KR101694256B1 - Continuous method of metal fluoride-based phosphors - Google Patents

Abstract

The present invention relates to a continuous production method of a metal fluoride-based phosphor, which puts a reactant produced by dissolving or making two or more metal precursors into slurry in a reactor, performs mixing and phosphor synthesizing reactions by vortex generated by fluid flow of the reactant, and discharges the synthesized phosphor along the fluid flow of a solution through an outlet and, more specifically, to a continuous production method of a metal fluoride-based phosphor where input, mixing and synthesis, and discharge are processed in a series of processes.

Description

TECHNICAL FIELD The present invention relates to a continuous process for preparing metal fluoride-based phosphors,

More particularly, the present invention relates to a method for continuously producing a metal fluoride-based fluorescent material, and more particularly, to a method for continuously producing a metal fluoride-based fluorescent material by introducing a reactant prepared by dissolving or slurrying two or more metal precursors into a reactor, ), And the synthesized phosphor is discharged through a discharge port in accordance with the flow of the solution, and the continuous introduction of the metal fluoride fluorescent material into the continuous process of introduction, mixing, synthesis, and discharge is carried out .

BACKGROUND ART Metal fluoride-based phosphors are widely applied to light emitting devices such as light emitting diodes, laser diodes, surface light emitting diodes, inorganic electroluminescence devices, and organic electroluminescence devices.

International Patent Publication WO-2012-128837 (Patent Document 1) discloses a metal fluoride-base phosphor having a composition represented by the following formula (I).

(I)

A _x [MF _y ]: Mn ⁴⁺

Wherein A is selected from Li, Na, K, Rb, Cs and combinations thereof; M is at least one element selected from the group consisting of Si, Ge, Ti, Zr, Al, Ga, In, Sc, , is selected from Bi, Gd, and combinations thereof; x is the absolute value that is determined from the charge of the MF _y ion, y is 5, 6 or 7)

In addition, the present inventors have developed a metal fluoride-based phosphor having a composition represented by the following formula (II), and filed a patent application in Korean patent application No. 10-2015-0134405.

[Formula II]

[AF] ₃ [MF _z ]: Mn ⁴⁺

Wherein A is an alkali metal element selected from Li, Na, K, Rb, Cs and combinations thereof; M is at least one element selected from the group consisting of Si, Ge, Ti, Zr, Al, Ga, In, , 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;

General methods for producing metal fluoride-based fluorescent materials include solid-phase and liquid-phase methods. In the method for producing a metal fluoride-based fluorescent material using the solid-phase method, the fluoride precursor is weighed to a desired ratio, mixed with induction 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 synthesized more conveniently than the vapor phase method or the liquid phase method. However, there is a high possibility that fluorine reacts with other elements during the reaction to synthesize a fluorophosphor phosphor of an undesirable composition. Therefore, the solid phase method is convenient in the 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 is advantageous in that it can produce a phosphor having a desired composition as compared with the solid phase method because the fluoride is converted into a solution state and reacted. In the liquid phase method, the so-called precipitation method, in which the fluoride precursor is dissolved in distilled water or hydrofluoric acid (HF), and then the solubility of each solution is used to precipitate fluoride phosphors, has been widely used. However, there are a number of problems to be overcome in order to synthesize a fluoride-based phosphor in large quantities using the precipitation method. As a typical problem, the amount of hydrofluoric acid (HF) used as a solvent must be increased as the fluoride used as a reactant is mass-produced. However, since hydrofluoric acid is a safe material in handling, there is a limit to use as a salting solvent. In addition, in order to mass-produce, the amount of synthesized in one batch increases, so that a secondary processing process must also be equipped with a large-scale apparatus.

Therefore, it is required to develop a new synthesis method which makes it possible to safely and mass-produce metal fluoride-based phosphors which are not easy to handle raw materials.

International Patent Publication No. WO12128837 Korean Patent Application No. 10-2015-0134405

It is another object of the present invention to provide a novel synthesis method capable of simultaneously solving the problems of solid-phase and batch-type liquid-phase processes and enabling mass production of metal fluoride-base phosphors. That is, according to the present invention, there is provided a method for continuously producing a metal fluoride-based phosphor by continuously preparing a reaction solution based on a liquid phase method, continuously injecting, mixing and synthesizing the phosphor into a reactor, and continuously discharging the synthesized phosphor .

It is still another object of the present invention to provide an apparatus for continuous production of a metal fluoride-base phosphor.

In order to solve the above problems, the present invention provides a method for producing a metal fluoride-based fluorescent material, comprising the steps of: injecting a reactant prepared by dissolving or slurring two or more metal precursors used for synthesizing a metal fluoride-based fluorescent material into an inlet of a reactor, ), A method of continuous production of a metal fluoride-based phosphor in which the synthesis, the synthesis, and the discharge of the synthesized phosphor are carried out in a continuous process so that the reacted materials are mixed and the synthesized phosphor is discharged according to the fluid flow of the reactant .

In addition,

A reaction material storage tank (21a, 21b) storing a reactant prepared by mixing a metal precursor used for synthesizing a metal fluoride phosphor with distilled water or hydrofluoric acid to prepare a solution or a slurry;

Metering pumps 22a and 22b for injecting the reactants stored in the reactant storage tanks 21a and 21b into the reactor through the inlet ports 20a and 20b of the reactor;

A reactor (10) for mixing the reactants by a vortex formed by reactants put into a solution or a slurry state, synthesizing the phosphor, and discharging the synthesized phosphor according to the flow of the reactant; And

A reservoir 31 of the metal fluoride-base phosphor discharged through the outlet 30 of the reactor; Wherein the metal fluoride-based phosphor is continuously produced.

The continuous production method of the present invention can solve the problems of a general solid phase method and a batch (Bach) type liquid phase method simultaneously. Particularly, although the present invention is based on the liquid phase method, the synthesis limit of the batch type liquid phase method can be overcome, and the fluoride phosphor can be mass-produced as much as the user desires by introducing a continuous process.

Further, according to the continuous production method of the present invention, it is possible to synthesize a metal fluoride-based phosphor more securely by injecting a small amount of reactant in a not-so-great reactor space, and to produce a metal fluoride-based phosphor in a narrow reactor at a rate of 1 to 50 g per minute It is possible to mass-produce metal fluoride-based fluorescent materials.

1 is a configuration diagram of a reaction apparatus used in a continuous production method according to the present invention.
Fig. 2 is an overall configuration diagram of the continuous production process of the metal fluoride-base phosphor including the reaction device of Fig.
3 is an electron micrograph showing the particle size and shape of the metal fluoride-based fluorescent material prepared according to the stirring speed.
4 is an electron micrograph showing the particle size and shape of the metal fluoride-based fluorescent substance prepared according to the feed rate of the reactant.
5 is an emission spectrum of K ₂ SiF ₆ : Mn ⁴⁺ and K ₂ TiF ₆ : Mn ⁴⁺ phosphors prepared by the continuous production method.
6 is an X-ray powder diffraction spectrum of the K ₂ SiF ₆ : Mn ⁴⁺ and K ₂ TiF ₆ : Mn ⁴⁺ phosphors prepared by the continuous production method.
7 is an emission spectrum of KMgF ₃ : Eu ²⁺ and KLaF ₄ : Yb ³⁺ , Tb ³⁺ phosphors prepared by the continuous production method.

Hereinafter, the present invention will be described in more detail.

According to the method of continuously producing the metal fluoride-base phosphor according to the present invention, the reaction product prepared by dissolving or slurrying the metal precursor used for synthesizing the metal fluoride-base phosphor is introduced into the inlet of the reactor, After the reactants are mixed by VORTEX and the phosphor synthesizing reaction is carried out, the synthesized phosphor is subjected to a continuous process of inputting, mixing, synthesizing and discharging so as to discharge according to the fluid flow of the reactant.

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, it is possible to produce a metal fluoride-based phosphor having a desired composition. In addition, in the present invention, the synthesized phosphor is continuously discharged out of the reactor according to the flow of the fluid formed in the reactor, and is separated and purified through simple filtration. Since the precipitation step for solidifying the phosphor is omitted, It is possible to mass-produce the phosphor. Further, in the case of the precipitation method for solidifying the phosphor, a large amount of hydrofluoric acid (HF) is used as a good solvent. However, in the present invention, since hydrofluoric acid (HF) is used only when the precursor compound is dissolved or slurried, It is environmentally friendly.

Further, the present invention makes it possible to carry out the mixing and synthesis reaction through the fluid flow of the reactant introduced into the reactor, and successively carry out the process of transporting the generated phosphor toward the discharge port. By controlling the flow of the reactant, the reaction rate can be controlled to control the generation rate of the phosphor. The fluid flow in the reactor can be controlled by adjusting the rate of feed and / or the rate of stirring of the reactants. The reaction rate can be controlled within the range of 1 ~ 50 mL / min based on the 100 mL reactor, and it is also possible to quantitatively control the feed rate by installing a metering pump. Further, if a stationary vortexor or a mechanical stirrer is installed in the reactor, the reaction rate is further increased and the amount of synthesized phosphor can be greatly increased. The stirring speed may be preferably in the range of about 10 to 1500 rpm.

According to the present invention, when a reactant is introduced at a rate of 10 mL / min per minute using a 100 mL reactor, metal fluoride-based fluorescent material is generated at a rate of approximately 5 g / min per minute, so that 14 kg / day is synthesized per day . In the case of synthesizing a phosphor using a general solid-phase method, the continuous production method of the present invention was compared with the synthesis of 1 kg / day per day in one electric furnace (capacity 20 L) Or more.

Also, in the continuous production method according to the present invention, it is possible to control the size and shape of synthesized phosphor particles by controlling the feeding rate and the stirring speed of the reaction material. That is, the addition rate of the reactant is controlled in a range of 1 to 50 mL / min (based on a volume of 100 mL reactor), the stirring speed is controlled at 10 to 1500 rpm, or the metal fluoride The size and shape of the 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 mu m.

According to the continuous production method according to the present invention, phosphor particles having a small size and a uniform size are synthesized as the reactant introduction rate is increased, and phosphor particles having a larger size are synthesized as the reaction rate of the reactant is lowered. When two or more reactants are charged into the reactor and reacted in a sufficient amount, sufficient seeds are formed, and small and uniform phosphor particles are synthesized. However, when the amount of reactant is insufficient, a small amount of seed is continuously subjected to crystal growth So that the particle size becomes larger. That is, as the agitation speed is increased in a state where the feed rate of the reactant is kept constant, the chance of seed generation is reduced, and the phosphor particles already formed can be grown to a large extent. In addition, it is also possible to control the shape of the phosphor particles formed through adjustment of the feed rate and stirring speed of the reactants to a hexahedron, a tetrahedron, or amorphous.

The method for continuously producing the metal fluoride-based fluorescent material according to the present invention is,

A first step of mixing the metal precursor used in the synthesis of the metal fluoride-based fluorescent material with distilled water or hydrofluoric acid to prepare a reaction product in a dissolved or slurry state;

A step of injecting the reactant into the reactor through a charging port using a metering pump;

A third step of synthesizing a metal fluoride-based fluorescent material by mixing and reacting with a vortex (VORTEX) generated by the fluid flow of the charged reactant;

And discharging the synthesized metal fluoride-based fluorescent material through the outlet of the reactor according to the fluid flow of the reactant; And

Washing and drying the discharged phosphor to obtain a phosphor powder; .

In addition, the metal fluoride-based fluorescent material that can be produced by the continuous production method according to the present invention may have a composition formula represented by the following chemical formula (1).

[Chemical Formula 1]

A _a M _m F _f : R _r

Wherein A is an alkali metal element selected from Li, Na, K, Rb, Cs and combinations thereof; M is at least one element selected from the group consisting of Si, Ge, Ti, Zr, Al, Ga, In, B, f and r are each a metal element selected from the group consisting of Ta, Bi, Gd, and combinations thereof, R is an activator, a transition metal or rare earth metal having an oxidation number of +2, +3, +4, 0 < / = 2, 0 < f < 11, 0 &lt; r &lt; 2, provided that a and b can not be 0 at the same time)

A precursor compound derived from the metal A is selected from the group consisting of AF, AHF ₂ , A ₂ O, A ₂ CO ₃ , A _x [MF _y ], and A _x [MF _y ]: R can be employed. As the precursor compound from which the metal M is derived, at least one compound selected from H _x [MF _y ], A _x [MF _y ] and A _x [MF _y ]: R can be adopted. As the precursor compound from which the metal R is derived, at least one compound selected from A _x [MF _y ]: R can be adopted. A, M, and R used in the definition of the precursor compound are each as defined in Formula 1, x is an absolute value determined from the charge of MF _y ion, and y may be an integer of 5, 6, or 7.

In addition, FIG. 1 illustrates one embodiment of a reaction apparatus applicable to the present invention, and the present invention is not limited thereto.

Referring to FIG. 1, the reactor 10 is provided with inlet ports 20a and 20b for injecting reactants prepared in a solution or slurry state, and an outlet 30 for discharging the synthesized phosphor to the reactor according to the flow of the reactant .

Considering 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.

The reactor 10 is provided with a charging port 20 and a discharging port 30. The charging port 20 and the discharging port 30 may be provided one by one or two or more respectively, It is also possible to arbitrarily adjust the position of the movable member 30. That is, it is possible to more easily control the reaction pattern by dividing the precursor compound used in the synthesis of the phosphor into two or more kinds of inlet ports and dividing the reactants into two. In addition, the number of the inlet 20 and the outlet 30 may be arbitrarily adjusted to control the flow of the fluid formed in the reactor. In the case of providing a plurality of the inlet ports 20, the positions of the inlet ports 20 may be separately provided in the lower part and the middle part of the reactor so that the reactants react with time differences. Depending on the circumstances, the inlet 20 and the outlet 30 may be connected to enable continuous particle growth. The reactants charged into the two or more inlet ports 20 meet in the reactor and synthesize the metal fluoride-based phosphor simultaneously with the mixing, and the generated phosphor rises. The raised phosphor is discharged to the discharge port 30 according to the flow of the fluid.

In addition, when installing the reactor 10, the reactor 10 may be installed to have a vertical, horizontal, or constant slope with respect to the ground according to the reaction pattern.

A temperature controller 13 such as a heater or a heat exchanger is attached to the reactor 10 to control the temperature of the reactant. In addition, a temperature control jacket 12 capable of circulating the heat exchange medium may be provided outside the reactor to adjust the temperature of the reactant. In addition, a temperature control device 13 may be attached to the reaction material storage tank so that the temperature of the reaction solution may be adjusted in advance, and the reaction solution may be supplied to the reactor 3 to maintain the temperature of the reaction solution at a constant level.

In addition, a fixed vortexor or a mechanical stirrer may be further provided in the reactor 10 to control the intensity of the vortex and the flow of the fluid. In the present invention, a vortex (VORTEX) is formed by a solution or a slurry-like reaction product introduced through the inlet ports (20a, 20b) of the reactor, and the reactant is mixed and synthesized by using the flow, The produced phosphor is transported to the discharge port (30) and discharged from the reactor. In addition, if the vortexor or the agitator is installed in the reactor, the intensity of the vortex can be adjusted more easily, thereby controlling the reaction rate, and the phosphor prepared by controlling the flow direction of the fluid can be easily moved toward the outlet 30 And can be discharged.

The mechanical stirrer 11 installed in the reactor 10 may have a propeller shape, a ribbon shape, a screw shape, a rod shape or a cylindrical shape, or an agitator composed of a combination of these may also be used. However, the present invention is not limited by the shape of the agitator, and an agitator suitable for the purpose can be selected.

It will be apparent to those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

[Example]

Representative embodiment. Continuous production of phosphors

A method of manufacturing the phosphor will be described with reference to the schematic view of the entire reaction apparatus shown in FIG.

The reactor (10) has a capacity of 100 mL and is made of Teflon or acid-resistant polymer that can withstand HF, and is sealed tightly to prevent leakage of HF, and peripheral accessories are coated with acid-resistant material. The reactor 10 is provided with two raw material input ports 20a and 20b and one phosphor discharge port 30. In the reactor 10, a propeller-type stirrer was installed to stir the reactant introduced into the reactor at a constant rate.

The precursor compounds used as the reaction raw materials are dissolved or slurried in distilled water or hydrofluoric acid and stored in the reaction material storage tanks 21a and 21b and are supplied through the tanks 20a and 20b through the metering pumps 22a and 22b, Was added to the reaction mixture. The synthesized phosphor rises to the upper part of the reactor in accordance with the flow direction of the fluid and is discharged to the discharge port 30 through the discharge port 30. The reactant enters through the two inlet ports to form a vortex in the reactor, . The phosphor discharged from the reactor is stored in a synthetic material reservoir 31.

The phosphors stored in the synthetic material reservoir 31 were subjected to post-treatment such as filtration and washing to prepare the desired metal fluoride-based phosphor.

In the above-described method of manufacturing a phosphor, the introduction, mixing, synthesis, and discharge of reactants proceed continuously.

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

The metal fluoride-base phosphor was continuously produced by the method of the above-mentioned representative embodiment. KF, K ₂ MnF ₆ , H ₂ SiF ₆ and HF were prepared as precursor compounds for the preparation of K ₂ SiF ₆ : Mn ⁴⁺ phosphor, and each precursor compound was weighed in consideration of the composition ratio. The prepared KF and K ₂ MnF ₆ were dissolved in hydrogen fluoride at a concentration of 1 to 5% and stored in the reactant storage tank 21 a and the H ₂ SiF ₆ solution was stored in the reactant storage tank 21 b. The reaction was carried out while the feed rate of the reactants shown in Table 1 and the stirring speed of the stirrer were maintained. After the reaction, the metal fluoride-base phosphor discharged through the outlet 3 of the reactor is stored in a synthetic material reservoir 31, filtered as a post-treatment process, washed with acetone, ethanol and dried to obtain K ₂ SiF ₆ : Mn ⁴⁺ phosphor.

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

FIG. 3 and FIG. 4 are photographs of a scanning electron microscope obtained by comparing the particle size and the shape of the metal fluoride-based fluorescent substance prepared by changing the stirring speed or the rate of feeding the reactants. FIG. 3 shows the results obtained when the feed rate of the reactant was kept constant at 10 mL / min and the stirring speed was maintained at 200, 400, 600, 800, 1,000 and 1,200 rpm (Examples 2 and 4 to 8) It is a photograph of a phosphor. 4 is a graph showing the relationship between the amount of the phosphor synthesized in the conditions (Examples 1, 9 to 11) in which the agitation speed was kept constant at 100 rpm and the feed rates of the reactants were maintained at 2.5, 5., It is a photograph.

According to FIG. 3 and FIG. 4, it can be seen that the synthesized phosphor particles can be controlled in size and shape by controlling the charging rate and / or stirring speed of the reactant.

Examples 14 to 27. Comparison of Structure and Optical Properties of Phosphors Produced by Continuous Manufacturing Method

The phosphors were prepared by the continuous production method according to Examples 1 to 13, except that the kinds and the composition ratios of the precursor compounds were changed to synthesize various metal fluoride phosphors shown in Table 2 below.

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

division constitutional formula Excitation wavelength (nm) Luminescent 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-based phosphors can be synthesized by the continuous production method according to the present invention, and the synthesized metal fluoride-based phosphors have various emission wavelengths.

5 and 6 show emission spectra and X-ray powder diffraction spectra of the K ₂ SiF ₆ : Mn ⁴⁺ and K ₂ TiF ₆ : Mn ⁴⁺ phosphors prepared by the continuous production method according to Example 12 and Example 14, Respectively. The emission spectrum of FIG. 5 shows the emission characteristics at an excitation wavelength of 450 nm, and it can be confirmed that K ₂ SiF ₆ : Mn ⁴⁺ and K ₂ TiF ₆ : Mn ⁴⁺ phosphors are red phosphors having a luminescent center wavelength of 630 nm . Also, it can be confirmed that the phosphor is well formed through the XRD spectrum of FIG.

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

10: Reactor
11: Stirrer 12: Temperature control jacket
13: Temperature control device
20: inlet
20a: first inlet 20b: second inlet
21a: first reactant storage tank 21b: second reactant storage tank
22a: first metering pump 22b: second metering pump
30: Outlet
31: Synthetic material storage tank

Claims (18)

As a method for continuously producing a metal fluoride-base phosphor having a composition formula represented by the following formula (1) by a liquid phase method,
(Step 1) In a first step, a metal precursor used for synthesizing a metal fluoride-based fluorescent material is mixed with distilled water or hydrofluoric acid to prepare a reaction product in a dissolved or slurry state;
(Step 2) The reactant is continuously introduced into the reactor through the inlet formed at one side of the reactor using a metering pump;
(Step 3) A cylindrical stirrer is installed inside the reactor to rotate at a constant interval from the inner wall of the reactor. While the cylindrical stirrer rotates at a constant speed in the range of 10 to 1500 rpm, the reactant introduced into the reactor flows into the fluid stream Mixing and reacting with the generated vortex (VORTEX) to synthesize a metal fluoride-base phosphor having a composition represented by the following formula (1);
(Step 4) In the fourth step, the synthesized metal fluoride-based fluorescent material is moved toward the outlet formed on the other side of the reactor according to the fluid flow of the reactant and discharged; And
(Step 5) 5 steps of washing and drying the discharged phosphor to obtain a phosphor powder; Lt; / RTI &gt;
The second step, the third step, and the fourth step in which the phosphor is synthesized by the reaction of the reactants in the reactor, the reaction mixture is mixed and reacted, and the phosphor synthesized from the reactor is discharged, A method for continuous production of a phosphor.
[Chemical Formula 1]
A _a M _m F _f : R _r
Wherein A is an alkali metal element selected from Li, Na, K, Rb, Cs and combinations thereof; M is at least one element selected from the group consisting of Si, Ge, Ti, Zr, Al, Ga, In, M, f and r are each a metal element selected from Ta, Bi, Gd and combinations thereof, R is an activator, a transition metal or rare earth metal having an oxidation number of +2, +3, +4, 0 < r < 2, provided that a and b can not be 0 at the same time)
The method according to claim 1,
Wherein the feed rate of the reactant introduced into the reactor in Step 2 is 1 to 50 mL / min (based on a reactor of 100 mL capacity).
delete The method according to claim 1,
Precursors of metal A, _{AF, AHF 2, A 2 O} , A 2 CO 3, A x [MF y] , and A _x [MF _y]: not less than one selected from R, the precursor of the metal M is H _x [MF _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, and R are as defined in formula 1, x is the absolute value that is determined from the charge of the MF _y ion, y is 5,6 or continuous process for producing a metal fluoride-based fluorescent material, it characterized in that the integer 7.
The method according to claim 1,
Wherein the reactor or peripheral accessory is coated with an acid-resistant material or made of an acid-resistant material to prevent contamination and breakage by hydrofluoric acid.
The method according to claim 1,
Wherein the reactor is controlled in terms of the kind of the reactant and the number or position of the discharge port through which the reactant is introduced and the discharge port through which the synthesized phosphor is discharged.
The method according to claim 1,
Wherein the reactor is installed so as to have a vertical, horizontal, or constant inclination.
The method according to claim 1,
Wherein the reactor is further equipped with a temperature control device such as a heater or a heat exchanger to adjust the temperature of the reactant.
The method according to claim 1,
Wherein a temperature control jacket capable of circulating a heat exchange medium is provided outside the reactor.
The method according to claim 1,
Wherein the vortex (VORTEX) is provided with a fixed vortexor or a mechanical stirrer inside the reactor to control the speed of the metal fluoride-based phosphor.
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