KR101250142B1 - Processing method of a long phosphorescence phosphor by combustion-reaction and its application for the fabrication of luminescent sheet - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a luminescent body powder of strontium-aluminum oxide (SrO-Al ₂ O ₃ ) system which exhibits yellow-green light emission characteristics, and has a very high luminance.
To this end, by mixing the strontium salt, aluminum salt, activator, the active agent in a molar ratio of 0.97: 2.0: 0.005: 0.01, adding a flux and heating and heat treatment using a reaction fuel to burn the reaction, It is characterized by producing a strontium-aluminum oxide (SrO-Al ₂ O ₃ ) -based photoluminescent powder exhibiting yellow-green light emission.
According to the above constitution, the strontium-aluminum oxide-based phosphor powder synthesized by the combustion reaction exhibits yellow-green light emission, and according to the appropriate amount of flux or reaction fuel in the process of manufacturing the phosphor powder, and the appropriate heat treatment temperature, In addition, there is an effect that can be greatly improved, and also by producing a light emitting sheet by mixing the phosphor powder and synthetic resin, there is also an effect that can be utilized as an auxiliary light in a dark environment or at night.

Description

Process for manufacturing a phosphorescent body powder using a combustion reaction method and a phosphorescent body powder, and a light emitting sheet produced using the phosphorescent body powder {Processing method of a long phosphorescence phosphor by combustion-reaction and its application for the fabrication of luminescent sheet}

The present invention exhibits a luminescence property of yellow-green color and has a very high luminescence brightness. A method of preparing a phosphorescent powder of strontium-aluminum oxide (SrO-Al ₂ O ₃ ) -based phosphorescent powder and the phosphorescent powder prepared by using the phosphorescent powder It relates to a light emitting sheet.

In general, when an external external stimulus is applied to the phosphor, light emission is performed. When the external stimulus is stopped, the afterglow time of the phosphor is usually very short, so that the light emission quickly disappears.

On the other hand, the photoluminescent material is a material having the property of absorbing energy by stimulating light having a relatively high level, such as a lamp or solar light, and then reducing it to low level visible light to emit light for a long time in a dark place. This is the case of photophosphor or phosphorescent material.

Such photoluminescent materials can be used as fluorescent paints used in emergency exit signs, military installations, clothing paints, lighting equipment, highways, railways, aircraft, ports and buildings, etc. It can also be widely used as watch, luminous decoration, luminous paint, fluorescent glaze.

Representative compounds used as such photoluminescent materials include sulfide-based photoluminescence such as CaS: Bi (violet luminescence), CaSrS: Bi (blue luminescence), ZnS: Cu (green luminescence), and ZnCdS: Cu (yellow to orange luminescence). Sieve is known.

However, the sulfide-based phosphors are not only chemically stable, but also suffer from various problems in actual use, such as poor light resistance in a humid place.

For example, zinc sulfide-based ZnS: Cu is one of the most widely used phosphors, and when moisture is present, it is decomposed by ultraviolet rays and turns black, or its brightness decreases. Is difficult and its use is extremely limited.

On the other hand, in order to solve the above problems, many researches on photoluminescent compounds are being conducted. In particular, compounds containing zinc sulfide as a main component are mixed with radiation materials to extend the duration of light emission. Here, light is emitted for a long time.

However, the radiation material used as the excitation source is not only harmful to the human body, it is not environmentally friendly, and there is a problem that many restrictions in terms of supply and demand of raw materials due to the handling regulations for the radiation material.

Therefore, in recent years, there has been a growing interest as the phosphorescent body of strontium-aluminum oxide (SrO-Al ₂ O ₃ ) which is chemically stable, has excellent durability, and does not contain a radioactive material as an excitation source, At present, many research and developments have not been progressed, and thus, there is a difficulty in implementing excellent luminescence and long afterglow characteristics, and accordingly, there is a problem that the use of the photoluminescent body is also extremely limited.

Republic of Korea Patent Registration No. 0174088 Republic of Korea Patent Registration No. 0350691 Korean Registered Patent Publication No. 0487067 Republic of Korea Patent Publication No. 0600934 Republic of Korea Patent Application No. 10-2008-0099706 Republic of Korea Patent Application No. 10-2008-0124055

The present invention has been made to solve the conventional problems as described above, to produce a luminescent powder of the strontium-aluminum oxide composition through the combustion reaction of the mixture to significantly improve the light emission intensity of the phosphor powder There is provided a method of manufacturing a phosphorescent body powder using a combustion reaction method, a phosphorescent body powder thereof, and a light emitting sheet manufactured using the phosphorescent body powder.

Another object of the present invention is to manufacture a light emitting sheet having a phosphor powder, and attaching it to various apparatuses for lighting to reduce the use of electric energy to reduce energy by using a combustion reaction method and a method for producing the phosphor powder It is to provide a photoluminescent powder and a light emitting sheet produced using the photoluminescent powder.

The phosphorescent powder manufacturing method of the present invention for achieving the above object, strontium salt (Sr (NO ₃ ) ₂ ), aluminum salt (Al (NO ₃ ) ₂ 9H ₂ O), activator, a study agent Strontium-aluminum oxide (SrO-Al ₂ O ₃₎ , which emits yellow-green light emission by mixing at a molar ratio of 0.97: 2.0: 0.005: 0.01, adding a flux, and heating and heat-treating the reaction fuel. A) phosphorescent powder is produced.

Further, another method of manufacturing the phosphorescent powder of the present invention is to mix strontium salt (Sr (NO ₃ ) ₂ ), aluminum salt (Al (NO ₃ ) ₂ .9H ₂ O), a flux, and a reaction fuel with distilled water. Dissolving the first solution; A second solution dissolving step of dissolving the activator and the study active agent by mixing with acidic water; Mixing and stirring the first solution and the second solution; Heating and burning the stirred mixed solution in a furnace to produce a powder of strontium-aluminum oxide composition; The resulting powder is subjected to a high temperature heat treatment in a hydrogen reducing atmosphere to prepare a strontium-aluminum oxide (SrO-Al ₂ O ₃ ) -based phosphorescent powder.

Here, the flux is boron oxide (B ₂ O ₃ ) is used, the reaction fuel is urea (NH ₂ CONH ₂ ) is used, the activator is europium oxide (Eu ₂ O ₃ ) is used, the active agent is deep oxide oxide Rossium (Dy ₂ O ₃ ) is used.

The reaction fuel is mixed at a molar ratio of 1: 0.5 to 3.0 with respect to a raw material in which strontium salt, aluminum salt, activator, and study agent are mixed.

In addition, the flux is mixed in a molar ratio of 1: 0.1 to 0.8 with respect to the raw material in which the strontium salt, the aluminum salt, the activator, and the study agent are mixed.

In addition, in the step of preparing the photoluminescent powder, the synthesized powder is heat-treated for 2 to 6 hours at a temperature of 1100 ~ 1500 ℃ in a hydrogen reducing atmosphere.

On the other hand, it is characterized in that the photoluminescent powder is produced by the above method.

In the light emitting sheet manufactured according to the present invention, the photoluminescent powder is mixed and dried with a synthetic resin and a resin hardener to form a soft photoluminescent layer, attaching a transparent resin layer on the surface of the photoluminescent layer, and attaching an adhesive layer on the back surface of the photoluminescent layer. It is characterized by being attached.

Here, the light emitting sheet is used to attach to any one of the luminous signs, billboards, billboards, decorations, lighting fixtures in the dark or blocked sunlight.

Through the above-mentioned means for solving the problem, the present invention, the strontium-aluminum oxide-based phosphor powder synthesized by the combustion reaction not only shows yellow-green light emission in the broad 450 ~ 600nm wavelength range, but also the flux or reaction in the manufacturing process of the phosphor phosphor powder There is an effect that can greatly improve the light emission intensity according to the appropriate amount of fuel, and according to the appropriate heat treatment temperature.

Furthermore, it is possible to manufacture a light emitting sheet by mixing phosphorescent powder and synthetic resin, and attach the light emitting sheet to luminous signs, billboards, signs, decorations, lighting fixtures, etc. There is also an effect.

1 is a strontium-aluminum oxide system according to the present invention Process drawing for manufacturing phosphorescent powder,
2 is a perspective view of a light emitting sheet manufactured by using a phosphor photoluminescent powder according to the present invention;
3 is strontium-aluminum oxide according to different heat treatment temperatures in the process of manufacturing the phosphor body according to the present invention Scanning electron microscope (SEM) images of the phosphors,
Figure 4 is an X-ray diffraction pattern of the strontium-aluminum oxide photoluminescent powder at different heat treatment temperatures in the manufacturing process of the photoluminescent powder according to the present invention.
5 is strontium-aluminum oxide prepared by the present invention A graph showing the excitation and emission spectra of the phosphor,
6 is a graph showing the emission spectrum of the strontium-aluminum oxide photoluminescent powder at different heat treatment temperatures in the process of manufacturing the photoluminescent powder according to the present invention;
7 is strontium-aluminum oxide according to the amount of flux added in the process of manufacturing the phosphor phosphor according to the present invention A graph showing the change in the luminescence intensity of the phosphor powder,
8 is strontium-aluminum oxide according to the mixing ratio of the reaction fuel in the manufacturing process of the phosphor phosphor according to the present invention A graph showing the change in the luminescence intensity of the phosphor powder,
9 is a graph showing the change in the light emission intensity of the light emitting sheet according to the mixing ratio of the photoluminescent powder in the light emitting sheet produced by the photoluminescent powder of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 shows a method of manufacturing a photoluminescent body using the combustion reaction method of the present invention, and includes a first solution dissolving step, a second solution dissolving step, a stirring step, a powder producing step, and a powder manufacturing step. .

Specifically, in the first solution dissolving step, strontium salt (Sr (NO ₃ ) ₂ ), aluminum salt (Al (NO ₃ ) ₂ .9H ₂ O), a flux, and a reaction fuel are mixed with distilled water to distilled water. By dissolving, a first solution is prepared.

Here, it is appropriate that boron oxide (B ₂ O ₃ ) or the like is used as the flux, and urea (NH ₂ CONH ₂ ) or the like is appropriate as the reaction fuel.

In the second solution dissolving step, a second solution is prepared by mixing and dissolving the activator and the study active agent with acidic water.

Herein, europium oxide (Eu ₂ O ₃ ), or the like, is appropriately used as the activator, and diprosium oxide (Dy ₂ O ₃ ), etc., is appropriately used as a study agent, and nitric acid (HNO) is used as an acidic water. ₃ ) and the like are appropriate.

At this time, looking at the composition mixing ratio of each of the raw materials, strontium salt, aluminum salt, the activator and the active agent is mixed in a molar ratio of 0.97: 2.0: 0.005: 0.01.

Subsequently, in the stirring step, the first solution and the second solution are mixed with each other and stirred.

In the powder producing step, the stirred mixed solution is introduced into a conventional electric furnace and heated and burned for about 5 minutes at a temperature of 500 to 700 ° C. under atmospheric pressure to produce a powder of strontium-aluminum oxide composition.

Finally, in the powder manufacturing step, the strontium-aluminum oxide (SrO-Al ₂ O ₃ ) -based powder was synthesized as described above by subjecting the powder synthesized and produced at the high temperature to a temperature of 1100 to 1500 ° C. for 2 to 6 hours in a hydrogen reduction atmosphere in the alumina boat. A photoluminescent powder is prepared. At this time, the elevated temperature is kept constant at about 3 ~ 10 ℃ / min.

On the other hand, Figure 2 shows a light emitting sheet 10 manufactured using the photoluminescent powder of the present invention, the light emitting sheet 10 is largely a photoluminescent layer 11, a transparent resin layer 12, and an adhesive layer ( 13) is configured to include.

Specifically, first, the photoluminescent powder is mixed with a liquid synthetic resin and then cured into a flexible thin plate to produce a soft photoluminescent layer 11. Here, the synthetic resin is a bisphenol-based soft epoxy resin used with a resin hardener (for example, polyamide), mixed sufficiently with the phosphor body powder, and then dried in a dryer of about 65 ~ 80 ℃ for several hours The photoluminescent layer 11 is manufactured.

At this time, the preferred mixing ratio of the synthetic resin, the resin hardener, and the photoluminescent powder may be mixed in a weight ratio of about 2: 1.0: 0.6, and may be mixed slightly differently without using a predetermined mixing ratio.

In addition, a transparent resin layer 12 made of a material such as vinyl is attached to the upper surface of the photoluminescent layer 11 to protect deterioration of the photoluminescent layer 11, and a light emitting sheet 10 is disposed on a bottom surface of the photoluminescent layer 11. The adhesive layer 13 is attached and configured to attach. In this case, the backing of the adhesive layer 13 may further include a cover (not shown) serving to protect the adhesive layer 13, and the transparent resin layer 12 may be omitted depending on the purpose.

In addition, the light emitting sheet 10 manufactured as described above may be used by being attached to any one of luminous signs, billboards, signs, decoration decorations, and lighting fixtures in a sun-blocked or dark environment, but is limited to the above examples. In addition, it is possible to attach to various apparatuses that can be utilized as an auxiliary lighting apparatus. That is, in order to attach the light emitting sheet 10, the light emitting sheet 10 may be adhesively fixed to the reflective plate 10 through the adhesive layer 13 on the rear surface thereof.

Referring to the operation and effect of the present invention configured as described in detail as follows.

In order to prepare the strontium-aluminum oxide-based photoluminescent powder according to the present invention, as shown in FIG. A powder of strontium-aluminum oxide composition is synthesized by mixing with a solution dissolved in water and subjecting to combustion.

The reaction fuel for inducing the combustion reaction is a molar ratio of 1: 0.5 to 3.0, based on the reaction fuel, of the ratio of the oxidizing agent (a raw material mixed with the strontium salt, the aluminum salt, the activator, and the study active agent). Mix. The flux, which promotes grain growth of the parent crystal and improves the luminescence intensity, is based on the ratio of the oxidizing agent (a raw material mixed with the strontium salt, the aluminum salt, the activator, and the active agent) based on the flux 1: Add in a molar ratio of 0.1-0.8.

The mixed solution prepared as described above is heated to a temperature of about 600 ° C. to cause a combustion reaction to synthesize a powder of strontium-aluminum oxide-based composition. Finally, the synthesized powder is placed in an alumina boat and heat-treated for 2 to 6 hours in a temperature range of 1100 to 1500 ° C. in a hydrogen reduction atmosphere to have luminescent properties. At this time, the temperature increase rate is kept constant at about 3 ~ 10 ℃ / min.

The light emitting sheet 10 including the resin as shown in FIG. 2 may be manufactured by mixing and drying the strontium-aluminum oxide-based photoluminescent powder of the yellow-green wavelength emission prepared above with a synthetic resin and a resin hardener, and the light emitting sheet 10 It can be used as an auxiliary lighting function by attaching it to luminous signs, billboards, signs, decorations, and lighting fixtures.

In addition, the strontium-aluminum oxide-based photoluminescent powder may be appropriately mixed with the light-emitting paint, and then applied to the above apparatuses.

(1) Physical Properties of Strontium-Aluminum-Ox Phosphor Powders Synthesized by Combustion

3 is a field emission scanning electron microscope of luminescent powders sintered for 3 hours by varying the strontium-aluminum oxide-based composition synthesized by a combustion reaction at a hydrogen reduction atmosphere at 100 ° C. intervals from 1100 ° C. to 1400 ° C. FE-SEM) photo, (a) is the initial powder form synthesized by the combustion reaction method, (b) is the powder form when the reaction temperature is 1100 ℃, (c) is the reaction temperature is 1200 ℃ Powder at the time, (d) is the powder when the reaction temperature is 1300 ° C, and (e) is the powder when the reaction temperature is 1400 ° C.

As shown in the photograph, it can be seen that particle growth occurred during the heat treatment process. That is, the particle size (thickness) of the initial powder is about several tens of nm, but when heat-treated at 1100 ℃ increased to several hundred nm, through this heat treatment at a high temperature of more than 1100 ℃ by the aggregation between the particles is active and crystal growth occurs You can check it. However, even if the heat treatment temperature was increased from 1100 ° C. to 1400 ° C., the particle size did not change significantly.

4 is a strontium-aluminum oxide-based photoluminescent powder according to the heat treatment temperature X-ray diffraction analysis results. Thus, the X-ray diffraction peaks, the initial powder synthesized by the combustion reaction and the powders heat-treated at 1100 ℃, 1200 ℃ produced some intermediate phases (SrAl ₂ O ₄ , Sr ₂ Al ₂ O _7, etc.) Above 1300 ° C., the intermediate phases disappear and only the strontium-oxide final crystal phase of the present invention is present.

(2) Phosphorescent Properties of Strontium-Aluminum-Ox Phosphor Powders

Figure 5 shows the excitation spectrum and the emission spectrum obtained for the strontium-oxide aluminum-based photoluminescent powder heat-treated at 1300 ℃ 3 hours.

The excitation spectrum exhibits excitation over a wide wavelength region of 220 nm to 470 nm and exhibits a maximum absorption peak at 369 nm. Since the wavelength range of 220 nm to 470 nm is also included in the sunlight, the strontium-aluminum oxide photoluminescent material is easily excited by sunlight and emits light, and the excitation intensity is significantly lowered at 320 nm or less. It can be seen that it is a photoluminescent material which can emit light even in ultraviolet rays having shorter wavelength than the existing ZnS: Cu-based.

In addition, the emission spectrum exhibits a broad emission spectrum of 450 to 600 nm with a maximum emission wavelength of 493 nm, which is an yellowish green emission region, and is similar to that of ZnS: Cu, which is widely used as a conventional photoluminescent material.

Figure 6 is a light emission spectrum according to the heat treatment temperature of the powder sample heat-treated for 3 hours in a hydrogen reducing atmosphere in the temperature range of 1100 ~ 1500 ℃.

As the excitation light source, light of 360 nm generated from the Xe lamp was used. As shown in the figure, the emission intensity increased as the heat treatment temperature increased. However, the powders heat-treated at 1550 ° C. and 1600 ° C., which are more than 1500 ° C., exhibited a decrease in luminescence intensity, because at some temperatures above 1500 ° C., partial partial dissolution occurred, and phase decomposition occurred to generate a second phase.

(3) effect of flux

7 is a graph showing the luminescence intensity measured with respect to the strontium-aluminum oxide-based photoluminescent body according to the amount of flux added.

As shown in the figure, when the addition amount of the flux is increased, the luminescence intensity is greatly increased, indicating the highest luminescence intensity at 0.5 mol, and decreasing rather than being added thereto. Therefore, it can be seen that the appropriate amount of flux is 0.5 mole.

(4) Effect of Reaction Fuel

8 is a mixed amount of the reaction fuel used to synthesize the powder of the strontium-aluminum oxide-based composition by the combustion reaction [reaction fuel / oxidizing agent (strontium salt, aluminum salt, activator, and a study agent) Raw material)].

As shown in the figure, when the amount of reaction fuel is increased, the luminescence intensity is greatly increased, and the mixing ratio of the oxidant and the reaction fuel shows the highest luminescence intensity at 1.5. Therefore, it can be seen that the proper mixing ratio of the reaction fuel is about 1.5 compared to the oxidizing agent.

(5) Luminous property of light emitting sheet

The light emitting sheet 10 was prepared by mixing the strontium-aluminum oxide-based photoluminescent powder described above with a synthetic resin, and the photoluminescent properties were examined.

Luminescent luminance (intensity) was measured by mixing different weight ratios of the photoluminescent powder mixed with the synthetic resin and the resin hardener.

That is, the mixing ratio of the synthetic resin and the resin hardener is fixed at a weight ratio of 2.0: 1.0, the weight ratio of the phosphor powder is changed in the range of 25% to 50% by weight, and the Hg-lamp as the excitation light source to measure the luminous luminance. It was irradiated for about 10 minutes using (350 nm).

As shown in FIG. 9, the luminance of the phosphor was increased up to 40% by weight, and the luminance was increased in proportion to the amount of the phosphor. Therefore, it was found that the appropriate mixing ratio of the phosphorescent body powder in manufacturing the light emitting sheet 10 was about 40% by weight based on the mixing weight of the synthetic resin and the resin hardener.

On the other hand, the present invention has been described in detail only with respect to the specific examples described above it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, it is natural that such variations and modifications belong to the appended claims. .

10 light emitting sheet 11 light emitting layer
12: transparent resin layer 13: adhesive layer

Claims (9)

Strontium salt (Sr (NO ₃ ) ₂ ), aluminum salt (Al (NO ₃ ) _{2 ·} 9H ₂ O), activator, active agent in a molar ratio of 0.97: 2.0: 0.005: 0.01 By adding and reacting with a fuel to heat and heat the combustion reaction to produce a strontium-aluminum oxide (SrO-Al ₂ O ₃ ) -based phosphor body which exhibits yellow-green light emission. Body powder manufacturing method. A first solution dissolving step of dissolving strontium salt (Sr (NO ₃ ) ₂ ), aluminum salt (Al (NO ₃ ) ₂ .9H ₂ O), a flux, and a reaction fuel with distilled water;
A second solution dissolving step of dissolving the activator and the study active agent by mixing with acidic water;
Mixing and stirring the first solution and the second solution;
Heating and burning the stirred mixed solution in a furnace to produce a powder of strontium-aluminum oxide composition;
A method of manufacturing a photoluminescent powder using a combustion reaction method comprising the step of preparing a strontium-aluminum oxide (SrO-Al ₂ O ₃ ) -based photoluminescent powder by heat-treating the resulting powder at high temperature in a hydrogen reducing atmosphere. According to claim 1 or 2, wherein the flux is boron oxide (B ₂ O ₃ ) is used, the reaction fuel is urea (NH ₂ CONH ₂ ) is used, the activator is europium oxide (Eu ₂ O ₃ ) This is used, a method for preparing a photoluminescent powder using a combustion reaction method, characterized in that di- prosium oxide (Dy ₂ O ₃ ) is used. The reaction fuel according to any one of claims 1 to 2, wherein the reaction fuel is mixed at a molar ratio of 1: 0.5 to 3.0 with respect to a raw material in which a strontium salt, an aluminum salt, an activator, and an active agent are mixed. A method of manufacturing a photoluminescent powder using a combustion reaction method. The method of claim 1, wherein the flux is mixed with a strontium salt, an aluminum salt, an activator, and a study agent in a molar ratio of 1: 0.1 to 0.8 with respect to a raw material. A method of manufacturing a photoluminescent powder using a combustion reaction method. The method of claim 2, wherein in the step of preparing the photoluminescent powder, the synthesized powder is heat-treated at a temperature of 1100-1500 ° C. for 2 to 6 hours in a hydrogen reducing atmosphere. . A photoluminescent powder using the combustion reaction method, which is prepared by the method according to claim 1 or 2. The photoluminescent powder prepared according to claim 7 is mixed with a synthetic resin and a resin hardener and dried to form a soft photoluminescent layer 11, and the transparent resin layer 12 is attached to the surface of the photoluminescent layer 11. The light emitting sheet manufactured using the photoluminescent powder characterized by attaching the adhesive layer 13 to the back surface of the photoluminescent layer (11). The method of claim 8, wherein the light emitting sheet is manufactured using a photoluminescent powder, characterized in that attached to any one of the luminous signs, billboards, billboards, signs, decoration decorations, lighting fixtures in the sun is blocked or dark environment. Luminous sheet.

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