JP2012087035A - Method for producing light accumulator, light accumulator produced by the same and accessory using light accumulator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a light accumulator which can be produced simply and easily and has a surface luster and good luminescent performance, a light accumulator produced by the same and an accessory using the light accumulator.SOLUTION: In the method for producing a light accumulator 1 by firing a mixture containing at least a light accumulating pigment 2 and glass frit, the mixture is melted while being fired to form an intermediate light accumulator, and the surface of the intermediate light accumulator is heated so that the light accumulating pigment 2 near the surface may be burned down, thereby making the surface 1c smooth.

Description

  The present invention relates to a method of manufacturing a phosphorescent body, a phosphorescent body manufactured by the method, and a jewelry using the phosphorescent body. More specifically, the present invention relates to a method for producing a phosphor, which is obtained by firing a mixture containing at least a phosphorescent pigment and glass frit, a phosphor that has been produced by the method, and a jewelry using the phosphor.

  Conventionally, as a method for producing a phosphorescent body as described above, for example, those described in Patent Documents 1 and 2 are known. In Patent Document 1, the end portions of two rod-shaped glasses are heated to form spherical molten glass, granular luminous stones are attached to one molten glass, and the molten glass is mixed to obtain the luminous glass on the molten glass body. Are mixed evenly. However, the work of mixing phosphorescent stones is complicated, and skilled techniques are required to mix phosphorescent stones evenly.

  Moreover, in patent document 2, the light-emitting part is included by grind | pulverizing the sheet glass which mixed the phosphorescent material and the glass material, and grind | pulverized, and formed the particle | grains which consist of a phosphorescent material and a glass material, and baking again the particle | grains. A granular part is formed. Therefore, the production efficiency of the granular part including the light emitting part is low, and the manufacturing process is complicated. In addition, variations in the size and shape of the granular portion may occur.

JP 2004-10409 A JP 2007-112585 A

  In view of such conventional circumstances, the present invention provides a method for producing a phosphorescent material having a glossy surface and good luminous performance that can be produced easily and easily, a phosphorescent material produced thereby, and an accessory using the phosphorescent material. The purpose is to provide.

  In order to achieve the above object, a feature of the method for producing a phosphor according to the present invention is that a phosphor comprising a phosphor containing at least a phosphorescent pigment and a glass frit is fired, and the mixture is fired and melted. An intermediate phosphor is formed, and the surface is smoothed by heating the surface so that the phosphorescent pigment near the surface of the intermediate phosphor is burned off.

  According to the said structure, since it should just heat so that the phosphorescent pigment of the surface vicinity of an intermediate phosphor may burn out, manufacture of a phosphor is simple and easy. In addition, the surface can be formed smoothly only by heating the surface, and a phosphorescent material having gloss and good light emitting performance can be obtained. Furthermore, since the phosphorescent pigment in the vicinity of the surface of the intermediate phosphor is subject to burning, there is little influence on the luminous performance of the entire phosphor, and the luminous performance is not deteriorated. In such a case, the heating temperature in the vicinity of the surface of the intermediate phosphor is preferably 900 ° C. or more and 1400 ° C. or less.

  Moreover, it is good to mix | blend the said luminous pigment with 1 to 30 weight% with respect to the total amount of the said luminous pigment and the said glass frit. If it is within this numerical range, the melted mixture has appropriate fluidity and can be easily formed into a desired shape. Moreover, the light emission performance is not deteriorated.

  The mixture may be fired into a rod shape and melted so that the intermediate phosphor is wound around a rod-shaped holding member. By firing in a rod shape, the intermediate phosphor can be easily generated. And a spherical luminous body can be easily manufactured by winding and forming an intermediate luminous body on a rod-shaped holding member.

  Moreover, you may form the said intermediate | middle luminous body in the recessed part provided in the jig | tool. By forming the concave portion into an arbitrary shape, a phosphorescent body having a predetermined shape can be easily obtained.

  The luminous body manufactured by the method for manufacturing a luminous body according to any one of the above is preferably a spherical body having an average diameter of 5 mm to 50 mm. In such a case, the phosphorescent material may be an accessory such as a necklace or a bracelet.

  According to the method for producing a phosphorescent body according to the present invention, the phosphorescent body produced thereby, and the features of the accessory using the phosphorescent body, the phosphorescent body that can be easily and easily manufactured and has a glossy surface and good luminous performance. It became possible to get.

  Other objects, configurations, and effects of the present invention will become apparent from the following embodiments of the present invention.

It is a figure which shows the luminous body based on this invention, (a) is a front view, (b) is the A section partial enlarged view of (a). It is a figure which shows typically a rod-shaped object manufacturing process. It is a figure which shows an intermediate | middle luminous body production | generation process typically. FIG. 2 is a view corresponding to FIG. 1 showing an intermediate phosphor. It is the B section partial enlarged view of Drawing 4 (b), and (a) is a figure showing typically the state after a heating process, and (b) after a heating process. It is an enlarged photograph of the surface of the luminous body which concerns on this invention. It is an enlarged photograph of the surface of an intermediate phosphor. It is sectional drawing which shows typically the tool used by other embodiment of this invention.

Next, a first embodiment of the present invention will be described with reference to FIGS.
The phosphorescent body 1 according to the first embodiment of the present invention is a spherical sintered body formed by firing a mixture containing at least the phosphorescent pigment 2 and glass frit. As shown in FIG. 1A, the spherical luminous body 1 is composed of a surface layer portion 1a and a central portion 1b, and the surface 1c of the luminous body 1 is formed smoothly. As shown in FIG. 2B, the surface layer 1a is composed of a glass component 3 formed by melting glass frit. The central portion 1b is formed by dispersing the phosphorescent pigment 2 in a glass component 3 formed by melting glass frit.

  Inside the phosphor 1, the phosphorescent pigment 2 is mixed almost uniformly in the glass component 3 of the central portion 1 b. Thereby, it can be made to light-emit in all directions from the center part 1b. Moreover, as shown in FIG. 6, since the surface 1c of the luminous body 1 is formed smoothly, gloss and gloss are imparted and the design is improved. Moreover, the surface layer portion 1a made of the glass component 3 also functions as a coating layer for protecting the central portion 1b containing the phosphorescent pigment 2. Therefore, the light emission (afterglow) performance can be improved.

  Moreover, as shown to Fig.1 (a), the through hole 1d is formed in this luminous body 1. FIG. For example, by passing a string or a chain through the through hole 1d, the phosphorescent body 1 can be used for accessories (jewelry) such as a bracelet or a necklace. The particle diameter of the phosphor 1 is preferably 5 to 50 mm, for example.

  Here, as the phosphorescent pigment, for example, a pigment obtained by adding and firing a rare earth element activator and a coactivator containing an alkaline earth metal aluminate compound as a main component is used. Examples of the alkaline earth metal include at least one metal element such as calcium, strontium, and barium, and alloys of these metal elements and magnesium. Examples of the rare earth element activator include europium and dysprosium. Examples of the co-activator include elements such as lanthanum, cerium, praseodymium, neodymium, samarium, cadmium, terbium, and dyspronium. In addition to the oxide phosphors described above, phosphorescent pigments include CaS: Bi (purple blue light emission), CaSrS: Bi (blue light emission), ZnS: Cu (green light emission), ZnCdS: Cu (yellow to orange light emission). It is also possible to use sulfide phosphors such as In addition, you may use the above-mentioned compound by mixing suitably, Furthermore, what has a luminous property in another inorganic fluorescent pigment or an organic fluorescent pigment can also be used.

  The glass frit includes at least one alkaline earth metal oxide selected from the group consisting of, for example, silicon oxide, aluminum oxide, boron oxide and alkali oxide, and selected from the group consisting of calcium oxide, strontium oxide and magnesium oxide. A glass frit containing is used. The glass material is not limited to the above material, but a glass material that melts (liquefies) at a temperature at which the above phosphorescent pigment can exist in a solid state may be used. Moreover, it is desirable to use a highly transparent glass material after heating. The light emission of the phosphorescent pigment is not hindered and the light emission performance is prevented from being lowered.

  Next, the manufacturing process of the phosphor 1 according to the first embodiment will be described. This manufacturing process generally includes a temporary sintered body generating step of firing the phosphorescent pigment 2 and the glass frit to produce the temporary sintered body 10, and an intermediate phosphorescent body by melting a part of the produced temporary sintered body 10. The intermediate luminous body production | generation process which produces | generates 20 and the heating process which heats the surface 20a of the intermediate luminous body 20 are comprised.

  In the temporary sintered body generation step, as shown in FIG. 2, for example, a firing mold 11 having a groove 12 formed in a predetermined shape is used. In the present embodiment, heat-resistant gypsum is used for the firing mold 11, and the groove 12 (for example, width 10 mm, length 37 cm) is formed in the heat-resistant gypsum 11 by NC milling. In the present embodiment, a rod-shaped body is generated as the temporary sintered body 10. By making the temporary sintered body 10 into a rod-like body, workability in a later process can be improved.

  The rod-shaped body 10 is manufactured by first filling the grooves 12 with the above-mentioned phosphorescent pigment 2 and glass frit powder, and pressing and compacting them with a constant pressure. In order to make the filling amount constant, the depth is adjusted. Here, the content rate of the luminous pigment 2 can be selected in the range of 1% to 30% (mass ratio) with respect to the total amount of the luminous pigment 2 and the glass frit. If it is in this numerical range, it is possible to shape | mold into the luminous body 1 of a desired shape, without reducing luminous performance.

  In the present embodiment, the content rate of the phosphorescent pigment 2 is set in the range of 10% to 20% (mass ratio). In the case where the content of the phosphorescent pigment 2 is 20% or more, the stick-shaped body 10 is melted too much in the subsequent intermediate phosphor generation process. Therefore, the work efficiency of what can be formed into a spherical shape is reduced. On the other hand, when the content rate of the luminous pigment 2 is 20% or more, it is too viscous and too soft. Therefore, although it can be formed into a spherical shape, the working efficiency is reduced as described above. That is, when the spherical phosphor 1 is generated, the intermediate phosphor 20 can be easily formed into a spherical shape in the intermediate phosphor formation step, and the spherical phosphor 1 can be obtained as long as it is within the above numerical range. Become.

  Then, the heat-resistant gypsum 11 filled with the phosphorescent pigment 2 and the glass frit powder in the groove 12 is placed in a furnace 13 and fired at about 800 ° C. At the firing temperature, the glass frit described above is melted, but the phosphorescent pigment 2 is hardly melted. Thereby, the rod-shaped body 10 in which the phosphorescent pigment 2 is dispersed in the glass component 3 is obtained.

Next, an intermediate luminous body production | generation process is demonstrated.
As shown in FIG. 3, the tip 10 a of the rod-like body 10 is beaten and melted by the flame 21 a of the burner 21. The melted tip 10 a is wound around the rod-shaped holding member 22. As the holding member, for example, an iron needle 22 is used, and an end portion is provided with a peeling portion 23 made of gypsum. By providing the peeling portion 23, the generated intermediate phosphor 20 can be easily separated from the iron needle 22, and the working efficiency is improved. The winding is performed while the tip 10a is rolled with the burner 21 and the iron needle 22 is rotated, so that a spherical intermediate phosphor 20 is generated. By wrapping around the iron needle 22, a through hole 20 c is formed in the intermediate phosphor 20. The through hole 20 c becomes the through hole 1 d of the phosphor 1.

  Here, the temperature of the flame 21a of the burner 21 is about 1200 to 1400 ° C. On the other hand, the temperature of the tip 10a of the rod-like body 10 melted by the burner 21 is about 800 ° C. Therefore, at the tip 10a of the rod-shaped body 10, the glass component 3 is melted again, but the phosphorescent pigment 2 is not burned out. When the temperature of the rod-shaped body 10 itself is increased to about 1200 ° C., the phosphorescent pigment 2 in the rod-shaped body 10 is burned out and the fluidity of the glass component 3 is increased (viscosity is reduced), and the melted tip 10a is melted. Is difficult to wind around the iron needle 22. Therefore, the melting temperature of the rod-shaped body 10 is less than 900 ° C., preferably 800 ° C., at which the viscosity can be wound around the iron needle 22 in a spherical shape.

  When fired at this firing temperature, the tip 10a has an appropriate fluidity (viscosity), so that it can be easily wound around the iron needle 22 to obtain a spherical intermediate phosphor 20 as shown in FIG. it can. In addition, the phosphorescent pigment 2 is mixed substantially uniformly in the process of winding in a spherical shape. Therefore, the phosphorescent pigment 2 is dispersed substantially uniformly in the generated intermediate phosphor 20 and the phosphorescent pigment 2a is also present near the surface 20a of the intermediate phosphor 20 as shown in FIG. 4B. Become. The phosphorescent pigment 2a becomes rough on the surface 20a, and as shown in FIG. 7, irregularities are formed on the surface 20a. As shown in FIG. 3, a plurality of intermediate phosphors 20 may be continuously formed on the iron needle 22.

Next, the heating process will be described.
As shown to Fig.5 (a), the unevenness | corrugation is formed in the surface 20a of the intermediate | middle luminous body 20 with the luminous pigment 2a of the surface 20a vicinity. Therefore, by heating the surface 20a of the intermediate phosphor 20 at a temperature at which the phosphorescent pigment 2a burns away, the phosphorescent pigment 2a in the vicinity of the surface 20a is burned out and the surface 20a is made smooth.

  In this heating step, the surface 20a of the intermediate phosphor 20 is uniformly heated by the burner 21 at 900 to 1400 ° C. Thereby, as shown in FIG.5 (b), the luminous pigment 2a which exists in the surface 20a of the intermediate | middle luminous body 20 is burned out. On the other hand, since the temperature of the central portion 20b of the intermediate phosphor 20 does not rise as much as the surface 20a, the phosphorescent pigment 2b present in the central portion 20b is not burned out. For this reason, even if the phosphorescent pigment 2a in the vicinity of the surface 20a is burned out, the luminous performance of the phosphorescent body 1 as a whole is maintained without deteriorating.

  Moreover, since the surface 20a of the intermediate phosphor 20 need only be rubbed with the burner 21, the phosphorescent pigment 2b in the central portion 20b is not oxidized. Therefore, it is not necessary to separately provide a coating layer made of the glass component 3 or the like on the surface 1c of the phosphor 1 and light emission performance can be maintained. Moreover, since it is only burned by the burner 21, it can be processed easily and easily.

  Furthermore, since the glass component 3 in the vicinity of the surface 20a is also softened by the heating, the surface 20a of the intermediate phosphor 20 becomes smooth. In this manner, a spherical phosphor 1 having gloss and gloss is generated on the surface 1c.

  Here, an enlarged photograph of the surface of the spherical phosphor 1 is shown in FIG. 6, and an enlarged photograph of the surface of the spherical intermediate phosphor 20 is shown in FIG. These magnified photographs were taken at the same location under the same photographing conditions (magnification rate 20%, phosphorescent pigment content rate 10%). As shown in FIG. 7, irregularities are formed on the surface of the intermediate phosphor 20 by phosphorescent pigment. However, when the surface of the intermediate phosphor 20 is heated as described above, a spherical phosphor 1 as shown in FIG. 6 is obtained. As shown in the figure, by heating, the phosphorescent pigment in the vicinity of the surface is burned out, and the glass component is softened to make the surface smooth.

  The produced phosphor 1 is placed on the ash so as not to be directly exposed to air, and is gradually cooled to prevent cracks due to a rapid temperature drop.

Finally, the possibility of other embodiments is mentioned. In the following embodiments, the same members and the like as those in the above embodiments are denoted by the same reference numerals.
In the said embodiment, the spherical luminous body 1 was manufactured. However, the shape of the phosphor 1 is not limited to a sphere, and can be formed into a suitable shape such as a cube, a rectangular parallelepiped, a polygonal column, or a plate. For example, when forming into a rectangular parallelepiped, as shown in FIG. 8, a forming scissor 30 may be used as a forming jig. The melted tip 10a may be put into the recess 31 of the forming scissors 30 and press-molded. Moreover, the through-hole 32 which penetrates rod-shaped holding members, such as the iron needle 22, is provided in this recessed part 31, and you may make it a through-hole be formed in the phosphorescent body formed. The size of the phosphor is not limited to the above numerical range.

  In the said embodiment, the intermediate | middle luminous body formation process and the heating process were demonstrated as another process. However, these steps can be continuously performed as a series of operations.

  Moreover, in the said embodiment, although the temporary sintered compact was formed in rod shape, it is not restricted to rod shape. However, in the case of a rod shape, the workability of the subsequent process is good, and the above embodiment is more advantageous when generating a spherical phosphor with a through hole.

  INDUSTRIAL APPLICABILITY The present invention can be used as a phosphorescent body manufacturing method, a phosphorescent body manufactured thereby, and a jewelry using the phosphorescent body. In particular, the spherical phosphor can be used for accessories such as necklaces, bracelets, and rosaries. In addition to accessories such as accessories, it can also be used for tiles such as mosaic tiles, aggregates for construction, and the like.

1: phosphorescent material, 1a: surface layer portion, 1b: center portion, 1c: surface, 1d: through hole, 2: phosphorescent pigment, 3: glass component, 10: pre-sintered body (rod-like body), 11: mold for firing Frame (heat-resistant gypsum), 12: groove, 13: furnace, 20: intermediate phosphor, 20a: surface, 20b: central part, 20c: through hole, 21: burner, 21a: flame, 22: iron needle (bar-shaped holding member) ), 23: peeling part (gypsum), 30: forming jig, 31: recess

Claims (8)

A method for producing a phosphor, comprising firing a mixture containing at least a phosphorescent pigment and glass frit,
A method for producing a phosphor, wherein the mixture is fired and melted to form an intermediate phosphor, and the surface is heated so that the phosphorescent pigment in the vicinity of the surface of the intermediate phosphor is burned off, thereby smoothing the surface. The method for producing a phosphor according to claim 1, wherein a heating temperature in the vicinity of the surface of the intermediate phosphor is not less than 900 degrees and not more than 1400 degrees. The method for producing a phosphor according to claim 1 or 2, wherein the phosphorescent pigment is blended in an amount of 1 wt% to 30 wt% with respect to a total amount of the phosphorescent pigment and the glass frit. The method for producing a phosphor according to any one of claims 1 to 3, wherein the mixture is baked into a rod shape and melted, and the intermediate phosphor is wound around a rod-shaped holding member. The manufacturing method of the luminous body in any one of Claims 1-3 which forms the said intermediate luminous body in the recessed part provided in the jig | tool. The luminous body manufactured by the manufacturing method of the luminous body in any one of Claims 1-5. The luminous substance according to claim 6, which is a spherical body having an average diameter of 5 mm to 50 mm. A jewelry using the phosphor of claim 6 or 7.