloy composition. Provided are a method for producing an alloy composition for a raw material.

The present invention was specifically implemented through the following examples.

Example

In order to apply to the melting experiment in a glove box (glove box) under a nitrogen atmosphere was weighed for each composition, put into a glass bottle and shaken sufficiently, no separate mixing was carried out. Each metal mixed in the glass bottle was melted using a high frequency induction heating apparatus. Melting was performed in a carbon crucible in a heating apparatus, and the alloy was prepared in an ingot form after pouring into a carbon mold. Melting conditions were carried out by manually adjusting the output value while visually checking the state of the powder, and when the powder was sufficiently melted, the mixture was kept at the same temperature for about 30 seconds to induce mixing with each other.

Example 1

After preparing a binary alloy of Ca / Si, Ca / Al, Al / Si in the conditions selected from the state diagram of the binary metal, respectively, re-weighed to the molar ratio to prepare a final alloy.

[Example 2]

After preparing binary alloys of Sr / Si, Sr / Al, and Al / Si, respectively, under the conditions selected from the state diagrams of the binary metals, the final alloys were prepared after re-weighing according to the molar ratio.

[Example 3]

After preparing the binary alloys of Ba / Si, Ba / Al, Ba / Si under the conditions selected from the state diagram of the binary metal, respectively, and re-weighed to the molar ratio to prepare the final alloy.

Comparative Example 1

A primary alloy of Ca / Al, which is a low melting point metal, was prepared first, and then the final alloy was prepared by melting the primary alloy and Si simultaneously.

Comparative Example 2

A primary alloy of Sr / Al, which is a low melting point metal, was prepared first, and then the final alloy was prepared by melting the primary alloy and Si simultaneously.

[Comparative Example 3]

A primary alloy of Ba / Al, which is a low melting point metal, was prepared first, and then the final alloy was prepared by melting the primary alloy and Si simultaneously.

Claims (3)

In the alloy composition for phosphor raw materials represented by the general formula M1aM2bM3c,
M1 is a divalent metal element containing at least one alkaline earth metal element, M2 is a trivalent metal element, M3 is a tetravalent metal element containing at least Si, and the range of a is 0.5 <a < 2, the range of b is 0.5 <b <2, the range of c is 1 <c <4, alloy composition for phosphor raw material. The method of claim 1,
Said M1 is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, said M2 is at least one element selected from the group consisting of Al, Ga, In, and Sc, said M3 The alloy composition for phosphor raw materials, wherein is at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr, and Hf. In the method for producing an alloy composition for phosphor raw material as defined in claim 1 or 2,
A method for producing an alloy composition for phosphor raw materials, after the production of a binary primary alloy, followed by melting the primary alloy (by a high frequency induction heating method) to produce a final alloy composition.

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