JP5431995B2 - Fluorescent material for aqueous fluorescent paint and method for producing the same - Google Patents

Description

The present invention relates to a fluorescent material for aqueous fluorescent paint and a method for producing the same. More specifically, for example, the present invention relates to a fluorescent material for water-based fluorescent paint that is useful for building materials such as a luminous paint, a luminous tile that can be visually recognized in the dark, an evacuation guidance display board, and the like, and a manufacturing method thereof.

  Conventionally, various researches have been made in order to effectively utilize shells such as scallops as industrial waste, instead of treating them as industrial waste. For example, as a method for effectively utilizing scallop shells, a method for producing a phosphor by firing a scallop shell at a temperature exceeding 100 ° C. (see, for example, Patent Document 1), shell powder and alumina and / or water A method for producing a phosphorescent phosphor by sintering a raw material containing an aluminum oxide powder and an activator (see, for example, Patent Document 2), and a powder obtained by pulverizing a shell after firing it is Ca-α. -A method used as a raw material for producing sialon phosphors (for example, see Patent Document 3) is known.

  However, since all phosphors using conventional shells use solid shell powder that is insoluble in water, for example, when used in paints, the dispersibility and smoothness of the formed coating film Since there are disadvantages in that it is inferior in the property (leveling property) and the fluidity of the paint is lowered, there is a great restriction on its application development.

  Therefore, in recent years, the development of functional materials with excellent water solubility by effectively utilizing shells discarded as industrial waste has been awaited.

JP 2004-359923 A JP 2007-131773 A JP 2007-177075 A

  This invention is made | formed in view of the said prior art, and makes it a subject to provide the fluorescent material which can be used suitably for uses, such as a water-based paint, and its manufacturing method, for example.

The present invention
(1) A fluorescent material containing, as an active ingredient, an extract obtained by baking a shell powder obtained by firing shells with water , wherein the shell comprises a scallop shell, a mussel shell, and a shellfish shell And at least one kind of shell selected, wherein the fired powder of the shell is a fired powder obtained by firing the shell at a temperature of 150 to 400 ° C., and the extract contains the fired powder of the shell at 5 to 60 ° C. A fluorescent material for aqueous fluorescent paint, which is an extract extracted in water, wherein the baked powder contained in the extract is removed ,
(2) an aqueous fluorescent paint fluorescent material containing as an active ingredient an extract composed evaporated to dryness and the solid product according to prior SL (1),
( 3 ) An aqueous fluorescent paint comprising the fluorescent material for an aqueous fluorescent paint according to (1) or ( 2) ,
( 4 ) A method for producing a fluorescent material for an aqueous fluorescent paint , in which a fired powder of shells obtained by firing and pulverizing shells is dispersed in water, and the fired powder of shells is removed from the obtained dispersion. The shell is at least one shell selected from the group consisting of a scallop shell, a mussel shell and a shellfish shell, and the shell is fired at a temperature of 150 to 400 ° C. The method for producing a fluorescent material for water-based fluorescent paints, wherein the fired powder obtained by extraction with water at 5 to 60 ° C. and removing the fired powder contained in the obtained extract ,
( 5 ) The method for producing a fluorescent material for aqueous fluorescent paint according to ( 4 ), wherein the shell is pulverized after firing, and ( 6 ) the dispersion from which the fired powder of the shell is further removed is evaporated to dryness. (4) or manufacturing how an aqueous fluorescent paint fluorescent material according to (5)
About the.

ADVANTAGE OF THE INVENTION According to this invention, the fluorescent material for aqueous | water-based fluorescent paints which can be used effectively, for example, for applications, such as a water-based paint, and the manufacturing method of the same are conventionally used effectively as a raw material by the shell processed conventionally as waste. Is done.

It is an X-ray-diffraction figure of the baked powder of the shell obtained in Examples 1-3 of the present invention. It is a drawing substitute photograph which shows a state when white light or an ultraviolet-ray is irradiated to the fluorescent material obtained in Examples 1-3 of this invention. It is a graph which shows a fluorescence emission spectrum when the ultraviolet-ray with a wavelength of 370 nm is irradiated to the fluorescent material obtained in Examples 1-3 of this invention.

  The fluorescent material of the present invention contains, as an active ingredient, an extract obtained by extracting a fired powder of shells obtained by firing shells with water. Therefore, the fluorescent material of the present invention may be composed only of the extract, and as long as the extract contains the extract as an active ingredient, other components are included within the range in which the object of the present invention is not hindered. It may be included.

  The fluorescent material of the present invention can be produced by dispersing a fired powder of shells obtained by firing and pulverizing shells in water, and removing the fired powder of shells from the obtained dispersion. .

  A shell is used as a raw material for the fluorescent material of the present invention. According to the present invention, it is possible not only to effectively use shells that have been discarded as industrial waste, but also to provide an excellent fluorescent material despite the fact that the shells are used as raw materials. can do.

The shells used as a raw material for the fluorescent material of the present invention, from the viewpoint of fluorescence intensity, scallop shells, shells shells and turban of mussels are preferred. These shells may be used alone or in combination of two or more.

  As described above, the fluorescent material of the present invention can use not only conventional shells such as scallops but also shells such as mussels as a raw material. Blue mussels adhere to the intake pipes of coastal power plants such as nuclear power plants and thermal power plants and cause a decrease in water intake efficiency, so it is necessary to remove them regularly. Tons. According to the present invention, not only conventional scallop shells but also shells such as mussels adhering to the intake pipes of such power plants can be effectively utilized as functional materials instead of being discarded as industrial waste. it can.

  The fired powder of the shell used as the raw material of the fluorescent material of the present invention can be produced, for example, by firing and then pulverizing the shell, or by firing after smashing the shell. In general, shells are hard as they are, but become brittle when fired. In the present invention, it is preferable to produce a fired powder of shells by firing and firing the shells.

  Conventionally, when shells are used as phosphors, the shells must be sintered at a high temperature of 1127 to 1727 ° C. (1400 to 2000K) as described in paragraph [0027] of JP-A-2007-131773. I must.

  On the other hand, the method for producing a fluorescent material of the present invention has one major feature in that it is not necessary to sinter the shell at a high temperature as in the prior art. The method for producing a fluorescent material of the present invention is extremely excellent in terms of energy efficiency and productivity because the firing temperature of the shell can be markedly lowered as compared with the conventional method.

In the present invention, the firing temperature of the shell is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, more preferably 250 ° C. or higher, from the viewpoint of increasing the fluorescence intensity, and the combustion of the active ingredient contained in the shell is performed. from the viewpoint of suppressing, preferably 4 00 ° C. or less, more preferably 350 ° C. or less.

  Since the firing time of the shell varies depending on the type of shell, the firing temperature of the shell, and the like, and cannot be determined unconditionally, it is preferable to determine appropriately according to the type of shell, the firing temperature of the shell, and the like. The firing time of the shell is usually preferably 0.3 hours or more, more preferably 0.5 hours or more, and even more preferably 1 hour or more from the viewpoint of increasing the fluorescence intensity, and the productivity of the fluorescent material of the present invention is improved. From the viewpoint of improvement, it is preferably within 24 hours, more preferably within 20 hours, and even more preferably within 10 hours.

  In addition, the temperature increase rate at the time of baking a shell and the cooling rate after baking of a shell are not specifically limited. Usually, the temperature increase rate at the time of baking a shell should just be about 0.1-100 degrees C / min. Moreover, although the cooling rate after baking of a shell should just be about 0.1-100 degrees C / min, it is preferable not to perform forced cooling but to cool from a viewpoint of energy efficiency.

  The firing atmosphere when firing the shell is not particularly limited, and may be, for example, air or an inert gas such as nitrogen gas or argon gas, but from the viewpoint of productivity, it is air. It is preferable.

  The apparatus used when baking shells is not particularly limited. Examples of such an apparatus include a firing furnace such as an electric furnace.

  By firing the shell as described above, the fired shell can be obtained. After firing the shell, the fired shell may be cooled to room temperature.

  As described above, the shell may be pulverized before firing. However, since the shell before firing is hard while the shell after firing is brittle, it is preferable to grind after firing the shell. When the shell is pulverized after firing, the shell may be crushed to a certain size before firing so that the shell can be easily fired.

  When the shell is pulverized, for example, a pulverizer such as a ball mill, a bead mill, a sand mill, a roll mill, a vibration mill, or a jet mill can be used. It is usually preferable from the viewpoint of improving extraction efficiency that the shell is crushed so that the particle diameter of the crushed shell is 10 to 100 mesh (JIS mesh).

The fired shell powder obtained as described above is then subjected to extraction using water.
In the present invention, there is one major feature in that the fired powder of the shell is extracted with water. In the present invention, since water is used as the extraction solvent, it is possible to avoid adverse effects on the global environment as in the case of using an organic solvent.

  The water used as the extraction solvent may contain, for example, alcohols such as methanol and ethanol, acids such as inorganic acids and organic acids, alkalis, surfactants, and the like, as long as the object of the present invention is not impaired. Good. When an acid aqueous solution is used when extracting the fired powder of shellfish with water, the ingredients contained in the fired powder of shellfish are eluted in water by dissolving the fired powder of shellfish in the acid aqueous solution. However, it should be noted that the components extracted from the baked powder of shells may undergo modification such as hydrolysis. As described above, the concept of extraction in the present specification includes eluting the components contained in the fired powder of the shell into the water by dissolving the fired powder of the shell using an acid aqueous solution or the like. .

  Extraction of the components contained in the fired shell powder with water can be easily carried out, for example, by adding the fired shell powder to water and stirring.

  The amount of the shell fired powder per 100 mL of water is preferably 1 g or more, more preferably 3 g or more from the viewpoint of increasing extraction efficiency, and preferably 20 g from the viewpoint of improving the dispersibility of the shell fired powder in water. Below, more preferably 10 g or less.

The water temperature at the time of extracting the baked shell powder is preferably 5 ° C. or higher, more preferably 10 ° C. or higher from the viewpoint of enhancing extraction efficiency, and preferably 60 ° C. or lower from the viewpoint of operability.

  After adding the shell fired powder to the water, from the viewpoint of increasing the extraction efficiency, the mixture of the shell fired powder and water obtained by adding the shell fired powder is irradiated with ultrasonic waves, or the mixture It is preferable to suspend the fired powder of the shell in water by stirring with a stirring bar.

  The time required to extract the components contained in the fired shell powder into the water varies depending on the extraction temperature, the amount of the fired shell powder, etc., and cannot be determined unconditionally, but is included in the fired shell powder. From the viewpoint of sufficiently extracting the components contained in water, it is preferably 3 minutes or more, more preferably 5 minutes or more, and from the viewpoint of production efficiency, it is preferably 60 minutes or less, more preferably 30 minutes or less.

  As described above, the shell powder is dispersed in water, and the extract containing the components contained in the shell powder contains the shell powder. Is preferably removed.

  Examples of the method for removing the baked shell powder from the extract include, for example, a method of filtering the baked powder using a filter, a method of separating the baked powder by centrifugation, and the present invention is only such examples. It is not limited to.

  The residue separated from the extract has a color close to white, so it can be used as a white pigment instead of titanium white, zinc white, etc., as a building material such as cement admixture, as a raw material for calcium carbonate, or as a natural product. Because it is derived from a certain shell, it is used for agricultural fertilizers such as calcium supplements, chicken feed, food additives, dietary supplements, etc., and water that is safe for the human body is used as an extraction solvent. Since it itself has moisturizing properties, it is expected to be effectively used as a moisturizing agent used in cosmetics, for example.

  On the other hand, the extract from which the fired powder of the shell has been removed emits fluorescence and is excellent in phosphorescence, so that it can be used as it is as an active ingredient of the fluorescent material of the present invention.

  The fluorescent material of the present invention contains an extract obtained by extracting the fired powder of shellfish with water as an active ingredient, and emits fluorescence. For example, it is used in aqueous paints such as acrylic water-based paints. It can be used as an aqueous solvent. Thus, when the fluorescent material of the present invention is used as the solvent of the aqueous paint, the aqueous paint can be used as the aqueous fluorescent paint.

  In addition, since the fluorescent material of the present invention is excellent in luminous properties, for example, when a water-based paint containing the fluorescent material of the present invention is applied to the wall surface of a building, the inside of the building is caused by a power failure due to a disaster or the like. Even when it becomes dark, its wall surface is phosphorescent and emits light, so that it is possible to easily grasp the passage and evacuation route visually without lighting, Even so, there is an advantage that fluorescent characters and fluorescent images can be raised on the wall surface.

  In addition, in the said extract, when the calcium concentration eluted from the baking powder of a shell is high, a calcium component may precipitate with time. In that case, the calcium component may be precipitated by allowing the extract to stand for a while, and the precipitated calcium component may be removed.

  Furthermore, in the present invention, the extract can be used as a fluorescent material as it is, and a solid material obtained by evaporating and drying the extract can be used as the fluorescent material of the present invention.

  Examples of the method of evaporating and drying the extract include a method of drying the extract using an evaporator, a method of evaporating moisture contained in the extract by heating the extract, and the like. However, the present invention is not limited by such a method. Among these methods, from the viewpoint of not giving a strong heat history to the extract, a method of drying the extract using an evaporator or the like is preferable.

  After evaporating the extract to dryness, if necessary, it may be further dried under reduced pressure, or may be dried using a desiccant such as silica gel. The solid fluorescent material obtained by evaporating the extract to dryness can usually be obtained in a powder state.

  The solid fluorescent material obtained by evaporating and drying the extract liquid emits fluorescence as well as the extract liquid and has excellent phosphorescent properties, so that it can be used as a fluorescent material in a solid state as it is. .

  In addition, since this solid fluorescent material is solid, it has excellent storage stability, handleability, etc., and therefore, for example, luminescent materials used in luminescent excipients and organic solvent-based paints for various applications. It can be used as a pigment, a light emitting agent for building materials, and the like.

  Furthermore, since this solid fluorescent material itself has moisturizing properties, it is expected to be effectively used as a moisturizing agent used in cosmetics, for example.

  The fluorescent material of the present invention can be used in an aqueous fluorescent paint by blending into the aqueous paint. The water-based paint may be a commonly used water-based paint such as an acrylic water-based paint, and the present invention is not limited by the type of the water-based paint.

  The amount of fluorescent material blended in the water-based fluorescent paint varies depending on the type of paint and the required degree of fluorescence, and therefore cannot be determined unconditionally. It is preferable to determine appropriately according to the above.

  In addition, the fluorescent material of the present invention dissolves in a protic polar solvent such as water, ethanol, aqueous sodium hydroxide, etc., and exhibits fluorescence, so that it is also suitable for applications where these solvents are used. can do.

  The fluorescent material of the present invention obtained as described above usually has an emission wavelength in a wavelength region of 370 to 550 nm and an excitation wavelength in a wavelength region of 200 to 400 nm.

  As described above, the fluorescent material of the present invention has been effectively used as a raw material for shells that have been discarded as industrial waste in the past, has water solubility, emits fluorescence, and has excellent phosphorescent properties. Therefore, it can be suitably used for building materials such as phosphorescent paints, phosphorescent tiles that are visible even in the dark, evacuation guidance display boards, and the like.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited to such examples.

Examples 1-3
After crushing tuna shells (Example 1), scallop shells (Example 2) and mussel shells (Example 3) to a size of several centimeters, they are placed in a box-shaped electric furnace, Each shell was fired in the atmosphere under the firing conditions of a firing temperature of 300 ° C. and a firing time of 1 hour.

  The fired shells were allowed to cool to room temperature and then removed from the electric furnace, and about 100 g of each fired shell was placed in a ball mill (container: 5.1 liter nylon pot, medium: nylon 20 mm in diameter) By pulverizing with a ball of about 2 liters) for 24 hours, a fired shell shell powder having a particle size of about 10 to 100 mesh (JIS mesh) was obtained.

  The powder X-ray diffraction of the fired powder of each shell obtained in Examples 1 to 3 was examined. The powder X-ray diffraction was measured using a powder X-ray diffraction measurement apparatus [manufactured by Shimadzu Corporation, trade name: powder X-ray diffraction measurement apparatus XD-6100], and the measurement conditions were a voltage of 40 kV, Current: 20 mA, scanning mode: Continuous, scanning range: 5 to 80 ° C., scanning speed: 2.0 ° / min, atmosphere: air. The measurement results are shown in FIG.

  In FIG. 1, 1 is a powder X-ray diffraction of fired powder of tuna shell (Example 1), 2 is a powder X-ray diffraction of fired powder of scallop shell (Example 2), 3 is a fired powder of mussel shell The powder X-ray diffraction (Example 3) of is shown.

  Next, 25 g of the fired powder of each shell is added to 500 mL of water at 25 ° C., irradiated with ultrasonic waves at room temperature for 10 minutes using an ultrasonic cleaner, and then allowed to stand for 24 hours to be contained in the fired powder. An extract was extracted from which the components were extracted. In order to remove the calcined powder contained in the obtained extract, the extract is filtered with a suction filter using filter paper (No. 5), and the obtained filtrate is recovered to obtain a liquid. A fluorescent material was obtained.

  Next, the state before and after irradiating ultraviolet light (wavelength: 230 nm) to the liquid fluorescent material obtained above was observed. The result is shown in FIG.

  In FIG. 2, (a) is a photograph showing a state when white light A or ultraviolet light B is irradiated to a liquid fluorescent material using the fired powder of tuna shell obtained in Example 1, and (b) is The photograph which shows a state when white light A or ultraviolet-ray B is irradiated to the liquid fluorescent material using the baked scallop shell powder obtained in Example 2, (c) is the mussel obtained in Example 3 FIG. 3 is a photograph showing a state when white light irradiation (A in FIG. 2) or ultraviolet irradiation (B in FIG. 2) is performed on a liquid fluorescent material using a fired powder of sea shells.

  From the results shown in FIG. 2, it can be seen that the liquid fluorescent materials obtained in the respective examples do not emit light when irradiated with white light, but emit fluorescence when irradiated with ultraviolet rays. .

  Next, the fluorescence emission spectrum when the fluorescent material obtained in each example was irradiated with ultraviolet rays (wavelength: 370 nm) was examined using a fluorometer [manufactured by PerkinElmer, product number: LC55]. The result is shown in FIG.

  In FIG. 3, p is the fluorescence emission spectrum when the fluorescent material using the fired powder of the tuna shell obtained in Example 1 is irradiated with ultraviolet rays, and q is the fire of the scallop shell obtained in Example 2. Fluorescence emission spectrum when the fluorescent material using the powder is irradiated with ultraviolet rays, r is the fluorescence emission spectrum when the fluorescent material using the fired powder of mussel shell obtained in Example 3 is irradiated with ultraviolet rays. Show.

  From the results shown in FIG. 3, it can be seen that each of the fluorescent materials obtained in each example has a peak in the vicinity of a wavelength of 420 nm or 490 nm and gives a high-intensity fluorescence emission spectrum.

  Next, 100 mL of a 15 wt% calcium citrate aqueous solution was added to 100 mL of the liquid fluorescent material obtained in each example, and then about 1 M sodium hydroxide aqueous solution was added so that the pH would be about 12, thereby adding fluorescence. A white precipitate of calcium hydroxide containing the material was produced. The white precipitate was collected by filtration and dried to recover a white powder.

  The obtained white powder was irradiated with ultraviolet rays having a wavelength of about 360 nm for 10 minutes, and after 1 minute from the end of the irradiation, when the afterglow of the white powder was observed, afterglow (fluorescence) was observed. It was. From this result, it can be seen that the liquid fluorescent material obtained in each example has excellent afterglow properties because it has afterglow even after 1 minute has elapsed after irradiation of ultraviolet rays.

  Next, after immersing the filter paper in the liquid fluorescent material obtained in each example, and then lifting and drying, it was confirmed that all of the filter papers had phosphorescent properties.

  From the above results, the liquid fluorescent material obtained in each example not only has afterglow itself, but also exhibits afterglow even when the fluorescent material is completely dried. I understand.

Reference Example In Examples 1 to 3, when the residue collected during filtration was dried and the obtained powdery dried product was observed with the naked eye, the dried product was a shellfish shellfish as a raw material. In some cases, it was gray, in the case of using a scallop shell, it was white, and in the case of using a mussel shell, it was gray.

  Since these dry products are all in the form of powder, it is considered useful, for example, as a fluorescent pigment. Moreover, since these dry substances are all excellent in moisturizing property, it is considered that they are useful as, for example, fluorescent moisturizing agents used in cosmetics and the like.

Examples 4-6
Each liquid fluorescent material obtained in Examples 1 to 3 was evaporated to dryness at 80 ° C. using an evaporator to obtain a powdery (solid) fluorescent material. The obtained powdery fluorescent material exhibits yellow when using Sazae shells as a raw material (Example 4), and exhibits orange when using scallop shells (Example 5), When the blue mussel was used (Example 6), it was brown.

  Next, the powdery fluorescent material obtained above was pulverized in a mortar, and the powder X-ray diffraction of the obtained powder was examined in the same manner as described above. As a result, the X-ray diffraction of the powders of the respective fluorescent materials was the same as the X-ray diffraction of the calcined powder of Sazae shell, scallop shell, and mussel shell.

  From this, it can be seen that the components contained in the calcined powder obtained by calcining tuna shells, scallop shells and mussel shells are contained in each powdery fluorescent material.

  Next, when each of the powdery fluorescent materials obtained above was irradiated with ultraviolet rays (wavelength: 230 nm) in the same manner as in Examples 1 to 3, it was confirmed to emit fluorescence. From this, it can be seen that each of the powdery fluorescent materials obtained above has a light-emitting property by ultraviolet irradiation.

  5 g of each powdery fluorescent material obtained above was dissolved in water at 25 ° C., ethanol, 10% aqueous sodium hydroxide, acetone or hexane. As a result, each of the powdery fluorescent materials obtained above could be completely dissolved in water, ethanol and an aqueous sodium hydroxide solution, but could not be dissolved in acetone and hexane. This indicates that each of the powdery fluorescent materials obtained above is excellent in solubility in protic polar solvents such as water, ethanol, and sodium hydroxide aqueous solution.

  Next, when the aqueous solution of each powdery fluorescent material obtained above, ethanol solution and sodium hydroxide aqueous solution were irradiated with white light or ultraviolet rays (wavelength: 230 nm) in the same manner as in Examples 1-3, As in Examples 1 to 3, all of the solutions did not emit light when irradiated with white light, but were confirmed to emit fluorescence when irradiated with ultraviolet light. From this, it can be seen that each of the powdery fluorescent materials obtained above emits fluorescence when irradiated with ultraviolet rays even when dissolved in water, ethanol, sodium hydroxide aqueous solution or the like.

  As described above, it can be seen that the fluorescent material of the present invention is an effective use of shells that have been treated as waste as a raw material, and can be suitably used for, for example, paints.

  The fluorescent material of the present invention can be used as an aqueous solvent used for, for example, phosphorescent paints, phosphorescent tiles, and evacuation guidance display boards. Thus, when the fluorescent material of the present invention is used as a solvent for an aqueous paint, the aqueous paint can be used as an aqueous fluorescent paint.

  In addition, since the fluorescent material of the present invention is also excellent in luminous properties, when the water-based paint containing the fluorescent material of the present invention is applied to the wall surface of the building, the inside of the building becomes dark due to a power failure due to a disaster or the like. Even if it is a case, the wall surface is phosphorescent and emits light, so that it is possible to easily grasp the passage and evacuation route visually without lighting by electric lights, etc. Vivid fluorescent characters and fluorescent images can be highlighted on the wall.

  Furthermore, since the solid fluorescent material of the present invention itself has a moisturizing property, it is expected to be effectively used as a moisturizing agent used in cosmetics, for example.

Claims (6)

A fluorescent material containing, as an active ingredient, an extract obtained by extracting a baked powder of shells obtained by firing shells with water , wherein the shells are selected from the group consisting of scallop shells, mussel shells, and shellfish shells It is at least one kind of shell, and the fired powder of the shell is a fired powder obtained by firing the shell at a temperature of 150 to 400 ° C., and the extract extracts the fired powder of the shell in 5 to 60 ° C. water. A fluorescent material for an aqueous fluorescent paint, wherein the baked powder contained in the extract is removed . A fluorescent material for an aqueous fluorescent paint, comprising as an active ingredient a solid obtained by evaporating and drying the extract according to claim 1 . An aqueous fluorescent paint comprising the fluorescent material for an aqueous fluorescent paint according to claim 1 or 2 . A method for producing a fluorescent material for an aqueous fluorescent paint, wherein the fired powder of the shell obtained by firing and pulverizing the shell is dispersed in water, and the fired powder of the shell is removed from the obtained dispersion. The shell is at least one shell selected from the group consisting of a scallop shell, a mussel shell, and a shellfish shell, and is obtained by firing the shell at a temperature of 150 to 400 ° C. and firing the shell. A method for producing a fluorescent material for an aqueous fluorescent paint, wherein the fired powder is extracted with water at 5 to 60 ° C., and the fired powder contained in the obtained extract is removed . The manufacturing method of the fluorescent material for water-based fluorescent paints of Claim 4 which grind | pulverizes after baking a shell. Furthermore, the manufacturing method of the fluorescent material for water based fluorescent paints of Claim 4 or 5 which evaporates and solidifies the dispersion liquid from which the baked powder of the shell was removed.