JP2003073547A - Silicone having luminous property and product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicone having luminous property in which a state to be readily checked visually by luminescence of luminous fluorescent substance is continued for many hours and luminance can be kept for a long period of time by preventing the deterioration of the surface of a luminous substance and which is easily processed and has luminous properties and its product. SOLUTION: This silicone having luminous properties is obtained by mixing a luminous fluorescent substance, a powdery and granular luminous burned substance formed by mixing the luminous fluorescent substance with lead-free frit, heating the mixture and grinding the obtained glassy luminous burned substance or a fluorescent substance having luminous property being a mixture of the luminous fluorescent substance and the powdery and granular luminous fluorescent substance with silicone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone having a phosphorescent property, which comprises a phosphorescent phosphor of a specific composition and a silicone, and a silicone product using the same.

[0002]

2. Description of the Related Art Conventionally, it has been considered that silicone impregnated with a phosphor is used as a sealing material for buildings, etc. As the phosphor, ZnS type, SrS type, etc. are irradiated with visible light or ultraviolet rays. Then, it is known that the light energy is absorbed and stored, and even after the light irradiation is stopped, the stored energy is emitted again as light (emits light).

[0003]

Since most conventional phosphors have a long emission time (afterglow time) of about 1 to 2 hours, the present invention provides a long-lasting afterglow. It is an object of the present invention to provide a product having a high brightness, that is, a so-called phosphorescent property, which is excellent in so-called phosphorescent performance, and which has a phosphorescent property that is easily processed, and a material thereof.

[0004]

According to a first aspect of the present invention, at least silicone and the following general formula (M1-pq, EupQq) O.n (Al ₁ -mBm) ₂ O ₃ , 0. 0001 ≦ p ≦ 0.5, 0.0001 ≦ q ≦ 0.5, 1.5 ≦ n ≦ 3.0, 0 ≦ m ≦ 0.5 (where M in the composition formula is Mg, Ca, Sr At least 1 selected from the group of divalent metals consisting of Al, Ba, and Zn
Seed, Q is a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb
And at least one selected from the group consisting of Lu. ) A phosphorescent silicone characterized in that it is a mixture with a phosphorescent phosphor represented by (1).

A second aspect of the present invention is a powdery or granular phosphorescent phosphor which is mixed with at least silicone, and the phosphorescent phosphor according to claim 1 is contained in the composition. A phosphorescent silicone, which is formed by mixing and heating a lead-free frit containing at least CaO, MgO and ZnO and crushing the obtained glassy phosphorescent fired body. Is.

According to a third aspect of the present invention, the phosphorescent material mixed with at least silicone is the phosphorescent phosphor according to claim 1 or the powdery or granular material according to claim 2. It is a mixture of a phosphorescent fired body, which is a silicone having a phosphorescent property.

The above-mentioned inventions according to claims 1 to 3 specify a phosphorescent material to be mixed with silicone, and the phosphorescent phosphor specified in the present invention remains for a long time. By mixing with silicone, which is a phosphor that retains light and has high brightness and excellent phosphorescence, it is possible to provide a phosphorescent material that is easy to process such as molding, cutting, embedding, and fixing. It was

A fourth invention according to claim 4 is at least the following general formula: (M1-pq, EupQq) O.n (Al ₁ -mBm) ₂ O ₃ , 0.0001 ≦ p ≦ 0.5 , 0.0001 ≤ q ≤ 0.5, 1.5 ≤ n ≤ 3.0, 0 ≤ m ≤ 0.5 (where M in the composition formula is Mg, Ca, Sr, Ba, and Zn) At least one selected from the group of divalent metals
Seed, Q is a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb
And at least one selected from the group consisting of Lu. ) And a lead-free frit containing at least CaO, MgO and ZnO in the composition,
The method for using a silicone having a light-accumulating property according to any one of claims 1 to 3, for the purpose of utilizing a glass-like light-accumulating fired body obtained by mixing and heating.

A fifth invention according to claim 5 is claim 4
And a glass-like phosphorescent fired body according to any one of claims 1 to 3, which is used for the ship and the berth.

According to a sixth aspect of the present invention, the first aspect is the first aspect.
~ A phosphorescent silicone according to claim 3 and the glass-like phosphorescent fired body according to claim 4 are used as a fishing equipment, a fishing buoy, a fishing lure,
It is an invention relating to fishing floats and the like.

A seventh aspect of the present invention is the first aspect.
~ It is a safety tool characterized by using the silicone having a light-accumulating property according to claim 3 and the glass-like light-accumulating fired product according to claim 4, which is located by applying it to a protrusion, a rope or the like. Is to confirm.

An eighth invention according to claim 8 is claim 1
~ It is a diving tool characterized by using the phosphorescent silicone according to claim 3 and the glassy phosphorescent fired body according to claim 4, which is applied to wetsuits, underwater glasses, fins and the like. This makes it easier for the diver to see.

[0013]

EXAMPLE An embodiment of the silicone having a luminescent property of the present invention will be described below with reference to the drawings.

1 to 3 are schematic views showing that the phosphorescent silicone 10 of the present invention is a mixture of a phosphor and silicone. In FIG. 1, the silicone 2 and the phosphorescent phosphor 4 are It is mixed.

Silicone 2 is generally a chemical substance in which an inorganic siloxane bond (Si-O-Si) and an organic methyl group or phenyl group are present in the same molecule.
It is known that there are properties due to the siloxane bond of the main chain and due to the chemical structure of silicone, and the properties of silicone resin or silicone rubber are also widely known. The material and composition of the silicone are not limited, but in the present invention, the translucent silicone is most suitable because the silicone and the phosphorescent phosphor are mixed.

The phosphorescent phosphor 4 is similar to the "afterglow phosphor" disclosed in Japanese Patent No. 2951902. Specifically, the phosphorescent phosphor has a specific composition represented by the following general formula. (M1-pq, EupQq) O.n (A1 _1- mBm) ₂ O ₃ 0.0001 ≦ p ≦ 0.5, 0.0001 ≦ q ≦ 0.5, 1.5 ≦ n ≦ 3.0, 0 ≦ m ≦ 0.5, where M is at least 1 selected from the group of divalent metals consisting of Mg, Ca, Sr, Ba and Zn.
Seed, Q is a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb
And at least one selected from the group consisting of Lu. )

For the phosphorescent phosphor, the following raw materials are sufficiently mixed in a mixer so as to have the above composition, and 1200 in the air.
It is obtained by first baking at a temperature of about 1600 ° C. for several hours, then performing secondary baking at a temperature of about 1200 ° C. to 1600 ° C. in a weak reducing atmosphere, crushing the baked product, and sieving.

Raw materials for the phosphorescent phosphor include SrO and A
A metal oxide such as l ₂ O ₃ , Eu ₂ O ₃ or a compound such as SrCO ₃ which easily becomes an oxide at a high temperature during firing is suitable. Besides, nitrates, oxalates, hydroxides and the like can be used. Since the light emission characteristics depend on the purity of the raw materials, it is necessary that these raw materials have a purity of 99.9% or higher, and more preferably 99.99% or higher.

By including boron in the composition of the phosphorescent phosphor, the crystallinity of the phosphor matrix (aluminate) is improved as boric aluminate. In addition, the afterglow time (the time after which light of the phosphorescent phosphor can be visually recognized in the dark after the light irradiation is stopped) and the afterglow brightness are improved, for example, the emission center and the capture center are stabilized and the luminous brightness is increased. . In order to introduce boron into the composition, a method of adding a compound containing boron as a flux and firing it is effective. As such a compound, boric acid or a borate of an alkaline earth element can be used, and boric acid is particularly preferable. Most of the added boric acid is introduced into the composition of the phosphorescent phosphor. Boron is preferably added so that the amount m of boron substituting for aluminum belongs to the range of 0.0001 to 0.5, more preferably 0.005 to 0.25, and most preferably 0.
It is around 05. The introduction of boron is effective not only for improving the light emitting performance of the phosphorescent phosphor but also for lowering the coefficient of thermal expansion of the glassy phosphorescent material.

The above-mentioned phosphorescent phosphor basically exhibits strong luminescence due to divalent Eu which is an activator, but since divalent Eu absorbs in a wide range from visible light to ultraviolet region, it seems to be like natural light. Excited in a wide range of wavelengths, it emits light with high efficiency.
Therefore, it is excited by not only sunlight but also artificial lighting such as an incandescent lamp and a fluorescent lamp to emit light.

The activator and co-activator introduced into the phosphorescent phosphor are related to the fluorescent color and the afterglow brightness, and their concentration range is important for practical use. For example, the preferable range of the concentration p of the activator Eu introduced into the phosphorescent phosphor is 0.001 to 0.0.
It is 6.

The coactivator is Mn, Zr, Nb, Pr, N.
d, Gd, Tb, Dy, Ho, Er, Tm, Yb and L
Although it has already been described that the co-activator is at least one selected from the group consisting of u, it is preferable to use two types of co-activators selected from the above group.
In the case of using these two types, the first coactivator and the second coactivator can be considered separately. Dy, Nd, Pr, Ho and Er are mainly used as the first coactivator. When the divalent metal M in the phosphor composition formula is Sr,
Dy, Pr, Tm, Ho and Er are effective in improving the afterglow brightness, and in this case, the emission color is in the blue-green range.

When Dy is selected as the first coactivator, the optimum range of Dy concentration q which affects the light emission performance is 0.00.
It is 05 to 0.03. When Dy is selected as the first co-activator and Mn is selected as the second co-activator, Mn
The preferred range of the concentration q is 0.0001 to 0.06, and the more preferred range is 0.0005 to 0.02. When Dy is selected as the first coactivator and Tm is selected as the second coactivator, the preferable range of the Tm concentration q is 0.0003 to 0.02, and the more preferable range is 0.
It is 0004 to 0.01. Dy as the first coactivator
And when Lu is selected as the second coactivator,
The preferable range of the Lu concentration q is 0.0001 to 0.06.
Therefore, a more preferable range is 0.0004 to 0.04. When Dy is selected as the first coactivator and Nd is selected as the second coactivator, the preferable range of the Nd concentration q is 0.0001 to 0.08, and the more preferable range is 0.0003. Is about 0.04.

Dy is selected as the first coactivator and the second is
When Yb is selected as the co-activator, the preferable range of the Yb concentration q is 0.0002 to 0.04, and the more preferable range is 0.0003 to 0.01. When Dy is selected as the first coactivator and Zr is selected as the second coactivator, the preferable range of the Zr concentration q is 0.002 to 0.002.
It is 0.70. Select Dy as the first co-activator,
When Er is selected as the second coactivator, the Er concentration q
Is preferably 0.0001 to 0.03, and more preferably 0.0005 to 0.02. Dy is selected as the first coactivator and Pr is selected as the second coactivator.
When Pr is selected, the preferable range of Pr concentration q is 0.00
01 to 0.04, more preferably 0.0005
Is about 0.03.

The total number of moles of the oxide of the divalent metal, the activator and the co-activator and the total number of moles of alumina and boric acid are approximately 1: 2,
That is, in the case of n = 2, when the substitution of boron is as low as about 1 mol%, SrAl ₄ O ₇ to be produced from the charged composition.
However, when the concentration of boron is higher than this, Sr ₄
It becomes a mixture of the Al ₁₄ O ₂₅ structure and the SrAl ₁₂ O ₁₉ structure.

Of these crystal structures, the Sr ₄ Al _{1 4} O ₂₅ structure is particularly important as the matrix of the phosphorescent phosphor.
This belongs to the orthorhombic system. By introducing a predetermined amount of boron, the crystal structure changes and the afterglow property is improved. Especially n =
In the vicinity of 1.75, blue-green light emission with a peak wavelength of 490 nm becomes the strongest, and a high-purity phosphorescent phosphor having an Sr ₄ Al ₁₄ O ₂₅ structure as expected from the amount of raw material charged can be obtained. This phosphorescent phosphor is excellent in heat resistance and weather resistance.
The phosphorescent phosphor having the Sr ₄ Al ₁₄ O ₂₅ structure is 1.5 ≦ n
It is obtained in the range of ≤3.0, particularly as the main component in the range of 1.7≤n≤2.1.

On the other hand, when the total number of moles of oxides of the divalent metal, the activator and the co-activator and the total number of moles of alumina and boric acid are approximately 1: 1, that is, n = 1. The crystal structure is a SrAl2O4 type monoclinic system, and green light emission having a peak at a wavelength of 520 nm is exhibited. Although this phosphor also exhibits afterglow property, it is not suitable for use in a phosphorescent phosphor that requires high afterglow property because heating after it is heated at a high temperature causes a significant decrease in afterglow brightness.

FIG. 2 is a schematic diagram showing that the phosphor mixed with silicone is a powdery or granular phosphorescent fired product comprising the phosphorescent phosphor and lead-free frit. The granular and granular phosphorescent fired bodies 6 are mixed.

The powdery or granular phosphorescent fired body 6 to be mixed with the silicone 2 is mixed with the phosphorescent phosphor and the lead-free frit and heated, and the obtained glassy phosphorescent fired body is crushed. When the phosphorescent phosphor and the lead-free frit are mixed and heated, the temperature is preferably 800 to 850 ° C., and the time is 6 to
It is desirable to bake for 8 hours.

A frit is a glass component that melts at low temperatures. The lead-free frit contains at least CaO, MgO, and ZnO in its composition.
₂ , Al ₂ O ₃ , K ₂ O, Na ₂ O, B ₂ O ₃ may be contained. However, the lead-free frit does not contain lead such as lead oxide or cadmium such as cadmium oxide. If these components are contained, when a phosphorescent material is added to the frit and baking is performed, lead or cadmium may react with the phosphorescent material and the frit may turn black.

The preferable composition ratio of the lead-free frit is Si.
O ₂ is 25% by weight or more and 60% by weight or less, Al ₂ O ₃ is 5% by weight or more and 15% by weight or less, CaO is more than 0, and 10
% By weight, MgO is more than 0, 2% by weight or less, Zn
O is more than 0 and 2% by weight or less, K ₂ O is 2% by weight or more and 4% by weight or less, Na ₂ O is 4% by weight or more, 8% by weight
Below, B ₂ O ₃ is 10% by weight or more and 25% by weight or less.

The lead-free frit is obtained by weighing oxide compounds and carbonate compounds having the above composition and mixing and dissolving them. By using such a lead-free frit, it does not react with the phosphorescent phosphor even in a high temperature atmosphere during firing, and the function of the phosphorescent phosphor can be sufficiently exerted. Lead-free frit also has excellent weather resistance, heat resistance, corrosion resistance, and stain resistance.

The phosphorescent phosphor and the lead-free frit are
Mixing and heating, the resulting glass-like luminous phosphor,
The phosphorescent phosphor retains the afterglow for a long time and has high brightness, which is excellent in so-called phosphorescence performance, and the weather resistance, heat resistance, corrosion resistance, and stain resistance of lead-free frit. It is something. Its properties are not impaired when ground into powder and granules.

FIG. 3 is a schematic diagram showing that the phosphor mixed with silicone is a mixture of the phosphorescent phosphor and the powdery or granular phosphorescent fired product. Phosphor 4 and powdery or granular phosphorescent fired body 6 are mixed.

FIG. 4 is an example of a method of using a silicone having a light-accumulating property for the purpose of utilizing a glass-like luminous phosphor. In FIG. 4A, the entire surface of the glass-like luminous phosphor 8 is covered with the silicone 10 having luminous properties. FIG. 4A shows an example in which the light-accumulating silicone 10 is used as a buffer material and an adhesive material. The glass-like luminous phosphor is obtained by mixing and heating the luminous phosphor and the lead-free frit.

The glass-like luminous phosphor is capable of keeping afterglow for a long period of time and having high brightness, that is, excellent so-called luminous performance by using the above-mentioned phosphorescent phosphor. At least CaO, MgO and Z
It is a glass-like fired body that uses lead-free frit containing nO, and is feared to be broken or broken due to excessive impact.

By coating the glass-like luminous phosphor with the phosphorescent silicone of the present invention, it is protected by elasticity, which is one of the characteristics of the silicone, even under an excessive impact. Further, even when the glass-like luminous phosphor is cracked, crushed or otherwise damaged due to excessive impact, the glass-like luminous phosphor is covered and protected so that the shape of the glass-like luminous phosphor is not significantly impaired.

Next, a ship and a quayside quay buffer, which is one of the present invention, has the glass-like phosphorescent fired body according to claim 4 and the phosphorescent property according to claims 1 to 3. This is a shoreside shock absorber characterized by using silicone.
It is installed at the periphery of the quay or on the edge of a ship and serves as an indicator at night or in a dark place.By irradiating ultraviolet rays with a black light, etc., it retains its luminous performance and shines brightly, and also as an illumination. It can be used.

As a mode of use, firstly, a glass-like material which is provided with a recess in a conventional quayside cushion and is coated with silicone having a light-accumulating property shown in FIG. The phosphorescent fired body according to claim 4, which is embedded, may be attached to or protruded from the surface of a conventional quayside buffer body, and the glassy phosphorescent fired body according to claim 4 and claims 1 to 1. If the phosphorescent silicone described in item 3 is used, the form of use is not specified because of the ease of processing, which is one of the characteristics of silicone.
It is not specified considering that it can be utilized both in shape and as illumination.

The fishing equipment, which is one of the present invention, relates to the use of a silicone product having a luminous property and is utilized as a member for fishing buoys, fishing lures and the like. The glassy phosphorescent fired body and powdery and granular phosphorescent fired bodies have excellent weather resistance, heat resistance, corrosion resistance, and stain resistance, and the phosphorescent phosphor is seawater. By keeping the afterglow for a long time and the state of high brightness without being eroded by the coating, and by coating with the phosphorescent silicone of the present invention, the elasticity, which is one of the characteristics of silicone even in excessive impact, It is protected.

The fishing buoys are generally used for day and night by mooring them to position marks such as fishing nets and rafts, or route markings, and are easily damaged by excessive impact, and at night. In addition, there were problems such as positively indicating the position of the buoy. A buoy is wholly or partially coated with the light-accumulating silicone according to claims 1 to 3 of the present invention. Alternatively, the glass-like luminous phosphor according to claim 4 is attached to a buoy using silicone having a luminous property so as to maintain a state easily visible at night for a long time and prevent damage to the buoy. When used in combination with a flashing lamp or irradiated with ultraviolet light from a black light, it retains its luminous performance and shines clearly.

A fishing lure, which is one of the silicone products having a light-accumulating property, takes advantage of the habit that many fish gather in the luminous body, and the lure body is the glass-like luminous luminous body. Some lures are made of the luminous silicone of the present invention, or prefabricated lures are coated with the luminous silicone of the present invention. By irradiating with, the luminous performance can be further enhanced.

A security tool using the phosphorescent silicone according to any one of claims 1 to 3 and the glass-like phosphorescent calcined material according to claim 4 is applied to a protrusion, a rope or the like. To confirm the whereabouts. In the case of the protrusion, the protrusion is covered with silicone having a light-accumulating property so that the location can be confirmed and the elasticity of the silicone protects the body during contact.

The use of the light-accumulating silicone of the present invention is various, but particularly in the case of liquid silicone, so-called post-molding such as fixing or embedding is possible, so that it can be applied to a long string-like object such as a rope. Suitable for use,
As a method, as shown in FIG. 5, the entire spiral portion 14 of the rope 12 is partially or partially embroidered using the light-accumulating silicone 10 of the present invention. Or it sticks. Luminescent ropes are suitable for rescue at night and as ropes for territory, and are suitable for nighttime safety. By radiating ultraviolet rays with black light, the luminous performance can be further enhanced.

Hitherto, various methods have been extensively tried to give a diving tool a fluorescent color so that the diver can easily see it. However, most of them have a short afterglow time and a low luminance, that is, they have a poor so-called luminescent property, and thus, they have a long term. The phosphor is further deteriorated by use.

The light-accumulating silicone according to claims 2 and 3 of the present invention and the glass-like light-accumulating fired body according to claim 4 have excellent light-accumulating performance, and further have weather resistance,
Since it has properties such as heat resistance, corrosion resistance, and stain resistance, it is suitable for parts of diving equipment that is immersed in seawater, such as wet suits, underwater glasses, fins, etc., and it is easy to apply it to existing products. . At the time of diving, the light storage performance is enhanced by irradiating ultraviolet rays with a black light in advance.

It is widely known that the silicone is packaged in the tubular container, and the silicone having the phosphorescent property of the present invention is also packaged in the tubular container to expand the range of use.

[0048]

As described above, according to the inventions described in claims 1 to 3, as a phosphor, a general formula (M1-pq, EupQq) O.n (A1 _1- mBm) ₂ O ₃ , 0.0001 ≤ p ≤ 0.5, 0.0001 ≤ q ≤ 0.5, 1.5 ≤ n ≤ 3.0, 0 ≤ m ≤ 0.5 (where M in the composition formula is Mg, Ca At least 1 selected from the group of divalent metals consisting of Sr, Sr, Ba, and Zn
Seed, Q is a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb
And at least one selected from the group consisting of Lu. The range of specifications was expanded by mixing or impregnating silicone with a phosphorescent substance capable of high afterglow brightness and long-time light emission by using a phosphorescent phosphor expressed as). Further, according to the invention of claim 4, the glassy phosphorescent fired product capable of high afterglow brightness and long-term light emission is provided with the high afterglow brightness of the present invention and long-time light emission. High light storage performance could be maintained by protecting with silicone having.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a mixed state of a phosphorescent silicone of the present invention in which a phosphorescent phosphor is mixed.

FIG. 2 is a schematic diagram showing a mixed state of the silicone having a phosphorescent property of the present invention in which powdery and granular phosphorescent fired products are mixed.

FIG. 3 is a schematic diagram showing a mixed state of the silicone having a phosphorescent property of the present invention in which a phosphorescent phosphor and a powdery or granular phosphorescent fired product are mixed.

FIG. 4 (a) Example of use as a protective material of the present invention (A) Example of use as a cushioning material of the present invention

FIG. 5: Example of processing according to the present invention

[Explanation of symbols]

2 silicone 4 Luminescent phosphor 6 Powdery and granular phosphorescent fired bodies 8 Glass-like luminous phosphor 10 Silicone with luminous properties 12 rope 14 Spiral part of rope

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B63B 59/02 B63C 11/02 B63C 11/02 C08K 3/22 C08K 3/22 C09K 11/08 B C09K 11 / 08 11/64 CPM 11/64 CPM A01K 85/00 ZF term (reference) 2B107 BA70 BB07 4H001 CA04 CA05 CF02 XA05 XA08 XA12 XA13 XA20 XA30 XA38 XA56 YA25 YA40 YA41 YA71 YA41 YA71 YA71 CP031 DE066 DE076 DE086 DE096 GT00

Claims (8)

[Claims] 1. At least silicone and the following general formula: (M1-pq, EupQq) O.n (Al ₁ -mBm) ₂ O ₃ , 0.0001 ≦ p ≦ 0.5, 0.0001 ≦ q ≦ 0.5, 1.5 ≦ n ≦ 3.0, 0 ≦ m ≦ 0.5, (M in the composition formula is selected from the group of divalent metals consisting of Mg, Ca, Sr, Ba, and Zn. At least 1
Seed, Q is a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb
And at least one selected from the group consisting of Lu. ) A phosphorescent silicone, characterized in that it is a mixture with a phosphorescent phosphor represented by (1). 2. A powdery and granular phosphorescent fired body, which is mixed with at least silicone, is a lead-free frit containing the phosphorescent phosphor according to claim 1 and at least CaO, MgO and ZnO in the composition. Silicone having a light-accumulating property, characterized in that it is formed by mixing and heating, and crushing the obtained glassy light-accumulating fired body. 3. The phosphorescent substance mixed with at least silicone is a mixture of the phosphorescent phosphor according to claim 1 and the powdery or granular phosphorescent calcined substance according to claim 2. Characteristic silicone that has a luminous property. 4. At least the following general formula: (M1-pq, EupQq) O.n (Al ₁ -mBm) ₂ O ₃ , 0.0001 ≦ p ≦ 0.5, 0.0001 ≦ q ≦ 0.5 , 1.5 ≦ n ≦ 3.0, 0 ≦ m ≦ 0.5, where M is at least selected from the group of divalent metals consisting of Mg, Ca, Sr, Ba, and Zn. 1
Seed, Q is a co-activator, Mn, Zr, Nb, P
r, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb
And at least one selected from the group consisting of Lu. ) Is mixed with a lead-free frit containing at least CaO, MgO and ZnO in the composition, and the mixture is heated, for the purpose of utilizing the glassy phosphorescent fired body obtained. The method of using the silicone having a luminous property according to any one of claims 1 to 3. 5. A berthing quay buffer for ships and quays, comprising the glass-like luminous phosphor of claim 4 and the silicone having luminous properties of claims 1 to 3. 6. A fishing equipment, characterized by using the phosphorescent silicone according to any one of claims 1 to 3 and the glass-like phosphorescent fired body according to claim 4. 7. A safety tool using the silicone having a light-accumulating property according to any one of claims 1 to 3. 8. A diving equipment, characterized by using the phosphorescent silicone according to any one of claims 1 to 3 and the glass-like phosphorescent calcined product according to claim 4.