JP2019137574A - Glass-coated fluorescent aggregate and method for producing the same - Google Patents

Abstract

To provide a glass-coated fluorescent aggregate capable of preventing fluorescent characteristics from being degraded due to oxidation and hydrolysis and capable of being used for a member to be installed outside; to provide a method for producing the same; and to provide a fluorescent concrete member.SOLUTION: A glass-coated fluorescent aggregate 100 includes a glass 110 and a sulfide-based fluorescent material 120 dispersed in the glass, wherein an SiO concentration is 31.5 wt.% or more and 49 wt.% or less. Accordingly, fluorescent characteristics are prevented from being degraded due to oxidation and hydrolysis, and the fluorescent aggregate can be used while being put in a concrete outside.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass-coated fluorescent aggregate that emits fluorescence upon receiving excitation light, a method for manufacturing the same, and a fluorescent concrete member.

  Conventionally, phosphors are used in a wide variety of applications such as signs, automobiles, railways, aviation parts, building materials, toys, miscellaneous goods, and the like. For example, as described in Patent Document 1, it is proposed to use a fluorescent material whose function is degraded by exposure to water, such as a strontium aluminate-based fluorescent material, as described in Patent Document 1. ing.

  Further, sulfide-based materials as disclosed in Patent Documents 2 and 3 are also known as fluorescent materials. The deterioration of the function due to contact with water or oxygen is common to the case of the strontium aluminate fluorescent material. In order to improve this weather resistance, it is known to be used as a composite with other materials. For example, Patent Document 4 discloses that a phosphor layer using a sulfide-based phosphor is provided on the surface of a glass bead base layer. Patent Document 2 discloses a polymer plastic, and Patent Document 5 discloses a sulfide fluorescent material powder sandwiched between glass plates.

Japanese Patent Publication No. 06-062940 Japanese Patent No. 5738299 Japanese Patent No. 2933779 JP 2005-307717 A Special table 2007-523221 gazette

  As said sulfide type fluorescent material, what added Cu as an activator to ZnS is known, for example. Such materials are oxidized and hydrolyzed when exposed to the outside air, and the deterioration of the fluorescence characteristics gradually proceeds.

  The present invention has been made in view of such circumstances, can prevent deterioration of fluorescence characteristics due to oxidation and hydrolysis, and can be used for a member installed outdoors, and a method for producing the same. An object of the present invention is to provide a fluorescent concrete member.

(1) In order to achieve the above object, the glass-coated fluorescent aggregate of the present invention comprises glass and a sulfide-based fluorescent material dispersed in the glass, and the SiO ₂ concentration is 31.5 wt% or more and 49 wt%. % Or less. Thereby, deterioration of the fluorescence characteristic by oxidation and hydrolysis can be prevented, and it can be used by being embedded in concrete outdoors.

  (2) Moreover, the glass-coated fluorescent aggregate of the present invention is characterized by further comprising a translucent resin film for coating the glass. Since the glass is thus covered with the resin, it is difficult for outside air to come into contact with the fluorescent material, and deterioration of the fluorescence characteristics can be prevented.

  (3) The fluorescent concrete member of the present invention is a fluorescent concrete member that emits fluorescence upon receiving excitation light, and is a hardened cement body and the above (1) or (2) embedded in the surface of the hardened cement body And a glass-coated fluorescent aggregate. Thereby, the fluorescent concrete member which prevented the deterioration of the fluorescence characteristic is realizable.

(4) Moreover, the manufacturing method of the glass covering fluorescent aggregate of this invention is a manufacturing method of the glass covering fluorescent aggregate which emits fluorescence in response to excitation light, Comprising: And mixing so that the waste bottle glass powder is contained in the range of 45 wt% to 70 wt% in an internal ratio, and the mixed material in an inert atmosphere or a reducing atmosphere at 800 ° C. or more and 950 ° C. or less. in the firing, the fired material was cooled and crushed solidified body obtained by the cooling, and the glass containing SiO ₂ less 31.5Wt% or more 49 wt% the sulfide fluorescent material Producing a glass-coated fluorescent aggregate that is substantially formed. Thereby, it is possible to manufacture the glass-coated fluorescent aggregate by preventing the fluorescent aggregate from falling off from the concrete while preventing the deterioration of the fluorescent characteristics.

  (5) Moreover, the manufacturing method of the glass covering fluorescent aggregate of this invention is characterized by using an external combustion type furnace in the said baking process. Thereby, the atmosphere can be controlled and firing can be performed in an inert atmosphere or a reducing atmosphere.

  ADVANTAGE OF THE INVENTION According to this invention, deterioration of the fluorescence characteristic by oxidation and hydrolysis can be prevented, and it can use for the member installed outdoors.

(A), (b) is sectional drawing which shows the glass covering fluorescent aggregate and fluorescent concrete member of this invention, respectively. (A), (b) It is a fluorescent concrete member which has sectional drawing which shows the glass-coated fluorescent aggregate which each has a resin film, and a resin film on the surface. (A), (b) It is a graph which shows the emission spectrum of the glass covering fluorescent aggregate formed by the specific mixing | blending, respectively.

  Next, embodiments of the present invention will be described with reference to the drawings.

[First Embodiment]
(Configuration of glass-coated fluorescent aggregate)
FIG. 1A is a cross-sectional view showing a glass-coated fluorescent aggregate 100. As shown in FIG. 1A, the glass-coated fluorescent aggregate 100 is substantially formed of glass 110 and a sulfide-based fluorescent material 120. “Substantially” means that impurities other than these may be contained. Since the sulfide-based fluorescent material 120 is dispersed in the glass 110, the sulfide-based fluorescent material 120 is covered with the glass 110 on the glass-coated fluorescent aggregate 100. As a result, even when used as an outdoor material, such as embedded in concrete, the sulfide-based fluorescent material 120 is not directly exposed to the atmosphere, and oxidation and hydrolysis are prevented, preventing deterioration of fluorescent properties over a long period of time. it can.

  The average particle size of the glass-coated fluorescent aggregate 100 is preferably 2 mm or more and 10 mm or less. It is preferable that the particle size is larger than the vitrified material of the sulfide-based fluorescent material 120 used for paint for displaying the center of a road or a pedestrian crossing because it is embedded in concrete.

The glass-coated fluorescent aggregate 100 contains 31.5 wt% or more and 49 wt% or less of SiO ₂ . When the glass-coated fluorescent aggregate 100 has a high silicic acid content, the alkali of the cement hardened body reacts with the silicic acid content of the glass-coated fluorescent aggregate 100 when embedded in a concrete member, so that the so-called alkali aggregate reaction becomes remarkable. This increases the risk that the glass-coated fluorescent aggregate 100 will fall off the concrete member. Since the glass-coated fluorescent aggregate 100 has a SiO ₂ content of 49 wt% or less, an alkali aggregate reaction does not occur between the hardened cement body and SiO ₂ .

Although the SiO ₂ content of the glass-coated fluorescent aggregate 100 can be reduced as much as possible in terms of technical effects, the proportion of the sulfide-based fluorescent material 120 increases accordingly. By setting the SiO ₂ content to 31.5 wt% or more, the amount of the sulfide-based fluorescent material 120 can be suppressed and the cost of the material can be reduced.

  For the sulfide-based fluorescent material 120, zinc sulfide (ZnS) using Cu as an activator can be used. Zinc sulfide (ZnS) is easily available and preferable, but calcium sulfide (CaS), magnesium sulfide (MgS), strontium sulfide (SrS), and barium sulfide (BaS) may be used. The sulfide-based fluorescent material 120 has a particle size of several to several tens of μm.

  Fluorescence extinguishes immediately when excitation light is stopped, while phosphorescence is a phenomenon in which light emission continues even after the excitation light stops. Strictly speaking, fluorescence and light storage are different phenomena, but “fluorescent materials” include not only fluorescent materials but also phosphorescent materials. When used for display on the road, it is preferable that afterglow occurs for a long time after the excitation light is applied, and in that respect, it is suitable to be phosphorescent. The sulfide-based fluorescent material 120 is preferably of a type that emits yellow light with a wavelength of, for example, 430 to 580 nm so that light emission on the road can be easily detected.

(Method for producing glass-coated fluorescent aggregate)
An example of the manufacturing method of the glass covering fluorescent aggregate 100 comprised as mentioned above is demonstrated. First, the sulfide-based fluorescent material 120 and the translucent waste bottle glass powder are mixed so that the waste bottle glass powder is contained in the range of 45 wt% or more and 70 wt% or less. As the sulfide-based fluorescent material 120, a commercially available material (for example, a phosphorescent pigment GSS manufactured by Nemotorumi Materials Co., Ltd.) can be used. A material called soda glass is used for the bottle glass, and most of the main components are occupied by three components of SiO ₂ , CaO and Na ₂ O.

  Next, the mixed material is fired at 800 ° C. or higher and 950 ° C. or lower in an inert atmosphere or a reducing atmosphere, preferably in an inert atmosphere. Specifically, for example, firing can be performed in a nitrogen atmosphere. In this way, the firing is performed under the condition that the glass powder is melted and the sulfide-based fluorescent material 120 is sufficiently covered. In particular, if the sulfide-based fluorescent material 120 is coated using waste bottle glass, the glass-coated fluorescent aggregate 100 can be manufactured at a low cost. In the firing step, it is preferable to use an external combustion furnace (kiln). Thereby, the atmosphere can be controlled and firing can be performed in an inert atmosphere or a reducing atmosphere.

Next, the fired material is cooled, and the solidified body obtained by cooling is crushed. As a result, a glass-coated fluorescent aggregate 100 containing 31.5 wt% or more and 49 wt% or less of SiO ₂ is obtained. Thus, when a commercially available zinc sulfide-based phosphorescent material is mixed with waste glass powder and baked at 850 to 950 ° C. in an inert atmosphere or a reducing atmosphere, the fluorescence is maintained and the fluorescent material coated with inorganic glass is used. Aggregates can be obtained easily. Further, it is possible to prevent the fluorescent aggregate from falling off from the concrete while preventing the deterioration of the fluorescent characteristics.

(Configuration of fluorescent concrete member)
The glass-coated fluorescent aggregate 100 can be used by being embedded in a concrete member. FIG. 1B is a cross-sectional view showing the configuration of the fluorescent concrete member 200. As shown in FIG. 1B, the fluorescent concrete member 200 includes a cement hardened body 210 and a glass-coated fluorescent aggregate 100, and the glass-coated fluorescent aggregate 100 embedded in the surface of the cement hardened body 210. The part emits fluorescence upon receiving excitation light. Such a fluorescent concrete member 200 can be used for pavement on the road or on both sides of the road, and can be used for guidance and warning display. In particular, both sides of the road are suitable because the surface is less likely to wear. The hardened cement body 210 may be mixed with fine aggregates such as river sand in addition to the glass-coated fluorescent aggregate 100.

  The thickness of the fluorescent concrete member 200 is preferably 10 mm or more and 50 mm or less. Thereby, the glass-coated fluorescent aggregate 100 can be appropriately embedded while maintaining the strength. Moreover, it is preferable that the cement hardened body 210 is formed as a result of mixing at a water / cement ratio of 0.35 to 0.50. Thereby, while ensuring the extraction amount of the light by fluorescence, the intensity | strength as a member is maintainable.

  The hardened cement body 210 is a binder mainly composed of lime, and is manufactured by pulverizing, calcining and firing limestone and clay. The hardened cement body 210 is preferably ordinary portland cement, but may be early strong portland cement, moderately hot portland cement, low heat portland cement, blast furnace cement, silica cement or the like. Since it can be used as a concrete member having a fluorescent function, the fluorescent concrete member 200 can be installed as a part of the road as it is and can be easily applied to the road.

(Method for producing fluorescent concrete member)
A method for manufacturing the fluorescent concrete member 200 configured as described above will be described. A rectangular mold is prepared, and the mold is filled with a cement mortar mixed with cement paste or sand kneaded at a water / cement ratio of 0.35 to 0.40. And the vibration is given, pressing the poured material with a press board.

  Then, before the cement paste or cement mortar is hardened, the glass-coated fluorescent aggregate 100 is embedded on the surface. By spreading on the surface of the cement paste or cement mortar, the glass-coated fluorescent aggregate 100 is embedded in the hardened cement body 210 leaving an exposed surface.

  Then, the material is transferred to the curing room as it is and cured for a predetermined period. By removing the mold after the cement material has hardened, the fluorescent concrete member 200 in which the glass-coated fluorescent aggregate 100 is embedded in the hardened cement body 210 can be generated. In the above example, the glass-coated fluorescent aggregate 100 is embedded in the poured material. The glass-coated fluorescent aggregate 100 is dispersed on the bottom of the formwork, and cement mortar is filled so as to fill the gaps between the glass-coated fluorescent aggregate. It may be poured.

[Second Embodiment]
In the above embodiment, the glass-coated fluorescent aggregate 100 is a mixture of the glass 110 and the sulfide-based fluorescent material 120 itself, but the mixture of the glass 110 and the sulfide-based fluorescent material 120 is translucent. More preferably, it is coated with a resin film 330. FIG. 2A is a cross-sectional view showing a configuration of a glass-coated fluorescent aggregate 300 having a resin film 330. In the glass-coated fluorescent aggregate 300, since the mixture of the glass 110 and the sulfide-based fluorescent material 120 is covered with the resin film 330, the outside air hardly comes into contact with the sulfide-based fluorescent material 120, and the sulfide-based fluorescent material 300 Deterioration of the fluorescence characteristics of the material 120 can be prevented. FIG. 2B shows a fluorescent concrete member 400 having a resin film 330 on the surface. As shown in FIG. 2B, the fluorescent concrete member 400 can be formed by covering the fluorescent concrete member body in which the glass-coated fluorescent aggregate 100 is dispersed and embedded in the hardened cement body 210 with a resin film 330. .

  The resin film 330 has translucency and transmits visible light. “Translucent” means not only when light is transmitted like “transparent”, but also when the transmitted light is diffused, and the shape on the other side cannot be clearly recognized through the material such as frosted glass or milky white. Including cases.

  The material of the resin film 330 is preferably a material that transmits light having a wavelength of 350 to 450 nm as excitation light. In particular, it is preferable to have excellent transparency to excitation light having a wavelength of 350 nm or more and 370 nm or less. Thereby, the resin film 330 transmits excitation light and generates fluorescence. The resin film 330 can be formed of, for example, a resin mainly made of urethane, acrylic, or polyester, a silicon resin, an epoxy resin, or the like.

[Experiment and evaluation]
In accordance with the above production method, glass-coated fluorescent aggregates having fluorescent material contents of 50 wt% and 30 wt% were respectively produced, and the fluorescence spectrum was measured (JIS K 0120). The respective SiO ₂ contents were 34.7% and 48.5%. FIG. 3A is a graph showing an emission spectrum of a glass-coated fluorescent aggregate having a fluorescent material content of 50 wt%. FIG. 3B is a graph showing an emission spectrum of a glass-coated fluorescent aggregate having a fluorescent material content of 30 wt%.

Example 1
As the zinc sulfide-based fluorescent material, phosphorescent pigment GSS manufactured by Nemotomi Material Co., Ltd. was used. As the inorganic glass composition, a transparent bottle glass pulverized to a particle size of 50 μm or less with a ball mill was used. 50 parts by mass of the fluorescent material and 50 parts by mass of the inorganic glass composition are mixed (compound (1)), and then, using the mixed raw material, the mixture is molded by a uniaxial pressure molding machine, and has a diameter of 40 mm and a height. A 10 mm disk-shaped pellet was produced.

  A glass-coated fluorescent aggregate was obtained by holding at 850 ° C. for 1 hour in a nitrogen atmosphere with an atmosphere-type fast heating furnace (SBA-2025D manufactured by Motoyama Co., Ltd.). The nitrogen gas used was an industrial grade having a nitrogen concentration of 99.95 percent and was circulated at 1.8 liters per minute. When the emission spectrum of the glass-coated fluorescent aggregate was measured after cooling, yellow fluorescence having a peak at an emission wavelength of 518 nm was expressed at an excitation wavelength of 350 nm (FIG. 3A). The glass-coated fluorescent aggregate retained the phosphorescent properties.

(Example 2)
A glass-coated fluorescent aggregate was obtained by holding at 850 ° C. for 1 hour in the same manner as in Example 1 except that the firing atmosphere was reduced gas. As the reducing gas, a mixed gas of 3 volume percent hydrogen and 97 percent nitrogen was used. When the emission spectrum of the glass-coated fluorescent aggregate was measured after cooling, yellow fluorescence having an emission wavelength of 464 and 511 nm was expressed at an excitation wavelength of 350 nm (FIG. 3A). The obtained glass-coated fluorescent aggregate retained the luminous characteristics as in Example 1.

(Comparative Example 1)
A pellet was prepared in the same manner as in Example 1, and the glass-coated fluorescent aggregate was obtained by holding it at 850 ° C. for 1 hour in an atmosphere with a furnace bottom elevating electric furnace (NHV-1515D manufactured by Motoyama Co., Ltd.). Obtained. When the emission spectrum of this glass-coated fluorescent aggregate was measured after cooling, fluorescence with an emission wavelength of 521 nm was expressed at an excitation wavelength of 350 nm (FIG. 3A). However, when compared with Example 1 and Example 2, yellow phosphorescent emission was significantly reduced.

(Example 3)
30 parts by mass of a zinc sulfide-based phosphorescent material and 70 parts by mass of an inorganic glass composition were mixed (formulation (2)), and a disk-shaped pellet was produced in the same manner as in Example 1, and the temperature was maintained at 850 ° C. in a nitrogen atmosphere. A glass-coated fluorescent aggregate was obtained by holding for 1 hour. When the emission spectrum of the glass-coated fluorescent aggregate was measured, yellow fluorescence having a peak at an emission wavelength of 518 nm was expressed at an excitation wavelength of 350 nm (FIG. 3B). The obtained glass-coated fluorescent aggregate retained the luminous properties.

Example 4
A glass-coated fluorescent aggregate was obtained by holding at 850 ° C. for 1 hour in the same manner as in Example 3 except that the firing atmosphere was reduced gas. When the emission spectrum of the obtained glass-coated fluorescent aggregate was measured after cooling, yellow fluorescence having an emission wavelength of 466 and 511 nm was expressed at an excitation wavelength of 350 nm (FIG. 3B). This glass-coated fluorescent aggregate retained the phosphorescent characteristics as in Example 3.

[Comparative Example 2]
A pellet was prepared in the same manner as in Example 3, and the glass-coated fluorescent aggregate was obtained by holding it at 850 ° C. for 1 hour in an atmosphere with a furnace bottom elevating electric furnace (NHV-1515D manufactured by Motoyama Co., Ltd.). Obtained. After cooling, when the emission spectrum of the obtained glass-coated fluorescent aggregate was measured, fluorescence with an emission wavelength of 517 nm was expressed at an excitation wavelength of 350 nm (FIG. 3B). However, even when the ratio of the sulfide-based phosphorescent material was increased, the yellow phosphorescent emission was greatly reduced as compared with Example 3 and Example 4.

  From the above, the method for producing a glass-coated fluorescent aggregate of the present invention can suppress deterioration due to hydrolysis and oxidation even when a sulfide-based phosphorescent material is used, so that a fluorescent material that can be used outdoors can be produced. it can. Whether a similar glass coating was possible with a commercially available sulfide-based phosphorescent material ZnS (Cu) was examined. A zinc sulfide phosphor is cheaper than strontium aluminate. A phosphorescent aggregate that can withstand outdoor use can be provided without requiring complicated steps.

100 Glass-coated fluorescent aggregate 110 Glass 120 Sulfide-based fluorescent material 200, 400 Fluorescent concrete member 210 Cement hardened body 300 Glass-coated fluorescent aggregate 330 Resin film

Claims (5)

Glass,
A sulfide-based fluorescent material dispersed in the glass,
A glass-coated fluorescent aggregate having a SiO ₂ concentration of 31.5 wt% or more and 49 wt% or less.   The glass-coated fluorescent aggregate according to claim 1, further comprising a translucent resin film that coats the glass. A fluorescent concrete member that emits fluorescence in response to excitation light,
Hardened cement,
A fluorescent concrete member comprising: the glass-coated fluorescent aggregate according to claim 1 or 2 embedded in a surface of the hardened cement body. A method for producing a glass-coated fluorescent aggregate that emits fluorescence in response to excitation light,
Mixing the sulfide-based fluorescent material and the waste bottle glass powder so that the waste bottle glass powder is contained in a range of 45 wt% or more and 70 wt% or less in an internal ratio;
Baking the mixed material at 800 ° C. or higher and 950 ° C. or lower in an inert atmosphere or a reducing atmosphere;
The fired material is cooled, the solidified body obtained by the cooling is crushed, and is substantially formed of glass containing 31.5 wt% to 49 wt% of SiO ₂ and the sulfide-based fluorescent material. Producing a glass-coated fluorescent aggregate.   The manufacturing method according to claim 4, wherein an external combustion furnace is used in the firing step.