JP2009096879A - Molding material composition for light-accumulating ceramic, molded article of light-accumulating ceramic using the composition, method for producing the same and method for producing light-accumulating pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded article having an optional three-dimensional form and emitting accumulated light from whole of the article, to provide the molded material requiring no coking treatment by reinforcing waterproofness of the molded article itself, and to provide a general grade light-accumulating pigment which can achieve light-accumulating signs for escape and induction, which can be achieved only by using a specific grade light-accumulating pigment excellent in afterglow characteristic. <P>SOLUTION: The molding material composition of the light-accumulating ceramics is prepared by blending 5 to 60 pts.mass aqueous dispersion obtained by dispersing by combining the oxide of at least one element among elements belonging to the third long period and the oxide of at least one element among elements belonging to a second short period in water, an alcohol or a mixed liquid of water and the alcohol based on 100 pts.wt. mixture obtained by blending by a ratio of 1 to 4 pts.mass powdery or granular light-accumulating pigment, 0.5 to 3 pts.mass glass frit and 4 to 8 pts.mass glass beads. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention enhances the water resistance, which is a weak point of phosphorescent pigments, and is a phosphorescent ceramic molding material composition for multiple uses that possesses high afterglow luminance, a phosphorescent ceramic molded body using this composition, The manufacturing method and the manufacturing method of a luminous pigment are related.

Conventionally, it is known to apply a phosphorescent pigment to the surface of a plate glass and use it as a decoration for a show window or the like. Such known ones consist of a sheet glass surface coated with a phosphorescent pigment, and are not only easily altered by direct exposure to the natural environment such as sunlight, air, and wind and rain, but are also susceptible to scratches and the like. There were problems in terms of vulnerability to chemical properties, wear resistance, and contamination resistance.

In order to solve the above problems, the inventor of the present application forms a cosmetic agent layer containing a phosphorescent substance in the middle between the plate-like glass layer and the foamed glass material layer, and fires under a low oxygen concentration by a reduction firing method. Thus, a patent application relating to the invention of “laminated foamed glass and a method for producing the same” capable of maintaining the original physical properties of the phosphorescent substance or fluorescent substance while avoiding the influence of oxygen as much as possible was made (see Patent Document 1). . The laminated foamed glass according to the present invention has been well received by eliminating the drawbacks that the phosphorescent pigment changes in quality upon contact with water or scratches.
JP 2005-119931 A Japanese Patent No. 3257842 Japanese Patent No. 3257947

  In addition, in traditional methods of manufacturing ceramics, which are traditional ceramics, materials such as clay, silica, and limestone are kneaded with water and molded and fired, but the moldability of intermediate molded products before firing is improved. In order to do this, an oily binder or an aqueous binder is blended with a solvent together with a solvent. However, when the oil-based binder is applied to the molded product of the present invention, a part of the oil-based binder component is carbonized due to the heat in the firing kiln, and it adheres to the phosphorescent pigment, greatly improving the phosphorescent performance of the molded body. There was a problem of lowering.

  In order to solve the above-mentioned problems, the present inventor has eagerly studied materials that replace oil-based binders, and as a result, silicon dioxide, phosphorus pentoxide, sulfur trioxide, potassium oxide, chromium oxide, iron oxide, etc., instead of oil-based binders. An inorganic oxide composed of a combination of at least one oxide of elements belonging to the third long period and at least one oxide of elements belonging to the second short period is water or By using the composition of the present invention containing an aqueous dispersion dispersed in a mixed solution of water and alcohol, the phosphorescent performance is not lowered by the heat of the firing kiln, and more vivid light is emitted, and the water resistance is enhanced. As a related product, it has been fully used, and even when the molding pressure is low, it has been found that the firing shrinkage rate is small, and the present invention has been completed. The main purpose is not limited to the first flat plate-like glass, but in a molded body having an arbitrary three-dimensional form, a molded body that emits light as a whole can be obtained, and second, the water resistance of the molded body itself. By strengthening the properties, it is possible to obtain molded products that do not require caulking, and thirdly, phosphorescent evacuation / guidance signs that could only be achieved with special grade phosphorescent pigments that have excellent afterglow characteristics. The object is to obtain a molded article that can be achieved by using a luminous phosphor of a grade and a luminous pigment comparable to the special grade.

  In order to solve the above-described problems, the present invention provides powder or granular luminous pigment in a ratio of 1 to 4 parts by mass, glass frit in a range of 0.5 to 3 parts by mass, and glass beads in a ratio of 4 to 8 parts by mass. For 100 parts by mass of the blended mixture, at least one kind of oxide of elements belonging to the third long period and at least one kind of oxide of elements belonging to the second short period were combined. A phosphorescent ceramic molding material composition comprising 5 to 60 parts by mass of an aqueous dispersion in which an inorganic oxide powder is dispersed in water, alcohol, or a mixture of water and alcohol (claim 1). ).

  In order to solve the above problems, the present invention provides a foaming agent comprising at least one of alkali silicate, calcium carbonate, dolomite, and silicon carbide in the phosphorescent ceramic molding material composition. It is preferable to use the phosphorescent ceramic molding material composition described above, wherein 0.1 to 5.0 parts by mass of 100 parts by mass of the mixture is blended in an aqueous dispersion.

  In order to solve the above problems, the present invention is characterized in that the alcohol is at least one of propanol, ethanol, butoxypropan-1-ol and diacetone alcohol. It is preferable to use a phosphorescent ceramic molding material composition (claim 3).

In order to solve the above-mentioned problems, the present invention uses a glass frit having a thermal expansion coefficient of 5 × 10 ⁻⁶ / ° C. or less, and the phosphorescent ceramic molding according to any one of the above, A material composition is preferable (claim 4).

  In order to solve the above-mentioned problems, the present invention is preferably a luminous ceramic molded body obtained by molding any of the molding material compositions described above (Claim 5). ).

  Further, in order to solve the above-mentioned problems, the present invention comprises a plate-like press-molded product of any one of the molding material compositions described above and a surface layer plate-like glass, which are fired after drying. It is preferable that the plate-like luminous ceramic molded body is characterized.

  In order to solve the above-mentioned problems, the present invention is characterized by comprising a step of extruding and / or press-molding the molding material composition according to any one of the above, a drying step and a firing step. It is preferable to use the method for producing a luminous ceramic molded body.

  In order to solve the above-mentioned problems, the present invention comprises at least 1-4 parts by mass of powder or granular luminous pigment, 0.5-3 parts by mass of glass frit, and 4-8 parts by mass of glass beads. It comprises a step of firing a mixture blended in a proportion in a firing kiln, a step of compressing and crushing the fired product, and a step of sieving and classifying the compressed and crushed product, and emits afterglow with high brightness. (8).

  When a conventional ceramic composition uses a conventional oil-based binder, the compounding agent is carbonized in the firing kiln and the phosphorescent performance is greatly reduced, whereas the phosphorescent ceramic molding material composition of the present invention is At least one of oxides belonging to the third long period such as potassium oxide, chromium oxide and iron oxide, and elements belonging to the second short period such as silicon dioxide, phosphorus pentoxide and sulfur trioxide. Afterglow luminance characteristics without degrading phosphorescent performance by using an aqueous dispersion in which an inorganic oxide combined with at least one of the above oxides is dispersed in water, alcohol or a mixture of water and alcohol It has the effect of improving the quality. When the molding pressure at the time of molding is relatively low pressure, the phosphorescent ceramic molding material composition of the present invention is transformed into an ordinary ceramic composition, while it shrinks significantly when the molded product is subsequently fired. On the other hand, the firing shrinkage rate is suppressed to about 1/10 or less, and the moldability such as preserving and mold release is improved. Since it can be molded at a low pressure as described above, the glass bead particles (particle size 10 to 300 μm) adhere or mix in the form of dots on the surface of the luminous pigment particles (particle size 50 to 500 μm). Has the effect of being amplified. That is, the glass bead particles in the blend composition remain spherical after molding and remain in the molded product, and melt-adhere in the presence of frit in the point contact state with the phosphorescent pigment particles. This is due to the mechanism by which light is reflected and amplified by spherical glass bead particles.

  Moreover, if a low expansion frit is used for the glass frit in the blended material, an effect of further improving the dimensional stability of the molded body is obtained. By constructing as described above, three-dimensional and various shapes of phosphorescent ceramic molded bodies can be obtained, and in applications such as interior decoration illumination, the phosphorescence / light emitting area is small, so it has high brightness and long-lasting afterglow performance. It is possible to fully cope with those required. Furthermore, since the oxide fine particles in the dispersion serve as a water-proofing sealant and are excellent in water resistance, it is economical without requiring special water-proofing treatment. In the case of a foam-molded product, the weight can be further reduced. Further, according to the method for producing a luminous pigment of the present invention, a high-grade luminous pigment having a high afterglow luminance can be produced using a normal-grade luminous pigment. If the phosphorescent pigment is used, it is possible to manufacture evacuation / guidance signs in public facilities that meet the standards of the Tokyo Fire Department.

  The best mode for carrying out the present invention will be described in detail below. However, the present invention is not limited to such an embodiment. The phosphorescent ceramic molding material composition according to the embodiment of the present invention comprises 1 to 4 parts by mass of powder or granular phosphorescent pigment, 0.5 to 3 parts by mass of glass frit, and 4 to 8 of glass beads. With respect to 100 parts by mass of the mixture blended at a ratio of parts by mass, at least any one of the oxides belonging to the third long period and at least one oxidation among the elements belonging to the second short period A phosphorescent ceramic molding material composition comprising 5 to 60 parts by mass of an aqueous dispersion obtained by dispersing an inorganic oxide powder combined with a product in water, alcohol or a mixture of water and alcohol. It consists of 5 to 60 parts by weight, preferably 10 to 30 parts by weight of an aqueous dispersion dispersed in water, alcohol or a mixture of water and alcohol.

  Here, the phosphorescent pigment used in the embodiment of the present invention is stimulated with some energy, and the sucked energy is released as light of visible light, ultraviolet light, infrared light or the like having a wavelength close thereto, and continues even after the stimulation is stopped. Thus, a phosphorescent substance or a fluorescent substance having the property of exhibiting this phenomenon, preferably in the form of powder or granules. As the former phosphorescent substance, for example, when zinc sulfide and cadmium sulfide crystals are added with a small amount of copper as an activator, yellow to red light is emitted depending on the composition, and zinc sulfide is activated with a small amount of copper. What was added as an agent exhibits a green light emission, and includes a wide range of phosphorescent paints obtained by mixing these phosphorescent pigments together with a color extender.

  The fluorescent substance is an optical effect that occurs when a certain substance is irradiated with light and emits light of another wavelength, that is, a substance that emits fluorescence as visible light when ultraviolet light hits a liquid or solid. As a fluorescent pigment mainly composed of oxides such as calcium, barium, magnesium, cadmium, sulfides, silicates, phosphates, tungstates, etc., and emits fluorescence and is insoluble or hardly soluble in solvents. Further, it also includes a fluorescent paint obtained by mixing with a color developing agent (vehicle), a luminous paint, a water-soluble fluorescent dye, and the like. In addition, there are organic and inorganic fluorescent materials, and some inorganic materials have a so-called phosphorescent property that emits fluorescence even after UV irradiation is stopped. It is a fluorescent substance that is accepted by society, and is included in the present invention.

In recent years, for (Sr, M ¹ ) O— (Mg, M ² ) O— (Si, Ge) O ₂ based fluorescent matrix (M ¹ = Ca, Sr, Ba, M ² = Be, Zn, Cd) Ln (Sc, Y, La, Ce, Pr, Nd, Sm, Cd, Tb, Dy, Ho, Er, Tm, Yb, Lu, In, Bi, Sn An Eu-activated silicate phosphorescent phosphor that emits blue to green light by being co-activated with (element) and containing a halogen element (a kind of element selected from F, Cl, Br, I) (See Patent Document 2 and Patent Document 3). Such phosphorescent phosphors are also included in the phosphorescent pigment used in the present invention.

The glass frit used in the embodiment of the present invention is a kind of raw material used for the basic material of glass coating, enamel products, etc., and is mixed with raw materials such as silica sand, feldspar, lime, etc., melted at high temperature, and rapidly cooled. The flakes, powders or granules obtained in this way can be used, and powders or granules of about 1 to 100 μm are preferred. The glass frit functions as an adhesive that melts and adheres the glass beads, the luminous pigment, and other compounding agents. A normal glass frit has a thermal expansion coefficient ^exceeding 5 × 10 ⁻⁶ / ° C., and a large thermal expansion coefficient not only deteriorates the dimensional stability of the molded product, but also between the glass beads and the molten glass frit. It is preferable to use a so-called low expansion coefficient glass frit having a small thermal expansion coefficient because stress generated during heat treatment may be concentrated and distortion may occur.

  The glass beads used in the embodiment of the present invention are granular glass beads, preferably having a particle size of 10 to 300 μm, more preferably 120 to 180 μm. By adding the glass beads, the light emitted from the phosphorescent pigment is reflected or refracted or scattered on the spherical glass beads, and the light intensity is increased, which contributes to the improvement of visibility and afterglow luminance. However, if the particle size is smaller than 100 μm, the effect of increasing the light intensity tends to be insufficient, and if the particle size is larger than 200 μm, uniform mixing with other raw materials is hindered, and a problem of crushing is likely to occur during molding. There is a fear.

Examples of inorganic oxides include, for example, at least one of elements belonging to the third long period, such as potassium oxide (K ₂ O), chromium oxide (Cr ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), etc. Or at least one of oxides and elements belonging to the second short period, such as silicon dioxide (SiO ₂ ), phosphorus pentoxide (P ₂ O ₅ ), sulfur trioxide (SO ₃ ), etc. And inorganic oxides in combination. It has been clarified in the process of the present invention that the combination of these inorganic oxides affects the color developability and afterglow luminance of the luminous pigment. That is, depending on the light emission color of the phosphorescent pigment, for example, in the case of a phosphorescent pigment exhibiting green emission, an oxide of an element belonging to the third long period of the periodic table (hereinafter referred to as oxide A), for example, oxidation An oxide combining potassium (K ₂ O), chromium oxide (Cr ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ) (hereinafter referred to as base oxide), and an oxide of an element belonging to the second short period ( (Hereinafter referred to as oxide B), for example, an inorganic oxide composed of a combination of silicon dioxide (SiO ₂ ), or the base oxide and sulfur trioxide (SO ₃ ) as a kind of oxide B An inorganic oxide composed of a combination of these is preferred. In the case of a luminous pigment exhibiting blue light emission, any inorganic oxide composed of silicon dioxide (SiO ₂ ) and phosphorus pentoxide (P ₂ O ₅ ), which is one of the base oxide and oxide B, is used. Was also confirmed to be excellent in color developability and afterglow brightness. In the case of mixed colors such as green and blue, it is preferable to employ a combination of inorganic oxides having a higher mixing ratio. In the case of yellow and red other than green and blue, when the inorganic oxide in which the oxide A and the oxide B are combined is used, color developability and afterglow luminance are improved.

  The dispersion medium is water, alcohol, or a mixture of water and alcohol depending on the combination of inorganic oxides as described in the section “Preparation of aqueous dispersion containing inorganic oxide” in Example 1. A combination that easily disperses from the above can be selected as appropriate. As the alcohol used for the dispersion medium, for example, any one of propanol, ethanol, butoxypropan-1-ol and diacetone alcohol is preferably used alone or in combination. As long as there is no other medium, you may use another medium. Furthermore, in order to maintain a uniform dispersion, for example, a dispersant, a viscosity modifier, a stabilizer, and other antiseptics such as 1,2-benzisothiazolone may be appropriately added.

  FIG. 1 is a production process diagram illustrating a process of producing a luminous ceramic molded body by molding a molding material composition. As shown in this figure, after adding the aqueous dispersion through the blending step 1 and the dry stirring step 2, the clay-like kneaded material kneaded 3 is extruded and press-molded 4 or a mold using a vacuum kneading machine. It is molded into a predetermined form by molding or handmade, dried at about 100 ° C. for about 2 hours, dried in a dryer 4 and then left for a while and then cured at about 500 to 850 ° C. for 10 minutes to 1 hour, preferably Is calcined 7 in a calcining furnace at about 790 ° C. for 30 minutes, and then gradually cooled to obtain the desired molded article. Depending on the shape and size of the molded product, the surface of the glass beads is maintained by maintaining the temperature and time of the firing kiln below the temperature at which the glass beads in the composition soften and above the temperature at which the frit melts. In addition, it is preferable to control the temperature and time so that the phosphorescent pigment powder is deposited as uniformly as possible through a melt frit. Alternatively, the plate-like press-molded product of the molding material composition is heated and dried, and the surface layer plate-like glass is stacked and set, and then fired 6 in an electric kiln. A ceramic product is obtained.

  In the molding material composition described above, in the phosphorescent ceramic molding material composition, a foaming agent comprising at least one of alkali silicates such as sodium silicate, calcium carbonate, dolomite, and silicon carbide is used as the mixture. If a phosphorescent ceramic molding material composition in which 0.1 to 5.0 parts by mass of 100 parts by mass is blended in an aqueous dispersion is molded in the same manner as described above, the foaming agent foams due to heat in the firing step. To obtain a foamed molded product. In addition, water glass 0.6 to 30 parts by mass, which is a concentrated aqueous solution of alkali silicate obtained by eutectic melting of quartz with alkali carbonate, is added to the aqueous dispersion, and the water content is adjusted appropriately as described above. A similar foaming effect is obtained.

  Next, FIG. 2 is a production process diagram showing a process of producing a luminous pigment that emits afterglow with high luminance. As shown in this figure, 1 to 4 parts by mass of powder or granular general-purpose phosphorescent pigment, 0.5 to 3 parts by mass of glass frit and 4 to 8 parts by mass of glass beads are mixed and used exclusively for 11 After calcination 12 in a vacuum firing kiln called Saya, the fired product is crushed 13 by compression crushing and crushing rolls, and then the crushed product is sieved and classified 14 to generate luminous afterglow. Pigments can be produced. If the phosphorescent pigment obtained by this production method is used, a phosphorescent ceramic molded body that emits higher afterglow luminance can be obtained than when a commercially available general-purpose phosphorescent pigment is used as it is.

Hereinafter, the present invention will be described with reference to examples. However, the present invention is not limited to these examples. The adjustment of the aqueous dispersion and the adjustment of the molding material composition will be described below. Here, the mass% of the inorganic oxide component for each aqueous dispersion is determined by fluorescent X-ray analysis (SQX), and the content of the inorganic oxide solid content is obtained when the aqueous dispersion is heated. The mass change was measured, the amount of the volatile component in the liquid was taken out, and the ratio was expressed as the ratio of the remaining solid content to the mass of the aqueous dispersion minus the mass of the volatile component. The test apparatus used was a thermal analyzer manufactured by Rigaku Corporation.
<Preparation of aqueous dispersion containing inorganic oxide>
Average volatile substances and average solids content in aqueous dispersion (unit: mass%)

Sample dispersion name 1st 2nd Average volatile content Average solid content
Aqueous dispersion 1 87.49 90.24 88.87 11.1
Aqueous dispersion 2 95.67 94.71 95.19 4.8
Aqueous dispersion 3 98.02 99.16 98.59 1.4

(Aqueous dispersion 1)
(The content of inorganic oxide solids is 11.1% by mass.)
Component name of inorganic oxide Content (mass% of inorganic oxide component)
Silicon dioxide (SiO ₂ ) 49.6
Potassium oxide (K ₂ O) 22.8
Chromium oxide (Cr ₂ O ₃ ) 14.5
Iron oxide (Fe ₂ O ₃ ) 13.3
Component name content of dispersion medium Content (% by mass with respect to the entire aqueous dispersion)
0-100 water
Ethanol 30-100

(Aqueous dispersion 2)
(The content of inorganic oxide solids is 4.8% by mass.)
Component name of inorganic oxide Content (mass% of inorganic oxide component)
Silicon dioxide (SiO ₂ ) 36.3
Phosphorus pentoxide (P ₂ O ₅ ) 24.4
Potassium oxide (K ₂ O) 22.0
Chromium oxide (Cr ₂ O ₃ ) 9.36
Iron oxide (Fe ₂ O ₃ ) 8.11
Component name content of dispersion medium Content (% by mass with respect to the entire aqueous dispersion)
0-100 water
1- (2-methoxy-2-methylethoxy) -2-propanol 60-100

(Aqueous dispersion 3)
(The content of inorganic oxide solids is 1.4% by mass.)
Component name of inorganic oxide Content (mass% of inorganic oxide component)
Sulfur trioxide (SO ₃ ) 23.7
Potassium oxide (K ₂ O) 27.6
Chromium oxide (Cr ₂ O ₃ ) 20.8
Iron oxide (Fe ₂ O ₃ ) 24.8
Component name content of dispersion medium Content (% by mass with respect to the entire aqueous dispersion)
0-100 water
Butoxypropan-1-ol 15-40
Diacetone alcohol 40-70

<Adjustment of molding material composition>
(Formulation 1)
Material name Number of blended parts (parts by mass)
Luminescent pigment powder (green) 30
(Particle size distribution: # 160, # 160 to # 100 +, # 160 to # 100−)
Low thermal expansion glass frit 10
Glass beads (# 120) 60
Aqueous dispersion 1 or 3 15

(Formulation 2)
Material name Number of blended parts (parts by mass)
Luminous pigment powder (mixed color of blue and green) 25
(Used by mixing the phosphorescent pigment powder in a ratio of green: blue = 5 g: 20 g)
Low thermal expansion glass frit 10
Glass beads (# 120) 65
Aqueous dispersion 2 15

[Examples 1, 2, 3]
The aqueous dispersions 1 and 2 are prepared in advance. The molding material compositions of Formulations 1 and 2 are prepared. In order to carry out the invention, three types of phosphorescent pigment powders (average particle size is 160 μm) with different particle size distributions according to Formulation 1 are used to press the clay-like kneaded material of the molding material composition into a plate shape. Were fired in the same manner as described in the section of the best mode, and three types of molded articles having different particle size distributions of the luminous pigment powder were obtained. These three types of plate-shaped molded bodies were used as afterglow luminance test samples. The results of the afterglow luminance test are shown in Table 1 and the graph of FIG.

The sample numbers (1-1, 4-1 and 5-1) in Table 1 and FIG. 3 are the particle size distributions (# 160, # 160 to # 100 +, # 160 to # 100) of the phosphorescent pigment powder, respectively. It corresponds to a sample of a molded body containing-). Measurement conditions afterglow luminance test was compliant to JIS Z9107, _{excitation: D 65} common light source 200 lx, 20 minutes, measured: afterglow luminance until after excitation is stopped 480 min, measurement temperature: 23 + -2 ° C., using equipment : _{D 65} common source F65D-a (Suga tester), luminometer: IM-5 (TOPCON), color luminance meter: BM-5A (TOPCON), a radio grapher Na riser NIM-1000 (Nemoto).

From Table 1 and the graph of FIG. 3, the afterglow luminance after 20 minutes has conventionally been 140 to 145.
What was (mcd / m ² ), this example reached about 172 to 189 (mcd / m ² ), and the afterglow brightness was improved by 20 to 30% compared to the conventional product. Become. Here, the conventional product refers to an existing glass molded product that does not use glass beads and an inorganic aqueous dispersion. Further, in the blends of Examples 1, 2, and 3, the blends using the aqueous dispersion 1 and the aqueous dispersion 3 are not greatly different in terms of color development and afterglow luminance, but the aqueous dispersion 2 was used. In the blending, the color developability and the afterglow brightness were superior to the conventional product, but it was confirmed that the blending was slightly lower than the blend using the aqueous dispersion 1 and the aqueous dispersion 3.

[Example 4]
Foam phosphorescence in the same manner as in Examples 1, 2 and 3, except that one part of Formulation 1 (particle size distribution: # 160) was mixed with 3.0 parts by mass of sodium silicate as a foaming agent in the aqueous dispersion. A ceramic product was obtained. The afterglow brightness of this example was almost the same as that of Example 1.
Normally, the specific gravity of the non-foamed product is about 2.5, whereas the specific gravity of the foamed product of this example is about 0.4, which is actually 1/6 of the weight of the non-foamed product. The degree of weight reduction can be adjusted as appropriate by changing the expansion ratio by changing the number of blended parts of the foaming agent.

[Example 5]
The plate-shaped press-molded product of the molding material composition used in Example 4 was heated and dried, and the surface layer plate-shaped glass was stacked and set, fired in an electric kiln, and the surface was coated with the surface layer glass. A foamed phosphorescent ceramic molded body was obtained. The afterglow brightness of this example was also almost the same as that of Example 1. As for the water resistance, no abnormality was found in the result of leaving it on the roof of the building for about 3 months.

[Example 6]
Using the molding material composition of Formulation 2, a molded product that three-dimensionally represents the element symbols was formed, and the other was the same as Example 3 to obtain a luminous ceramic molded body. The formed body was attached to a plate body such as a steel plate to produce a display (see FIGS. 4 and 5). It was proved that the afterglow luminance was much longer and stronger than the conventional product.

(Formulation 3)
Material name Number of blended parts (parts by mass)
Luminescent pigment powder (green) 30
Low thermal expansion glass frit 10
Glass beads (# 120) 60
After firing the mixture of Formula 3 in a vacuum firing kiln, the fired product is compressed and crushed and crushed with a crushing roll, and then the crushed product is sieved and classified using a 500 μm sieve, and a phosphorescent pigment Got. The ceramic molded body using this phosphorescent pigment has much longer and stronger afterglow luminance than the ceramic molded bodies using conventional general-purpose phosphorescent pigments, similar to the phosphorescent ceramic molded bodies of the previous examples. It was confirmed that

  By adopting the above-mentioned configuration, the present invention provides a phosphorescent ceramic molded article that is rich in water resistance and possesses a high afterglow luminance. Products for outdoor use, such as planters, color blocks, exterior wall materials, planter panel boards, flower pots, sound-absorbing fireproof blocks, veranda woody panels, rooftop greening materials, products that require fire resistance or incombustibility, such as building Widely used for interior and exterior materials, etc., it is extremely useful economically.

It is a manufacturing-process figure of the luminous ceramic molded object which concerns on a present Example. It is a manufacturing-process figure of the luminous pigment which concerns on a present Example. It is a graph which shows the afterglow brightness | luminance test result of an Example. It is the photograph which has arrange | positioned the luminous ceramic molded object of an Example under a fluorescent lamp. It is the photograph which image | photographed the luminous ceramic molded object which emits fluorescence in the state which turned off the fluorescent lamp of FIG.

Explanation of symbols

1: Mixing process 2: Stirring process 3: Aqueous dispersion addition kneading process 4: Extrusion / press molding process 5: Drying process 6: Surface glass setting / firing process 7: Product curing / firing process 11: Compounding process 12: Firing process 13: Compression crushing / crushing process 14: Sieve-classification process

Claims (8)

3rd long with respect to 100 parts by weight of a mixture containing 1 to 4 parts by weight of a powder or granular luminous pigment, 0.5 to 3 parts by weight of glass frit and 4 to 8 parts by weight of glass beads. An inorganic oxide powder obtained by combining at least one oxide of elements belonging to a period and at least one oxide of elements belonging to a second short period with water, alcohol, or water A molding material composition for phosphorescent ceramics, wherein 5 to 60 parts by mass of an aqueous dispersion dispersed in a mixed liquid of alcohol is blended. In the phosphorescent ceramic molding material composition, a foaming agent composed of at least one of alkali silicate, calcium carbonate, dolomite and silicon carbide is added in an amount of 0.1 to 5.0 parts by weight with respect to 100 parts by mass of the mixture. 2. The phosphorescent ceramic molding material composition according to claim 1, wherein a mass part is blended in an aqueous dispersion. 3. The phosphorescent ceramic molding material composition according to claim 1, wherein the alcohol is at least one of propanol, ethanol, butoxypropan-1-ol and diacetone alcohol. The glass frit having a thermal expansion coefficient of 5 × 10 ⁻⁶ / ° C. or less is used. The phosphorescent ceramic molding material composition according to claim 1, A phosphorescent ceramic molded body obtained by molding the molding material composition according to claim 1. A plate-shaped luminous ceramic molded body obtained by superimposing a plate-like press-molded product of the molding material composition according to any one of claims 1 to 4 and a surface layer plate-like glass and firing after drying. . A method for producing a luminous ceramic molded body comprising a step of extruding and / or press-molding the molding material composition according to any one of claims 1 to 4, and a drying step and a firing step. Firing at least one powder or granular luminous pigment 1 to 4 parts by weight, a mixture containing 0.5 to 3 parts by weight of glass frit and 4 to 8 parts by weight of glass beads in a firing kiln; A method for producing a luminous pigment, comprising a step of compressing and crushing a fired product and a step of sieving and classifying the compressed and pulverized product, and emitting afterglow with high brightness.