JPS60176933A - Production of light storing fluorescent glass fiber and glass spherule - Google Patents

Abstract

PURPOSE:To obtain the titled glass spherules having improved weather, water and heat resistance and durability, etc., by hot-drawing a glass tube packed with a specific light storing fluorescent powder, cutting the resultant glass fibers, and keeping the fibers at a temperature above the melting point of glass. CONSTITUTION:A glass tube 1, having 3-10mm. outside diameter and 2-9mm. inside diameter, packed with a light storing fluorescent powder 3, e.g. ZnS, having 15-50mu particle diameter in the hollow part 2 thereof, and made of soda-lime glass (softening point: 550-650 deg.C) is drawn at 30-200cm/sec speed into fiber form while softening the end (a) thereof at a temperature of the softening point or above in a heating furnace to give light storing fluorescent glass fibers 5, which are cut to afford cut fibers 5' having 3-15mm. length. The resultant fibers 5' are placed in a charging vessel 8, dropped by small portions into a releasable cylindrical body 6, made of a material without sticking glass, and heated to 1,000-1,300 deg.C by an outer peripheral heating furnace 7 while shaking the vessel 8, and deformed into a spherical form for 0.5-10sec passing through the cylindrical body 6 to give the aimed light storing fluorescent glass spherules 9, which are then collected into a receiver 10.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing luminescent fluorescent glass fibers and glass globules.

The purpose is to create a new phosphorescent glass fiber in which a phosphorescent phosphor is encapsulated in the center of the glass fiber, and a new phosphorescent glass fiber in which a phosphorescent phosphor is also encapsulated in a glass sphere. The purpose of the present invention is to provide luminescent brown glass beads, which have excellent weather resistance, heat resistance, water resistance, abrasion resistance, etc. due to c-N, and are therefore durable enough for outdoor use. The aim is to obtain various phosphorescent products.

Conventionally, zinc sulfide, gadmium sulfide, etc. have been used as luminescent phosphors, but Towara is mixed in its powder form into plastic materials such as vinyl chloride resin and molded into various products, or made into plastics. It is used by coating molded products. Its main uses include nighttime signs, decorations, and lighting, but all of them have the major disadvantage that they have a very short lifespan and the luminescence phenomenon caused by the fluorescence disappears in a short period of time. There is.

The reason is that these luminescent phosphors have poor weather resistance.
4 Water 1/T, abrasion resistance, etc. are not good at all, so when used outdoors such as traffic signs and road white lines, the effect disappears in about 12 to 3 days, making it impossible to use for practical purposes. Although it is used indoors for electric welding pulls, etc., it is considered extremely durable, as it loses its effectiveness within about six months to a year.

In view of the circumstances described in -F, the inventors conducted repeated research on lead content in order to improve the shortcomings of conventional phosphorescent phosphors, and as a result, they arrived at the method of the present invention in which phosphorescent phosphors are encapsulated within a glass body. In other words, the hollow part of the glass tube was filled with phosphorescent powder,
A first invention, which is a method for producing a luminescent and fluorescent glass fiber, characterized in that the end portions of a core glass tube are sequentially stretched from the end portion to form a fiber while being softened;
The phosphorescent glass fiber according to the first invention is cut into appropriate lengths and kept at a temperature equal to or higher than the melting point of the glass for a predetermined period of time to form a spherical shape due to surface tension. A second invention, a method for manufacturing phosphorescent glass spheres, was achieved.

First, the first aspect of the present invention will be explained.

FIG. 1 is a schematic front view showing one embodiment of the method for increasing the width of luminous fluorescent glass fibers.

As shown in this figure, the hollow part (2) of the glass tube (1) is filled with phosphorescent powder (3), and the end (a) of the glass tube (1) is
) is heated in a heating furnace (4) to a temperature equal to the softening temperature of the glass, and the end portion (a) is stretched while softening to form a glass tube (1) into a glass fiber (5). be.

In this way, the glass material (fibers (5)) are formed sequentially and continuously from this end (a), and the glass tube (1) is sent out little by little toward the end (a). The glass fibers (5) are continuously manufactured while compensating for the consumption of the glass fibers (5).

As a result, a novel phosphorescent glass fiber C1 is obtained in which the phosphorescent powder (3) is encapsulated in the center of the glass fiber (5). In other words, it is obtained as a fibrous material that is not protected by a luminescent phosphor or glass material.

In the present invention, as the glass tube ( ), for example, sorter glass having a softening point of 550 to 65 (1''C) can be used, and a diameter of 3 to 10 mm and an inner diameter of 2 to 9 mnr are suitable.

Note that this glass tube (1) is not limited to soda glass, and it goes without saying that other types of glass such as borosilicate glass can be used.

It is a substance that produces a light-emitting phenomenon due to fluorescence by gradually releasing it in a dark place. Specifically, it is a powder containing sulfide luminescent fluorescent powder such as zinc sulfide or 1-mium sulfide. Therefore, the thickness of the obtained glass fiber (5) ranges from about 50μ for a thin case to 0.5μ for a thick one. It has a diameter of about 'iJmrn.

The size of the glass fiber (5) may be appropriately selected depending on the purpose, such as the diameter and wall thickness of the glass tube (1), the shape of the end (a) (conditions, and the feed of the glass tube (1)). Of course, the surface can be set arbitrarily by adjusting the speed, the speed at the time of stretching, etc. This stretching speed is usually 30 to 200 r.
A speed of In/sec is a preferred range.

Next, the second aspect of the present invention will be explained.

FIG. 2 is a schematic front cross-sectional view showing one embodiment of a method for using luminescent fluorescent glass beads.

As shown in this figure, for example, a releasable cylinder (6) is installed in an inclined manner, and a furnace (7) is installed around the outer periphery of this 1*1 mold releasable cylinder (6). The inside of the releasable cylindrical body (6) of the lever is heated to 11 points or more of the glass at a temperature of, for example, 1000 to 300''C.

Then, the luminescent fluorescent glass fiber (5) obtained according to the first invention described above is cut into appropriate lengths, and heated little by little while being vibrated by the charging container (8). It falls into the releasable cylindrical body (6).

In this way, the glass fiber (5) is heated above its melting point and becomes fluid, and due to its surface tension, it naturally deforms into a spherical shape within a predetermined time while passing through the Type II cylindrical body (6). It becomes a small ball (9) and is stored in the receiver QQK.

The paris-repellent cylinder (6) is a cylinder made of a material to which molten glass does not adhere; for example, a cylinder made of carbon is preferable.

1. The cut length of this glass fiber (5) varies depending on the purpose, but it is usually suitable to have a length in the range of 3 to 15 pieces.

The residence time under temperature conditions above the melting point of this glass,
In other words, in the embodiment shown in FIG. 2, the time for passing through the releasable cylinder (6) varies depending on the heating conditions, but the
A range of 10 seconds is suitable.

In addition, this addition #! Even better results can be obtained by applying appropriate vibrations to the device itself.

Glass spheres manufactured in this way fQ)H approximately 0.3~
It has a straight line of about 2 degrees, and although it includes completely spherical shapes, it goes without saying that it also includes a considerable number of slightly deformed spherical shapes, and most of them are glass fibers (5)
are intricately intertwined, forming a spherical shape.

This heating means is not limited to the embodiment shown in FIG. It is also possible to drop the glass through a heating device without making contact with other objects, and it would be better if the vorticity was higher than the melting point of glass.

The method for producing the phosphorescent glass fiber and the phosphorescent glass globules of the present invention has been described above, and the phosphorescent material obtained in this way is completely encapsulated by the glass body. As a result, it is strengthened and strengthened, and its weather resistance, water resistance, abrasion resistance, heat resistance, etc. have been dramatically improved.

In the case of phosphorescent fluorescent glass fibers, if used as glass fibers for FRP, for example, FRP with phosphorescent fluorescent properties can be used.
It can also be crushed and mixed with plastic raw materials, combined with other glass materials and resins, or mixed into liquid materials, and can be used for various outdoor purposes. In addition, in the case of phosphorescent glass beads, it is possible to form a phosphorescent tile by attaching them to the surface of the tile at the same time as firing the tile. It is also possible to combine it with glass materials, attach it to the surface of the letters on road signs, mix it with white lines on roads, etc. to make the driving lines clear at night by emitting light, and use it for various indoor and other purposes. It can be applied to outdoor information boards, decorations, lights, displays, etc.

Example 1 Nine parts of the inside of a glass tube were filled with zinc sulfide powder as a luminescent fluorescent powder. Note that this glass tube was made of soda glass with an outer diameter of 5 mm, an inner diameter of 3 mm, and a softening point of F190''C.

One end of the glass tube 11111 filled with this powder was inserted into a cylindrical electric furnace made of nichrome wire and heated to about 65 (1"C). Eventually, this end became soft, so use a bottle set to remove the tip. The glass fibers were connected to a drawing device that pulled the glass fibers at a drawing speed of 75 (a) per second to form glass fibers continuously.

In this case, continuous production was possible by feeding the glass tube toward the tip at a rate of about 5 (7) minutes per minute.

As a result, glass fibers with a diameter of approximately Q, 15 mm were obtained.
The center was tightly packed with zinc sulfide.

The initial fluorescence brightness, afterglow time, etc. of this product are completely the same as those of the raw material 11 lead sulfide itself, and even after 6 months of use, it has completely maintained this state.
It has been found that its durability is extremely excellent.

This outdoor test] is currently ongoing and the final results of its durability are unknown, but at least (li)7-
Since no deterioration was observed during monthly tests, it was determined that it was almost semi-permanent.

By the way, when zinc sulfide powder was left outdoors under direct sunlight in midsummer, it began to turn black in about 60 hours, or about two and a half days, and its phosphorescent properties deteriorated.

Example 2 A device as shown in Fig. 2, in which the length of the carbon cylinder is 6 (
IDn with an inclination angle of 45 degrees was prepared, and the inside of this carbon cylinder was heated to about 10 to 1200°C in an electric furnace provided around the outer periphery of the carbon cylinder.

Then, the luminescent fluorescent glass fiber obtained in Example 1 was
It was cut into a length of 8 mm (5.6 mm on average) and dropped into the carbon cylinder described in -1-.

The residence time of this glass fiber in the cylinder is about 1 to 3 seconds, and the glass fibers are entangled in an R-shape from the bottom end of the cylinder due to surface tension.
A small glass ball fell and was stored in a receiver while being cooled in the air.

As a result, the diameter is about 0.4 to 1. (A large number of 1 mm glass globules were manufactured, and zinc sulfide existed in the spherules in a completely encapsulated state.

The phosphorescent glass spherules with phosphorescence exhibit the same phosphorescent properties as the raw material zinc sulfide, and, like the glass fibers of Example 1, their durability remains unchanged even after being left outdoors for 6 months. Fluorescence is the first. It has been determined that it has a semi-permanent phosphorescent property.

[Brief explanation of the drawing]

Figure 1 is an example of the manufacturing method of luminescent fluorescent glass fiber) J0
It is a schematic front cross-sectional view showing a Σ example. Figure 2 shows an example of the method for producing luminous fluorescent glass spheres.
It is a front sectional schematic diagram showing 100 IA1. (1) Glass tube, (2) Hollow part, (3) Luminescent fluorescent powder, (4) Heating furnace, (5) Glass fiber,
(6)・Releasable cylindrical body, (7)・Kayu (furnace), (8)...
Insertion container, (9)...Glass sphere, (10)...Receptacle Figure 1

Claims (1)

[Scope of Claims] 1. Filling the hollow part of a glass tube with luminescent fluorescent powder, and stretching the glass tube successively from the end thereof while heating and softening the end part to form a fiber-like powder. A method for producing characteristic luminescent fluorescent glass fibers. 2 Fill the hollow part of a glass tube with phosphorescent powder, and draw the end of the glass tube successively while heating and softening the end to form a fibrous glass. Then, this fibrous glass is A method for producing phosphorescent glass spherules, which comprises cutting the phosphorescent glass spherules into spherical shapes by surface tension by holding the spherules in the same shape for a predetermined period of time under conditions of a blackness higher than the melting point of the glass.