WO2017090955A1 - Method for continuously producing metal fluoride-based fluorescent substance - Google Patents

Abstract

The present invention relates to a method for continuously producing a metal fluoride-based fluorescent substance and, more particularly, to a method for continuously producing a metal fluoride-based fluorescent substance, wherein feeding, mixing and synthesis, and discharge processes are continuously performed such that a reactant prepared by dissolving or slurrifying two or more metal precursors is fed into a reactor, mixing and fluorescent substance synthesis are performed by vortexes generated by a fluid flow of the reactant, and the resultant synthesized fluorescent substance is discharged through an outlet according to a fluid flow of the solution.

Description

Continuous manufacturing method of metal fluoride phosphor

The present invention relates to a continuous manufacturing method of a metal fluoride-based phosphor, and more particularly, a reactant prepared by dissolving or slurrying two or more metal precursors is introduced into a reactor, and a vortex generated by fluid flow of the reactant (VORTEX In the continuous manufacturing method of the metal fluoride phosphor which performs the mixing and phosphor synthesis reaction, and the synthesized phosphor is discharged through the outlet according to the fluid flow of the solution. It is about.

Metal fluoride-based phosphors have been widely applied to light emitting devices such as light emitting diodes, laser diodes, surface light emitting diodes, inorganic electroluminescent devices, and organic electroluminescent devices.

WO 2012-128837 discloses a metal fluoride-based phosphor having a composition of the formula (A).

[Formula A]

A _x [MF _y ]: Mn ⁴⁺

(In Formula A, A is selected from Li, Na, K, Rb, Cs and combinations thereof; M is Si, Ge, Ti, Zr, Al, Ga, In, Sc, Y, La, Nb, Ta , Bi, Gd and combinations thereof; x is an absolute value determined from the charge of the MF _y ions, y is 5, 6 or 7)

In addition, the present inventors have developed a metal fluoride-based phosphor having a composition of the following general formula (B) and have filed a patent application as Korean Patent Application No. 10-2015-0134405.

[Formula B]

[AF] ₃ [MF _z ]: Mn ⁴⁺

(In Formula B, A is an alkali metal element selected from Li, Na, K, Rb, Cs and combinations thereof; M is Si, Ge, Ti, Zr, Al, Ga, In, Sc, Y La, Nb Is a metal element selected from Ta, Bi, Gd and combinations thereof; z is an integer of 3, 4 or 5, as determined by the oxidation number of the metal element M)

The general method for producing a metal fluoride-based phosphor is largely a solid phase method and a liquid phase method. In the method for producing a metal fluoride-based phosphor using the solid phase method, the fluoride precursor is weighed in a desired ratio, mixed in a mortar using acetone or ethanol, and reacted in a high temperature electric furnace. The use of the solid phase method has the advantage that the phosphor can be more conveniently synthesized than the gas phase method or the liquid phase method, but there is a high possibility that fluoride phosphors of an unwanted composition are synthesized by fluorine reacting with other elements during the reaction. The solid phase method is convenient in terms of method but has a disadvantage in that it is not easy to synthesize a fluoride-based phosphor having a desired composition.

On the other hand, the liquid phase method has an advantage that it is possible to produce a phosphor having a desired composition compared to the solid phase method because the fluoride is converted to a solution state and reacted. In the liquid phase method, a so-called precipitation method in which fluoride precursors are dissolved in distilled water or hydrofluoric acid (HF) and then precipitated using solubility of each solution to synthesize fluoride phosphors is most widely used. However, there are many problems to overcome in order to synthesize a large amount of fluoride-based phosphors by precipitation. As a representative problem, the amount of hydrofluoric acid (HF) used as a solvent needs to be increased as the fluoride used as a reactant is massed. However, hydrofluoric acid is limited to be used as a precipitation solvent because it is a material with significant safety in handling. In addition, in order to mass-produce, the amount synthesized in one batch is increased, so that the secondary treatment process also requires a large-scale device.

Therefore, there is a need for the development of a new synthetic method to enable safer and more bulky metal fluoride-based phosphors that are not easy to handle raw materials.

An object of the present invention is to solve the problems of the solid phase method and the liquid phase method of the batch type at the same time, and to provide a new synthesis method to enable mass production of metal fluoride-based phosphors.

That is, the present invention provides a method for continuously producing a metal fluoride-based phosphor that continuously reacts, prepares, mixes, synthesizes, and discharges the synthesized phosphors by continuously preparing a reactant as a solution based on a liquid phase method. .

In order to solve the above problems, the present invention is a method for continuously producing a metal fluoride-based phosphor by the liquid phase method,

(Step 1) Step 1 to prepare a reactant in the dissolved or slurry state by mixing the metal precursor used for the synthesis of metal fluoride-based phosphor in distilled water or hydrofluoric acid;

(Step 2) step 2 of continuously introducing the reactants into the reactor through an inlet formed on one side of the reactor using a metering pump;

(Step 3) The inside of the reactor is equipped with a cylindrical stirrer to rotate at regular intervals with the inner wall of the reactor, the reactant introduced into the reactor while the cylindrical stirrer rotates at a constant speed in the speed range of 10 ~ 1500 rpm is a fluid flow Mixing and reacting the resulting vortex (VORTEX) to synthesize metal fluoride-based phosphors;

(4 steps) 4 steps of discharging the synthesized metal fluoride-based phosphor toward the outlet formed on the other side of the reactor according to the fluid flow of the reactant; And

(5 steps) 5 steps of obtaining the phosphor powder by washing and drying the discharged phosphor; Including,

Continuous preparation of the metal fluoride-based phosphor in which the two, three, and four step processes in which the reactants are introduced into the reactor, the reactants are mixed and reacted with the synthesized phosphor, and the phosphors are discharged from the reactor are performed in a continuous process. The method is characterized by that.

The continuous manufacturing method of the present invention can solve the problems of the general solid-state method and the liquid phase method of the batch (Bach) type at the same time. In particular, the present invention is based on the liquid phase method, but overcomes the synthetic limitations of the batch type liquid phase method, and by introducing a continuous process, it is possible to massify the fluoride phosphor as desired by the user.

In addition, according to the continuous production method of the present invention, since a small amount of the reactant is added in a small reactor space, it is possible to safely synthesize the metal fluoride-based phosphor, and also produce up to 1 to 50 g per minute through a continuous process in a narrow reactor. Since this is possible, mass production of metal fluoride-based phosphors is also possible.

1 is a block diagram of a reaction apparatus used in the continuous production method according to the present invention.

FIG. 2 is an overall configuration diagram of a continuous manufacturing process of a metal fluoride phosphor including the reactor of FIG. 1.

Figure 3 is an electron scanning micrograph showing the particle size and shape of the metal fluoride-based phosphor prepared according to the stirring speed.

Figure 4 is an electron scanning micrograph showing the particle size and shape of the metal fluoride-based phosphor prepared according to the loading rate of the reactants.

5 is an emission spectrum of K ₂ SiF ₆ : Mn ^{4 +} and K ₂ TiF ₆ : Mn ^{4 +} phosphors prepared by a continuous manufacturing method.

6 is an X-ray powder diffraction spectrum of K ₂ SiF ₆ : Mn ^{4 +} and K ₂ TiF ₆ : Mn ^{4 +} phosphors prepared by a continuous manufacturing method.

7 is an emission spectrum of KMgF ₃ : Eu ^{2 +} and KLaF ₄ : Yb ^{3 +} and Tb ^{3 +} phosphors prepared by a continuous production method.

The present invention will be described in more detail as follows.

According to the continuous manufacturing method of the metal fluoride-based phosphor according to the present invention, a reactant prepared by dissolving or slurrying a metal precursor used for synthesizing the metal fluoride-based phosphor is introduced into the inlet of the reactor, and is produced by the fluid flow of the reactant. After mixing the reactants by VORTEX and carrying out phosphor synthesis reaction, the synthesized phosphor is discharged according to the fluid flow of the reactants, and the addition, mixing, synthesis, and discharge are performed in a continuous process.

That is, according to the continuous production method of the present invention, since the precursor compound is dissolved or slurried in distilled water or hydrofluoric acid and used as a reactant, a metal fluoride phosphor having a desired composition can be prepared. In the present invention, the synthesized phosphor is continuously discharged out of the reactor according to the fluid flow formed in the reactor and separated and purified through simple filtration, and the precipitation process for solidifying the phosphor is omitted. It is possible to mass-produce a phosphor by this. Furthermore, in the case of the precipitation method for solidifying phosphors, hydrofluoric acid (HF) is used in a large amount as a good solvent, but in the present invention, hydrofluoric acid (HF) is used only when dissolving or slurrying a precursor compound. It can be called environmentally friendly.

In addition, the present invention is capable of carrying out the process of mixing and synthesizing the reaction through the fluid flow of the reactants introduced into the reactor and carrying the resulting phosphor toward the outlet. Specifically, the reactants have a flow along the rotation direction of the cylindrical stirrer inside the reactor, and the phenomenon of mixing between the reactor and the stirrer occurs. The reactant generates a centrifugal force to go toward the inner wall of the reactor by the stirrer and is forced in the vertical direction of the centrifugal force by another reactant introduced into the reactor. This effect causes the internal reactant fluid to form different ring pair vortices, which affects the mixing and synthesis reactions. The reaction rate can be controlled by controlling the flow of the reactants to control the production rate of the phosphor.

In addition, the fluid flow in the reactor can be controlled by adjusting the input speed and / or stirring speed of the reactants. Based on the reactor of 100 mL capacity, the reaction rate of the reactants can be controlled within the range of 1 ~ 50 mL / min, it is also possible to quantitatively control the input rate by installing a metering pump. In addition, if a fixed vortexer or a mechanical stirrer is installed in the reactor, the reaction rate may be further increased, and thus the amount of phosphor synthesized may be further increased. Stirring speeds may preferably range from approximately 10 to 1500 rpm.

According to the present invention, when a reactant was added at a rate of 10 mL / min per minute using a 100 mL reactor, the metal fluoride phosphor was generated at about 5 g / min per minute, thus synthesizing 14 kg / day per day. Can be. In the case of the synthesis of the phosphor using a general solid-state method, compared with the synthesis of 1 kg / day per day in one electric furnace (capacity 20 L), the continuous manufacturing method of the present invention is 14 times the capacity of one electric furnace It has the above synthetic performance.

In addition, the continuous production method according to the present invention can also control the size and shape of the phosphor particles synthesized by adjusting the input speed and the stirring speed of the reactant. That is, the metal fluoride synthesized by varying the input speed of the reactant in the range of 1 to 50 mL / min (based on a capacity of 100 mL reactor), adjusting the stirring speed to 10 to 1500 rpm, or simultaneously controlling the input speed and the stirring speed. The size and shape of the system phosphor can be controlled. The size of the metal fluoride-based phosphor to be synthesized in the present invention may range from about 10 to 100 μm.

According to the continuous production method according to the present invention, the smaller the size and uniform phosphor particles are synthesized as the reaction rate of the reactant is faster, and the larger phosphor particles are synthesized as the reaction rate of the reactant is slower. When two or more reactants are introduced into the reactor and a sufficient amount is reacted, sufficient seeds are formed to synthesize small and uniform phosphor particles.However, when the amount of reactant is not sufficient, crystal growth is continuously continued in a small amount of seeds. The particle size is increased. That is, as the stirring speed is increased while maintaining the reaction rate of the reactant at a constant rate, the chance of seed generation is reduced, and thus, the phosphor particles already formed may be greatly grown. In addition, it may be possible to adjust the shape of the phosphor particles formed by controlling the input speed and the stirring speed of the reactants to be hexahedron, tetrahedron or amorphous.

Specifically, the method of continuously manufacturing the metal fluoride phosphor according to the present invention,

Mixing the metal precursor used for synthesizing the metal fluoride phosphor with distilled water or hydrofluoric acid to prepare a reactant in a dissolved or slurry state;

Continuously feeding the reactants into the reactor through an inlet formed on one side of the reactor using a metering pump;

The reactants introduced into the reactor are mixed and reacted by VORTEX generated by the fluid flow to synthesize metal fluoride-based phosphors;

4 steps of discharging the synthesized metal fluoride-based phosphor toward the discharge port formed on the other side of the reactor according to the flow of the reactant; And

Washing and drying the discharged phosphor to obtain phosphor powder; It includes.

In addition, the metal fluoride-based phosphor which may be prepared by performing the continuous manufacturing method according to the present invention may have a composition formula represented by the following formula (1).

[Formula 1]

A _a M _m F _f : R _r

(In Formula 1, A is an alkali metal element selected from Li, Na, K, Rb, Cs and combinations thereof; M is Si, Ge, Ti, Zr, Al, Ga, In, Sc, Y La, Nb Is a metal element selected from Ta, Bi, Gd and combinations thereof; R is a transition metal or rare earth metal having an oxidation number of +2, +3, +4 as an activator; and the subscripts a, b, f and r are each The number of elements, 0≤a≤3, 0≤b≤2, 0 <f≤11, 0 <r <2, provided that a and b cannot be 0 at the same time)

As a precursor compound used to prepare a metal fluoride-based phosphor having a compositional formula of Formula 1, the precursor compound from which metal A is derived may be AF, AHF ₂ , A ₂ O, A ₂ CO ₃ , A _x [MF _y ], and A _x One or more compounds selected from [MF _y ]: R may be adopted. As the precursor compound from which the metal M is derived, one or more compounds selected from H _x [MF _y ], A _x [MF _y ], and A _x [MF _y ]: R may be adopted. As the precursor compound from which the metal R is derived, one or more compounds selected from A _x [MF _y ]: R may be adopted. A, M and R used in the definition of the precursor compound are as defined in Formula 1, respectively, x is an absolute value determined from the charge of the MF _y ion, y may be an integer of 5, 6 or 7.

In addition, Figure 1 illustrates an embodiment of a reaction apparatus that can be applied to the present invention, the present invention is not limited thereto.

Referring to FIG. 1, the reactor 10 is provided with inlets 20a and 20b into which a reactant prepared in a solution or slurry state is introduced, and an outlet 30 for discharging the synthesized phosphor out of the reactor according to the fluid flow of the reactant. . In addition, the reactor 10 is provided with a cylindrical stirrer that rotates at regular intervals with the inner wall of the reactor. When the cylindrical stirrer rotates at a constant speed in a speed range of 10 to 1500 rpm, the reactant is caused by the vortex generated by the centrifugal force generated by the stirrer to the reactor wall and the force of moving the fluid in a direction perpendicular thereto. This mixes and reacts.

In view of the fact that the precursor compound used in the present invention is a fluoride, the reactor or surrounding accessories may be coated with an acid resistant material or made of an acid resistant material to prevent contamination and breakage by hydrofluoric acid.

In addition, the reactor 10 is provided with an inlet 20 and an outlet 30, the inlet 20 and the outlet 30 may be provided with one or two or more, respectively, and also the inlet 20 and outlet The position of 30 can also be adjusted arbitrarily. That is, by dividing the reactants through two or more inlets by dividing by the type of precursor compound used for the synthesis of the phosphor, it is possible to more easily control the reaction pattern. In addition, the number of inlets 20 and outlets 30 may be arbitrarily adjusted to control the flow of fluid formed in the reactor. In addition, in providing a plurality of inlets 20, the positions of the inlets 20 may be separately placed at the lower and middle portions of the reactor so that the reactants react with time difference. Depending on the situation, the inlet 20 and the outlet 30 may be connected to enable continuous particle growth and the like. The reactants introduced into the two or more inlets 20 are met in the reactor to mix and simultaneously synthesize a metal fluoride-based phosphor, the resulting phosphor is raised. Then, the raised phosphor is discharged to the discharge port 30 in accordance with the flow of the fluid.

In addition, in installing the reactor 10 may be installed to have a vertical, horizontal or constant inclination relative to the ground depending on the reaction pattern.

In addition, the reactor 10 is attached to a temperature control device 13 such as a heater or a heat exchanger to adjust the temperature of the reactants. In addition, a temperature control jacket 12 capable of circulating the heat exchange medium may be provided outside the reactor to control the temperature of the reactants. In addition, the temperature control device 13 may be attached to the reactant reservoir to adjust the temperature of the reactant in advance, and may be introduced into the reactor 3 so that the temperature of the reaction solution may be kept constant.

In addition, a fixed vortex or mechanical stirrer may be further installed inside the reactor 10 to control the strength of the vortex and the flow of the fluid. According to the present invention, a vortex (VORTEX) is formed by a reactant in a solution or a slurry flowing through the inlets 20a and 20b of the reactor, and the reactants are mixed and synthesized using the same, and the flow of the fluid is used. The manufactured phosphor is transported toward the outlet 30 to be discharged out of the reactor. In addition, if the vortex or agitator is installed inside the reactor, it is possible to more easily control the strength of the vortex and thereby to control the reaction rate, and the phosphor prepared by adjusting the direction of the fluid flow to the outlet 30 easily Can be induced and discharged.

The mechanical stirrer 11 installed in the reactor 10 has a cylindrical shape. However, the present invention is not limited by the shape of the stirrer, and a suitable stirrer can be selected according to the purpose.

The present invention proves that the present invention is actually applicable through the following examples, and those skilled in the art may variously change and modify the present invention through various variables based on the above description.

EXAMPLE

Representative Example. Continuous Preparation of Phosphors

Referring to the configuration of the overall reactor shown in Figure 2 will be described a method for producing a phosphor.

The reactor 10 has a capacity of 100 mL, and is made of Teflon or acid resistant polymer material that can withstand hydrofluoric acid, and is carefully sealed to prevent hydrofluoric acid from flowing out. The peripheral parts are coated with acid resistant material. The reactor 10 is provided with two raw material inlets 20a and 20b and one phosphor outlet 30. In addition, a cylindrical stirrer is installed inside the reactor 10 to stir the reactants introduced into the reactor at a constant speed.

The precursor compound used as the reaction raw material is dissolved or slurried in distilled water or hydrofluoric acid and stored in the reaction material storage tanks 21a and 21b, and a constant input speed through the inlets 20a and 20b using the metering pumps 22a and 22b. The reaction was poured into. The reactants introduced through the two inlets form a vortex in the reactor and proceed with mixing and phosphor synthesis reaction by the vortices formed, and the synthesized phosphor rises to the top of the reactor in accordance with the flow direction of the fluid outlet 30. To be discharged. Phosphor discharged out of the reactor is stored in the synthetic material reservoir (31).

Phosphors stored in the synthetic material storage tank 31 were prepared through the post-treatment process of filtration and washing with the desired metal fluoride-based phosphor.

In the method of manufacturing the phosphor described above, the process of adding, mixing, synthesizing, and discharging the reactants proceeds continuously.

Examples 1 to 13. Size and Shape Comparison of Phosphor Particles Prepared by Continuous Manufacturing Method

Metal fluoride phosphors were continuously manufactured by the method of the representative example. K ₂ SiF ₆ : Mn ^{4 +} KF, K ₂ MnF ₆ , H ₂ SiF ₆ , HF were prepared as precursor compounds, and each precursor compound was weighed in consideration of the composition ratio. The prepared KF and K ₂ MnF ₆ was dissolved in hydrogen fluoride at a concentration of 1 to 5% and stored in the reactant storage tank 21a, and H ₂ SiF ₆ The solution was stored in the reactant reservoir 21b. The reaction was carried out while maintaining the input speed of the reactants shown in Table 1 and the stirring speed of the stirrer. In addition, the metal fluoride-based phosphor discharged through the outlet 3 of the reactor after the reaction is stored in the synthetic material storage tank 31, filtered as a post-treatment process, washed with acetone, ethanol and dried, K ₂ SiF ₆ : the Mn ^{4 +} phosphor was obtained.

division	Feed rate of reactant (mL / min)	Stirring Speed (rpm)
Example 1	10	100
Example 2	10	200
Example 3	10	300
Example 4	10	400
Example 5	10	600
Example 6	10	800
Example 7	10	1000
Example 8	10	1200
Example 9	2.5	100
Example 10	5	100
Example 11	15	100
Example 12	15	50
Example 13	15	150

3 and 4 are attached electron scanning micrographs comparing the particle size and shape of the metal fluoride-based phosphor prepared by changing the stirring speed or the reaction rate of the reactant. Figure 3 is synthesized under the conditions (Examples 2, 4 to 8) to keep the input rate of the reactant constant 10 mL / min, the stirring rate is maintained differently at 200, 400, 600, 800, 1,000, 1,200 rpm Picture of phosphor. And, Figure 4 is maintained at a constant stirring speed of 100 rpm, the reaction rate of the reactants synthesized in the conditions (Examples 1, 9 to 11) is maintained differently at 2.5, 5. 10, 15 mL / min It is a photograph.

3 and 4, it can be seen that the synthesized phosphor particles can be controlled in size and shape by controlling the input speed and / or the stirring speed of the reactants.

Examples 14 to 27. Structure and Optical Properties of Phosphors Prepared by Continuous Production

Phosphors were prepared by the continuous manufacturing method according to Examples 1 to 13, but various metal fluoride-based phosphors shown in Table 2 were synthesized by changing the type and composition ratio of the precursor compounds differently.

The synthesized phosphors were analyzed for emission characteristics using excitation light of various wavelengths using a luminescence analyzer (PerKin Elmer Photo-Luminescence), and the results are shown in Table 2 below.

division	constitutional formula	Excitation wavelength (nm)	Luminous center wavelength (nm)
Example 12	K 2 SiF 6 : Mn 4 +	450	630
Example 14	K 2 TiF 6 : Mn 4 +	450	630
Example 15	Cs 2 GeF 6 : Mn 4 +	450	630
Example 16	K 2 GeF 6 : Mn 4 +	450	630
Example 17	K 2 TiF 6 : Mn 4 +	450	630
Example 18	KMgF 3 : Eu 2 +	254	358
Example 19	BaGdF 5 : Tb 3 +	365	543
Example 20	CaF 2 : Mn 2 +	365	495
Example 21	ZnF 2 : Mn 2 +	365	587
Example 22	AlF 3 : Fe 3 +	365	735
Example 23	Sr 2 AlF 5 : Eu 2 +	254	360
Example 24	MgF 2 : Mn 2 +	400	590
Example 25	YF 3 : Yb 3 + , Er 3 +	980	550, 660
Example 26	LiYF 4 : Nd 3 +	365	520, 580
Example 27	KLaF 4 : Yb 3 + , Tb 3 +	980	545

As can be seen from Table 2, various metal fluoride phosphors can be synthesized by the continuous production method according to the present invention, and the synthesized metal fluoride phosphors have various emission wavelengths.

5 and 6 show emission spectra and X-ray powder diffraction spectra of K ₂ SiF ₆ : Mn ^{4 +} and K ₂ TiF ₆ : Mn ^{4 +} phosphors prepared by the continuous preparation method according to Examples 12 and 14 ^; Each is attached. 5 shows emission characteristics at an excitation wavelength of 450 nm. It can be seen that the K ₂ SiF ₆ : Mn ^{4 +} and K ₂ TiF ₆ : Mn ^{4 +} phosphors are red phosphors having an emission center wavelength of 630 nm. . In addition, it can be confirmed that the phosphor was well formed through the XRD spectrum of FIG. 6.

7 is attached the emission spectra of the KMgF ₃ : Eu ^{2 +} and KLaF ₄ : Yb ³⁺ and Tb ³⁺ phosphors prepared by the continuous production method according to Examples 18 and 27. The emission spectrum of FIG. 7 shows emission characteristics at an excitation wavelength of 980 nm. The KMgF ₃ : Eu ^{2 +} phosphor is a UV A phosphor having an emission center wavelength of 358 nm, and the KLaF ₄ : Yb ³⁺ and Tb ³⁺ phosphors are It can be seen that the emission center wavelength is a green phosphor having a wavelength of 545 nm.

[Description of the code]

10: reactor

11: Stirrer 12: Temperature Control Jacket

13: temperature control device

20: inlet

20a: first inlet 20b: second inlet

21a: first reactant reservoir 21b: second reactant reservoir

22a: first metering pump 22b: second metering pump

30: outlet 31: synthetic material reservoir

Claims (10)

1. In the method for continuously producing a metal fluoride phosphor by the liquid phase method,

   (Step 1) Step 1 to prepare a reactant in the dissolved or slurry state by mixing the metal precursor used for the synthesis of metal fluoride-based phosphor in distilled water or hydrofluoric acid;

   (Step 2) step 2 of continuously introducing the reactants into the reactor through an inlet formed on one side of the reactor using a metering pump;

   (Step 3) The inside of the reactor is equipped with a cylindrical stirrer to rotate at regular intervals with the inner wall of the reactor, the reactant introduced into the reactor while the cylindrical stirrer rotates at a constant speed in the speed range of 10 ~ 1500 rpm is a fluid flow Mixing and reacting the resulting vortex (VORTEX) to synthesize metal fluoride-based phosphors;

   (4 steps) 4 steps of discharging the synthesized metal fluoride-based phosphor toward the outlet formed on the other side of the reactor according to the fluid flow of the reactant; And

   (5 steps) 5 steps of obtaining the phosphor powder by washing and drying the discharged phosphor; Including,

   Continuous preparation of the metal fluoride-based phosphor in which the two, three, and four step processes in which the reactants are introduced into the reactor, the reactants are mixed and reacted with the synthesized phosphor, and the phosphors are discharged from the reactor are performed in a continuous process. Way.
2. The method of claim 1,

   Method of continuously manufacturing a metal fluoride-based phosphor, characterized in that the input rate of the reactant introduced into the reactor in step 2 1 ~ 50 mL / min (based on a reactor of 100 mL capacity).
3. The method of claim 1,

   The reactor or peripheral accessory is a continuous manufacturing method of a metal fluoride-based phosphor, characterized in that coated with an acid resistant material or made of an acid resistant material in order to prevent contamination and damage by hydrofluoric acid.
4. The method of claim 1,

   The reactor is a continuous method of producing a metal fluoride-based phosphor, characterized in that the number or location of the inlet for the reactant is injected and the outlet for the synthesized phosphor is discharged to control the type or reaction pattern of the reactant.
5. The method of claim 1,

   The reactor is a continuous method of producing a metal fluoride-based phosphor, characterized in that installed to have a vertical, horizontal or a constant slope.
6. The method of claim 1,

   And a temperature control device such as a heater or a heat exchanger is further attached to the reactor to control the temperature of the reactant.
7. The method of claim 1,

   The outside of the reactor is a continuous manufacturing method of the metal fluoride-based phosphor, characterized in that the temperature control jacket capable of circulating the heat exchange medium.
8. The method of claim 1,

   The vortex (VORTEX) is a continuous manufacturing method of a metal fluoride-based phosphor, characterized in that the speed is adjusted by installing a fixed vortex or mechanical stirrer inside the reactor.
9. The method of claim 1,

   Metal fluoride-based phosphor is a continuous method of producing a metal fluoride-based phosphor having a formula of the formula (1).

   [Formula 1]

   A _a M _m F _f : R _r

   (In Formula 1, A is an alkali metal element selected from Li, Na, K, Rb, Cs and combinations thereof; M is Si, Ge, Ti, Zr, Al, Ga, In, Sc, Y La, Nb Is a metal element selected from Ta, Bi, Gd and combinations thereof; R is a transition metal or rare earth metal having an oxidation number of +2, +3, +4 as an activator; and the subscripts a, b, f and r are each The number of elements, 0≤a≤3, 0≤b≤2, 0 <f≤11, 0 <r <2, provided that a and b cannot be 0 at the same time)
10. The method of claim 8,

    The precursor of metal A is at least one selected from AF, AHF ₂ , A ₂ O, A ₂ CO ₃ , A _x [MF _y ] and A _x [MF _y ]: R, and the precursor of metal M is H _x [MF _at least one selected from _y ], A _x [MF _y ], and A _x [MF _y ]: R, and the precursor of the metal R is at least one selected from A _x [MF _y ]: R, wherein A, M And R is as defined in Formula 1, x is an absolute value determined from the charge of MF _y ions, y is an integer of 5, 6 or 7.

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