JP7009712B2 - Glass-coated fluorescent aggregate and its manufacturing method - Google Patents

Description

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

Conventionally, fluorescent materials have been used in a wide variety of applications such as signs, automobiles, railways, aviation parts, building materials, toys, and miscellaneous goods. Then, for example, it has been proposed to use a fluorescent material, such as a strontium aluminate-based fluorescent material, which hydrolyzes and its function deteriorates when exposed to water, as a complex with glass as described in Patent Document 1. ing.

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

Tokusho 06-062940 Gazette Patent No. 5738299 Patent No. 2933791 Japanese Unexamined Patent Publication No. 2005-307717 Japanese Patent Publication No. 2007-523221

As the above-mentioned sulfide-based fluorescent material, for example, one in which Cu is added as an activator to ZnS is known. When such a material is continuously exposed to the outside air, it is oxidized and hydrolyzed, and the deterioration of the fluorescent property gradually progresses.

The present invention has been made in view of such circumstances, and is a glass-coated fluorescent aggregate that can prevent deterioration of fluorescent characteristics due to oxidation and hydrolysis and can be used for a member installed outdoors, and a method for producing the same. Also, it is an object of the present invention 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. It is characterized by being less than%. This makes it possible to prevent deterioration of the fluorescent characteristics due to oxidation and hydrolysis, and it can be used by embedding it in concrete outdoors.

(2) Further, the glass-coated fluorescent aggregate of the present invention is further provided with a translucent resin film for coating the glass. Since the glass is covered with the resin in this way, it becomes difficult for the outside air to come into contact with the fluorescent material, and deterioration of the fluorescent characteristics can be prevented.

(3) Further, the fluorescent concrete member of the present invention is a fluorescent concrete member that emits fluorescence by receiving excitation light, and is a cement hardened body and the above-mentioned (1) or (2) embedded in the surface of the cement hardened body. ) Is provided with a glass-coated fluorescent aggregate. This makes it possible to realize a fluorescent concrete member in which deterioration of the fluorescent characteristics is prevented.

(4) Further, the method for producing a glass-coated fluorescent aggregate of the present invention is a method for producing a glass-coated fluorescent aggregate that emits fluorescence by receiving excitation light, and includes a sulfide-based fluorescent material and waste bottle glass powder. In the step of mixing the waste bottle glass powder so as to be contained in the range of 45 wt% or more and 70 wt% or less in the internal division, and the mixed material in an inert atmosphere or a reducing atmosphere at 800 ° C. or more and 950 ° C. or less. In the step of firing, the fired material is cooled, the solidified body obtained by the cooling is crushed, and the glass containing 31.5 wt% or more and 49 wt% or less of SiO ₂ and the sulfide-based fluorescent material are used. It is characterized by comprising a step of producing a glass-coated fluorescent aggregate that is substantially formed. This makes it possible to produce a glass-coated fluorescent aggregate by preventing the fluorescent aggregate from falling off from the concrete while preventing deterioration of the fluorescent characteristics.

(5) Further, the method for producing a glass-coated fluorescent aggregate of the present invention is characterized in that an external combustion type furnace is used in the firing step. Thereby, the atmosphere can be controlled and firing can be performed in an inert atmosphere or a reducing atmosphere.

According to the present invention, deterioration of fluorescent characteristics due to oxidation and hydrolysis can be prevented, and the member can be used for a member installed outdoors.

It is sectional drawing which shows (a) and (b) the glass-coated fluorescent aggregate and the fluorescent concrete member of this invention, respectively. (A) and (b) are a cross-sectional view showing a glass-coated fluorescent aggregate having a resin film and a fluorescent concrete member having a resin film on the surface. It is a graph which shows the emission spectrum of the glass-coated fluorescent aggregate formed in each of (a) and (b) a specific composition.

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

[First Embodiment]
(Composition 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 the glass 110 and the sulfide-based fluorescent material 120. By "substantially" is meant that impurities may be contained in addition to these. Since the sulfide-based fluorescent material 120 is dispersed in the glass 110, the sulfide-based fluorescent material 120 is coated on the glass-coated fluorescent aggregate 100 with the glass 110. As a result, the sulfide-based fluorescent material 120 is not directly exposed to the atmosphere even when used as an outdoor material such as by embedding it in concrete, and oxidation and hydrolysis are prevented, so that deterioration of fluorescent characteristics is prevented for a long period of time. can.

The average particle size of the glass-coated fluorescent aggregate 100 is preferably 2 mm or more and 10 mm or less. Since it is buried in concrete, it is preferably larger in particle size than the vitrifying material of the sulfide-based fluorescent material 120 used as a paint for displaying the center of a road or a pedestrian crossing line.

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

The content of SiO ₂ in the glass-coated fluorescent aggregate 100 can be reduced as much as possible in terms of technical effect, but the proportion of the sulfide-based fluorescent material 120 increases by that amount. 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.

As the sulfide-based fluorescent material 120, zinc sulfide (ZnS) having 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 is extinguished as soon as the irradiation of the excitation light is stopped, whereas phosphorescence is a phenomenon in which light emission continues even after the excitation light is cut off. Strictly speaking, fluorescence and phosphorescence refer to different phenomena, but the "fluorescent material" includes not only those having fluorescence but also those having phosphorescence. When used for display on a road, it is preferable that afterglow is generated for a long time after being irradiated with excitation light, and in that respect, phosphorescent light is suitable. Further, the sulfide-based fluorescent material 120 is preferably of a type that emits yellow light having a wavelength of, for example, 430 to 580 nm so as to easily detect light emission on the road.

(Manufacturing method of glass-coated fluorescent aggregate)
An example of a method for manufacturing the glass-coated fluorescent aggregate 100 configured as described above will be described. 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 in the internal division. As the sulfide-based fluorescent material 120, a commercially available material (for example, phosphorescent pigment GSS manufactured by Nemotrumi Material Co., Ltd.) can be used. A material called soda glass is used for the bottle glass, and most of the main components are composed of the three components of SiO ₂ , CaO, and Na _2O .

Next, the mixed material is calcined under an inert atmosphere or a reducing atmosphere, preferably under an inert atmosphere at 800 ° C. or higher and 950 ° C. or lower. Specifically, for example, it can be fired in a nitrogen atmosphere. In this way, 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 with waste bottle glass, the glass-coated fluorescent aggregate 100 can be manufactured at low cost. In the firing step, it is preferable to use an external combustion type furnace (kiln). As a result, 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 SiO ₂ in an amount of 31.5 wt% or more and 49 wt% or less can be obtained. As described above, when a commercially available zinc sulfide-based phosphorescent material is mixed with the powder of waste glass and fired at 850 to 950 ° C. in an inert atmosphere or a reducing atmosphere, the fluorescence is maintained and the fluorescence is coated with inorganic glass. Aggregate can be easily obtained. Then, it is possible to prevent the fluorescent aggregate from falling off from the concrete while preventing the deterioration of the fluorescent characteristics.

(Structure of fluorescent concrete member)
The glass-coated fluorescent aggregate 100 can also 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. 1 (b), 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 receives the excitation light and fluoresces. 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 displaying guidance or alerting. In particular, it is suitable on both sides of the road because the surface is less likely to wear. In addition to the glass-coated fluorescent aggregate 100, a fine aggregate such as river sand may be mixed with the cement hardened body 210.

The thickness of the fluorescent concrete member 200 is preferably 10 mm or more and 50 mm or less. As a result, the glass-coated fluorescent aggregate 100 can be appropriately embedded while maintaining the strength. Further, the cement hardened body 210 is preferably formed as a result of mixing at a water / cement ratio of 0.35 or more and 0.50 or less. As a result, it is possible to secure the amount of light extracted by fluorescence and maintain the strength as a member.

The cement hardened body 210 is a binder containing lime as a main component, and is produced by crushing, calcinating, and firing limestone, clay, and the like. It is preferable to use ordinary Portland cement for the hardened cement 210, but early-strength Portland cement, moderate heat Portland cement, low heat Portland cement, blast furnace cement, silica cement and the like may be used. 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 it is easy to apply to the road.

(Manufacturing method of fluorescent concrete member)
A method for manufacturing the fluorescent concrete member 200 configured as described above will be described. A rectangular formwork is prepared and the formwork is filled with cement paste mixed with water / cement ratio 0.35 or 0.40 or cement mortar mixed with sand. Then, the poured material is pressed by the press plate while vibrating.

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

Then, the material is carried to the curing room as it is and cured for a predetermined period. By removing the formwork after the cement material has hardened, the glass-coated fluorescent aggregate 100 can generate a fluorescent concrete member 200 embedded in the cement hardened body 210. In the above example, the glass-coated fluorescent aggregate 100 is embedded in the poured material, but the glass-coated fluorescent aggregate 100 is scattered on the bottom surface of the mold, and cement mortar is applied so as to fill the gaps in the glass-coated fluorescent aggregate. You may pour it.

[Second Embodiment]
In the above embodiment, the glass-coated fluorescent aggregate 100 is the mixture itself of the glass 110 and the sulfide-based fluorescent material 120, but the mixture of the glass 110 and the sulfide-based fluorescent material 120 is translucent. It is more preferable that it is coated with the resin film 330. FIG. 2A is a cross-sectional view showing the structure of the glass-coated fluorescent aggregate 300 having the 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, it becomes difficult for the outside air to come into contact with the sulfide-based fluorescent material 120, and the sulfide-based fluorescence It is possible to prevent deterioration of the fluorescence characteristics of the material 120. Further, FIG. 2B is a fluorescent concrete member 400 having a resin film 330 on the surface. As shown in FIG. 2B, the fluorescent concrete member body 100 in which the glass-coated fluorescent aggregate 100 is dispersed and embedded in the cement hardened body 210 can be coated with the resin film 330 to form the fluorescent concrete member 400. ..

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

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

[Experiment and evaluation]
According to the above manufacturing method, glass-coated fluorescent aggregates having a fluorescent material content of 50 wt% and 30 wt% were prepared, respectively, and their fluorescence spectra were measured (JIS K 0120). The SiO ₂ content was 34.7% and 48.5%, respectively. 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, the phosphorescent pigment GSS manufactured by Nemotrumi Material Co., Ltd. was used. As the inorganic glass composition, transparent bottle glass pulverized with a ball mill to a particle size of 50 μm or less was used. 50 parts by mass of the above fluorescent material and 50 parts by mass of the inorganic glass composition are mixed (blending (1)), and then molded by a uniaxial pressure molding machine using the mixed raw material, the diameter is 40 mm and the height is 40 mm. A 10 mm disk-shaped pellet was prepared.

A glass-coated fluorescent aggregate was obtained by holding at 850 ° C. for 1 hour in a nitrogen atmosphere using an atmosphere-type high-speed heating electric furnace (SBA-2025D manufactured by Motoyama Co., Ltd.). As the nitrogen gas, an industrial grade gas having a nitrogen concentration of 99.95% was used and distributed at 1.8 liters per minute. After cooling, the emission spectrum of the glass-coated fluorescent aggregate was measured and revealed yellow fluorescence having a peak at an emission wavelength of 518 nm at an excitation wavelength of 350 nm (FIG. 3A). The glass-coated fluorescent aggregate retained its 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 a reducing gas. As the reducing gas, a mixed gas of 3% by volume of hydrogen and 97% of nitrogen was used. After cooling, the emission spectrum of the glass-coated fluorescent aggregate was measured, and as a result, yellow fluorescence with emission wavelengths of 464 nm and 511 nm was exhibited at an excitation wavelength of 350 nm (FIG. 3A). The obtained glass-coated fluorescent aggregate maintained the phosphorescent characteristics as in Example 1.

(Comparative Example 1)
Pellets were prepared in the same manner as in Example 1, and the glass-coated fluorescent aggregate was prepared by holding the glass-coated fluorescent aggregate at 850 ° C. for 1 hour in an atmospheric atmosphere using an electric furnace for raising and lowering the bottom of the furnace (NHV-1515D manufactured by Motoyama Co., Ltd.). Obtained. After cooling, the emission spectrum of this glass-coated fluorescent aggregate was measured, and the fluorescence was exhibited at an excitation wavelength of 350 nm and an emission wavelength of 521 nm (FIG. 3A). However, as compared with Example 1 and Example 2, the 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 (blending (2)) to prepare disc-shaped pellets in the same manner as in Example 1, and the temperature was adjusted to 850 ° C. under 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. 3 (b)). The obtained glass-coated fluorescent aggregate retained its phosphorescent 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 a reducing gas. After cooling, the emission spectra of the obtained glass-coated fluorescent aggregate were measured, and as a result, yellow fluorescence with emission wavelengths of 466 and 511 nm was exhibited at an excitation wavelength of 350 nm (FIG. 3 (b)). This glass-coated fluorescent aggregate maintained the phosphorescent characteristics as in Example 3.

[Comparative Example 2]
Pellets were prepared in the same manner as in Example 3, and the glass-coated fluorescent aggregate was prepared by holding the glass-coated fluorescent aggregate at 850 ° C. for 1 hour in an atmospheric atmosphere using an electric furnace for raising and lowering the bottom of the furnace (NHV-1515D manufactured by Motoyama Co., Ltd.). Obtained. After cooling, the emission spectrum of the obtained glass-coated fluorescent aggregate was measured, and the fluorescence was exhibited at an excitation wavelength of 350 nm and an emission wavelength of 517 nm (FIG. 3 (b)). However, even when the proportion of the sulfide-based phosphorescent material was increased, the yellow phosphorescent emission was significantly reduced as compared with Examples 3 and 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 if a sulfide-based phosphorescent material is used, so that a fluorescent material that can be used outdoors can be produced. can. It was examined whether the same glass coating could be achieved with a commercially available sulfide-based phosphorescent material ZnS (Cu). We have realized the coating of zinc sulfide-based phosphorescent material, which is cheaper than strontium aluminate, with inorganic glass. It is possible to provide a phosphorescent aggregate that can withstand outdoor use without requiring a complicated process.

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

Claims (3)

A fluorescent concrete member that emits fluorescence in response to excitation light.
Cement hardened body and
It is provided with glass embedded in the surface of the hardened cement, a sulfide-based fluorescent material dispersed in the glass, and a translucent resin film for coating the glass, and the SiO ₂ concentration is 31.5 wt%. A fluorescent concrete member comprising: a glass-coated fluorescent aggregate having a content of 49 wt% or less. A method for manufacturing a fluorescent concrete member in which a glass-coated fluorescent aggregate that emits fluorescence in response to excitation light is embedded in the surface of a hardened cement .
A step of mixing the sulfide-based fluorescent material and the powder of the waste bottle glass so that the powder of the waste bottle glass is contained in the range of 45 wt% or more and 70 wt% or less in the internal division.
The step of firing the mixed material at 800 ° C. or higher and 950 ° C. or lower in an inert atmosphere or a reducing atmosphere, and
The fired material is cooled, and the solidified body obtained by the cooling is crushed to be substantially formed by the glass containing 31.5 wt% or more and 49 wt% or less of SiO ₂ and the sulfide-based fluorescent material. And the process of producing a mixture
A step of coating the mixture with a translucent resin film to produce a glass-coated fluorescent aggregate.
The process of filling the mold with cement paste mixed with water / cement ratio of 0.35 to 0.40 or cement mortar mixed with sand, and
A production method comprising a step of embedding the glass-coated fluorescent aggregate on the surface of the filled cement paste or cement mortar before the cement paste or cement mortar is solidified . The manufacturing method according to claim 2 , wherein an external combustion type furnace is used in the firing step.

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