JPH10273657A - Light storing adornment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light storing adornment capable of using in outdoors, excellent in light storing properties, heat resistance, water resistance, surface flatness, stain resistance and fanciness. SOLUTION: This light storing adornment is obtained by forming a light storing layer 2 containing a light storing fluorescent agent and a lead free glass frit on the surface of a substrate 1 and coating the surface of the light storing layer 2 with a lead free glass. The light storing layer preferably contains 35-95 pts.wt. of the light storing fluorescent agent, 65-5 pts.wt. of the lead free glass frit, where the thickness of the light storing layer is 30-800 μm, and thickness of the lead free glass layer is 10-300 μm. An earthenware, a porcelain, a glass, a crystallized glass, a vitreous enamel, etc., are used as the substrate 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a heat-resistant,
The present invention relates to a phosphorescent decorative article having excellent water resistance and surface smoothness.

[0002]

2. Description of the Related Art Luminescent property is a property of accumulating light energy of fluorescent lamps and sun rays and retaining afterglow in the dark.
An example of the use of this technology is a luminous safety sign board. Luminescent safety signboards are evacuation / guidance signs, rescue signs, danger / prohibition signs, etc. These consist of a luminous layer formed by applying luminous powder on the surface of a substrate made entirely of synthetic resin such as vinyl chloride. It is. Japanese Patent Application Laid-Open No. 4-51405 proposes a luminous wall covering material in which a luminous powder is applied to a wall covering material such as synthetic resin and paper as a safety sign by luminous storage. As the phosphorescent powder, for example, there is a zinc sulfide powder that emits fluorescence.

[0003]

However, the above-mentioned conventional luminous member is a combustible material such as a synthetic resin or a wall material made of paper. Therefore, when a luminous layer is formed on these surfaces to produce a luminous safety signboard, the luminous layer will act as a safety sign in the event of a sudden power outage, but in the event of a fire, the luminous layer will melt or burn with flammable materials. The effect as a safety sign cannot be obtained.

[0004] Further, when synthetic resin and the like are burned, smoke harmful to the human body may be generated, and evacuees may be damaged by this smoke. Also, even if a luminous layer made of synthetic resin is formed on the surface of a ceramic plate, which is a non-combustible material, the luminous layer formed of synthetic resin does not exhibit its effect because it melts or burns down in a fire in the same manner as above. Problems such as generation of harmful smoke occur.

Therefore, in order to obtain a safe phosphorescent decoration, a phosphorescent powder is applied together with a glass frit on a non-combustible ceramic substrate and baked.
It is conceivable to make the luminous layer incombustible. For example, various ceramic products using phosphorescent powder have been proposed in recent years. For example, Japanese Patent Application Laid-Open No. 60-226
No. 959 proposes a tile in which a synthetic resin layer containing a phosphorescent powder is formed on the surface of a ceramic tile.

[0006] However, when the phosphorescent powder is fired in an oxidizing atmosphere, the phosphorescent power may be very weak. Therefore, when the phosphorescent powder is directly baked on a substrate such as a ceramic in air, a phosphorescent layer having a phosphorescent effect cannot be formed.

Therefore, as a means for firing the phosphorescent powder without oxidizing it, it has been proposed to mix it with a glaze and fire it (Japanese Patent Application Laid-Open No. 58-173182, Japanese Patent Application Laid-Open No. H08-173182).
165140). However, in the case of glaze, 1000
It must be fired at a high temperature of at least 30 ° C for at least 30 minutes to 1 hour. In addition, fluorescent phosphors are not only easily oxidized, but also vulnerable to long-term high temperatures. Therefore, there is a problem that if the phosphorescent powder is mixed with the glaze and fired, a sufficient phosphorescent effect cannot be obtained.

Further, in the case of glaze, it is effective to cover the entire surface of the substrate with a luminous layer. However, a delicate character or pattern is partially formed on the surface of the substrate by the luminous layer, or the luminous layer and the luminous layer. It is not possible to freely create a decorative layer that is not used. In addition, it is difficult to freely form the luminous layer to an arbitrary thickness.

Further, when the luminous powder is pulverized, the luminous ability is reduced, and in some cases, the luminous property is lost. Therefore, the phosphorescent powder is not pulverized, but has an average particle size of 5
It is necessary to bake on the substrate while keeping the relatively large state of about 50 μm. However, when a phosphorescent powder that is not pulverized is used, the surface of the phosphorescent decorative article cannot be smooth, and dirt is likely to adhere.

Further, the luminous powder has low water resistance. Therefore, it cannot be used outdoors or in a pool where there is a risk of contact with water while the phosphorescent powder is exposed.

The present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a phosphorescent decorative article which can be used indoors and outdoors and has excellent heat resistance, water resistance and surface smoothness.

[0012]

According to the first aspect of the present invention, the surface of the substrate is
A luminous decorative article comprising: a luminous layer containing luminous powder and a lead-free glass frit; and a surface of the luminous layer coated with a lead-free glass layer.

In the present invention, the most remarkable point is that the luminous layer containing the luminous powder and the lead-free glass frit is covered with the lead-free glass layer.

Next, the operation and effect of the present invention will be described. In the phosphorescent decorative article of the present invention, the phosphorescent layer containing the phosphorescent powder is covered with a lead-free glass layer. Therefore, when these are fired on the substrate, oxidation of the phosphorescent powder can be suppressed. Therefore, even when firing in an oxidizing atmosphere, the luminous effect is not lost. Therefore, the phosphorescent decorative article of the present invention can obtain the same phosphorescent effect as before baking, and is excellent in heat resistance.

The luminous layer is covered with a lead-free glass layer. Therefore, since the phosphorescent decorative article of the present invention is not exposed to air or water, oxidation of the phosphorescent powder can be suppressed. Therefore, the luminous decorative article of the present invention can be used outdoors or on the waterside without deterioration of the luminous effect.

Further, as a glass layer for covering the luminous layer,
When leaded glass is used, the luminous powder may be blackened and the luminous ability may be reduced. However, in the present invention, since the light-storing layer is covered with a lead-free glass layer containing no lead, the light-storing layer does not turn black and exhibits excellent light-storing properties.

Further, since the light-storing layer is covered with the lead-free glass layer, the surface of the light-storing decorative article does not have a rough surface, and has excellent smoothness on the back surface. Therefore, dirt does not easily adhere to the surface. In addition, even if dirt adheres, the dirt can be easily removed by wiping or the like, and the stain resistance is strong.

The light-storing layer is formed by printing, spraying or brushing directly on the substrate, or by transferring it with a transfer paper prepared in advance. Therefore, it can be formed at an arbitrary position and with an arbitrary size and shape. Also, patterns such as patterns and characters can be represented. Furthermore, the luminous layer or the lead-free glass layer can be formed to have an arbitrarily selected layer thickness.

As described above, according to the present invention, it is possible to provide a luminous decorative article which can be used indoors and outdoors and has excellent luminous properties, heat resistance, water resistance, surface smoothness, stain resistance and decorativeness. it can.

Next, as in the second aspect of the present invention, the luminous layer preferably comprises 35 to 95 parts by weight of the luminous powder and 65 to 5 parts by weight of the lead-free glass frit. Thereby, excellent luminous properties can be exhibited. On the other hand, if the luminous powder is less than 35 parts by weight, or if the lead-free glass frit exceeds 65 parts by weight, the luminous action of the luminous layer may be weakened. The luminous powder is 95
Exceeding parts by weight or 5% lead-free glass frit
If the amount is less than part by weight, the luminous powder is oxidized and the luminous layer is whitened, so that the luminous effect may not be obtained.
More preferably, the luminous powder is 40 to 90 parts by weight, and the lead-free glass frit is 60 to 10 parts by weight. Within this range, a more excellent light storage effect can be obtained.

According to the third aspect of the present invention, it is preferable that the thickness of the lead-free glass layer is equal to or larger than the particle size of the luminous powder. Here, the particle size of the luminous powder refers to the average particle size of the luminous powder. As a result, the lead-free glass layer covers the entire surface of the phosphorescent powder, and the surface smoothness, heat resistance, and water resistance of the phosphorescent layer are further improved.

As in the invention of claim 4, it is preferable that the thickness of the luminous layer is 30 to 800 μm. 30μ
If the thickness is smaller than m, a sufficient light storing effect may not be obtained. On the other hand, when the thickness is larger than 800 μm, the luminous effect recognizable by humans is saturated, and there is a possibility that the luminous effect cannot be further improved. In addition, since a large amount of expensive phosphorescent powder is required, the cost of the phosphorescent decorative article may increase. More preferably, it is in the range of 50 to 500 μm. Within this range, the luminous layer can be easily formed,
A sufficient luminous effect can be obtained.

As in the invention of claim 5, the thickness of the lead-free glass layer is preferably from 10 to 300 μm.
Thereby, the luminous action of the luminous decorative article can be effectively exhibited. As described above, the thickness of the lead-free glass layer covering the luminous layer needs to be larger than the particle size of the luminous powder. Therefore, if the thickness is less than 10 μm, the phosphorescent powder may not be sufficiently coated.
On the other hand, if the thickness is more than 300 μm, the light storage effect may not be improved. From the viewpoint of the particle size of the phosphorescent powder to be coated, the thickness of the lead-free glass layer is preferably 20 to 300.
μm. Within this range, the phosphorescent powder can be sufficiently coated.

The average particle size of the luminous powder is 5 to 50 μm.
m is preferable. Thereby, an excellent luminous action can be exhibited. On the other hand, if it is less than 5 μm, the luminous action of the luminous layer may be reduced. If it exceeds 50 μm, the surface smoothness of the phosphorescent decorative article may be reduced.

Examples of the luminous powder include materials such as strontium aluminate and calcium aluminate to which europium and desprosium are added as activators, and zinc sulfide to which copper and cobalt are added as activators.

The lead-free glass frit serves as an adhesive for connecting the luminous powder in the luminous layer.
The lead-free glass frit includes, for example, borosilicate glass frit, soda-lime glass frit, aluminosilicate glass frit, borate glass frit, and phosphate glass that do not contain lead or cadmium. It is preferable to use a frit, an aluminate-based glass frit, or the like.

It is preferable that the lead-free glass layer has the same composition as the lead-free glass frit containing no lead or cadmium. Thereby, it can be fired at a low temperature of about 800 ° C., and a good covering layer can be formed.

Further, as in the invention of claim 6, it is preferable that the substrate is any one of pottery, porcelain, enamel, glass and crystallized glass.
Ceramic or the like can also be used.

The substrate is not limited to a plate-like body.
It also refers to those having the shape of the object itself serving as the phosphorescent decorative body (for example, the shape of a tableware, a vase). Examples of applications of this phosphorescent decoration include safety signboards, tableware, enameled kitchens, cooking utensils, pots, vase, figurines, toys, sanitary ware, electric tools such as insulators, tiles, and fine ceramic functional materials. is there.

In manufacturing the phosphorescent decorative article of the present invention, first, a phosphorescent layer is formed on the surface of a substrate having a desired shape.
That is, the phosphorescent powder, the lead-free glass frit, and the organic binder are mixed to produce a phosphorescent powder-containing paste.
The paste containing the luminous powder may be directly screen-printed on the substrate, painted with a brush, applied by spraying, or by preparing a transfer paper and transferring it to the substrate. A phosphorescent layer is formed on the substrate.

Next, a lead-free glass layer is formed on the surface of the luminous layer. That is, a lead-free glass paste is prepared by mixing a lead-free glass frit and an organic binder, and is directly screen-printed, brush-painted, sprayed, or the like onto the phosphorescent layer, or a transfer paper is prepared. Then, a lead-free glass layer is formed by a film forming means such as transferring to a luminous layer formed on the substrate. Thereafter, these are heated to a temperature higher than the vitrification temperature of the glass frit (for example, 600 ° C.).
C. to 850.degree. C.) to obtain a phosphorescent decorative article.

After forming the light-storing layer on the substrate, it is preferable to dry at room temperature, form a lead-free glass layer on the light-storing layer, and then bake. Thereby, the number of firings can be reduced and the cost can be reduced. As the organic binder contained in the above-mentioned luminous powder-containing paste and lead-free glass paste, for example, carboxymethylcellulose (hereinafter referred to as CMC), methylcellulose, ethylcellulose, acrylic resin, butyral resin and the like can be used.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 FIG. 1 shows a phosphorescent decorative article according to an embodiment of the present invention.
This will be described with reference to FIG. As shown in FIG. 1, the phosphorescent decorative article 5 of this embodiment has a phosphorescent layer 2 formed on the surface of a base 1, and the surface is covered with a lead-free glass layer 3. Luminous layer 2
Contains luminous powder and lead-free glass frit. As the base 1, a porcelain tile is used.

Next, a method for manufacturing a phosphorescent decorative article will be described. First, 50 parts by weight of a luminous fluorescent agent, 50 parts by weight of a lead-free glass frit, and 60 parts by weight of an organic binder were mixed to prepare a luminous powder-containing paste. The luminous powder used was strontium aluminate to which europium and desprosium were added as activators. As the lead-free glass frit, a borosilicate glass frit containing no lead or cadmium was used. As the organic binder, an acrylic resin dissolved in an organic solvent was used. Next, this phosphorescent powder-containing paste was printed on the surface of a porcelain tile by screen printing to form a phosphorescent layer and dried.

Next, a lead-free glass frit and an organic binder were mixed to prepare a lead-free glass paste. Lead-free glass frit is made of borosilicate glass that does not contain lead or cadmium. As the organic binder, an acrylic resin dissolved in an organic solvent was used. Then,
This lead-free glass paste was printed on the luminous layer by screen printing to form a lead-free glass layer.

This was fired while being kept at 840 ° C. for 10 minutes in an oxidizing atmosphere to obtain a phosphorescent decorative article. At this time, the lead-free glass layer covered not only the surface of the luminous layer but also the side surfaces. The thickness of the luminous layer in the luminous decorative article was 200 μm, and the thickness of the lead-free glass layer was 100 μm.

The thus obtained phosphorescent decorative article according to the present example does not deteriorate even when exposed to a flame and shows no change even when immersed in high-temperature water for a long time, exhibiting excellent phosphorescent properties. did. The surface was smooth, for example, like ordinary porcelain tableware.

Further, the phosphorescent decorative article of this example was stuck on the wall of a room or an underpass at regular intervals. And for the phosphorescent decorations,
The brightness of commonly used lighting (eg, 1000
(Looks) for 30 minutes, after which the lights were turned off. As a result, the tiles maintained their afterglow and could be clearly recognized by human eyes. Recognizable time was about 4 hours.

Embodiment 2 The luminous decorative article of this example is a luminous safety signboard as shown in FIG. That is, the phosphorescent decorative article 51 has a pattern 11 formed of characters, graphics, symbols, and the like representing safety signs formed on the surface of the base 10. This pattern 11 is composed of a green paint layer 40. Margin 12 around pattern 11
Is formed by the luminous layer 20 (see FIG. 5). The surface of the light storage layer 20 is covered with a lead-free glass layer 30. As the base 10, a porcelain tile is used.

Next, a method for manufacturing the phosphorescent decorative article of this embodiment will be described. First, as shown in FIG. 3, a green paint was screen-printed on the surface of the substrate 10 to form a pattern 11 with a paint layer 40 having a thickness of 10 μm. Next, as shown in FIG. 4, the same phosphorescent material-containing paste as in the first embodiment was screen-printed on the margin 12 on the surface of the substrate 10 to form the phosphorescent layer 20 having a thickness of 100 μm.

Then, as shown in FIG. 5, a lead-free glass paste was screen-printed on the surface of the luminous layer 20 to form a lead-free glass layer 30 having a thickness of 90 μm. Next, they were fired in an oxidizing atmosphere at 840 ° C. for 10 minutes. By firing, the lead-free glass layer flowed and covered the side surface of the luminous layer 20. Thus, the phosphorescent decorative article 51 shown in FIG. 2 was obtained.

In the luminous decoration of this embodiment, the margin 12 composed of the luminous layer 20 retains the afterglow in the dark and plays a role as a safety sign. It can be used indoors and outdoors, and has excellent heat resistance, water resistance, and surface smoothness.

Further, the phosphorescent decorative article of the present example was stuck on the wall surface of a room or an underpass at regular intervals. And for the phosphorescent decorations,
The brightness of commonly used lighting (eg, 1000
(Looks) for 30 minutes, after which the lights were turned off. As a result, the tiles persisted in the dark and were clearly visible to the human eye. Recognizable time was about 4 hours.

Thus, the phosphorescent decorative article of this example can be sufficiently used as an emergency blame sign even in the event of an emergency blame such as an earthquake, even if the power is turned off and lighting becomes impossible. Recognize. In this example, the paint layer 4
0 is green, but any color can be imparted by changing the type of paint.

Embodiment 3 As shown in FIG. 6, the phosphorescent decorative article of this embodiment has a phosphorescent layer 200.
It is a lighting fixture in which the pattern formed by is printed. That is,
The phosphorescent decorative article 52 has a decorative pattern 110 formed on the surface of the base 100. This decorative pattern 110 is formed from the luminous layer 200. Also, as shown in FIG.
The surface of the light storage layer 200 is covered with a lead-free glass layer 300. The substrate 100 is made of milk glass and has a hat (cap) shape.

In manufacturing the above luminous luminaire, a luminous layer composed of 70 parts by weight of luminous powder and 30 parts by weight of a low melting point lead-free glass frit was printed on a mount for transfer by screen printing. Further, a lead-free glass layer was printed so as to cover the light-storing layer, and a transfer paper comprising a 70 μm-thick lead-free glass layer was formed on the light-storing layer having a thickness of 70 μm. The produced phosphorescent transfer paper was transferred to a substrate, and
Heat treatment was performed at 10 ° C. for 10 minutes to obtain a lighting glove 53. The lighting glove 53 was attached to the main body 54 of the lighting fixture to make the luminous decoration 52 of this example. In FIG. 6, reference numeral 549 denotes a leg of the lighting fixture.

After lighting the luminous decorative lighting fixture of this example with a 20 W incandescent lamp for 20 minutes, the lighting was turned off. As a result, the decorative pattern 110 formed by the luminous layer 200, which was almost invisible at the time of lighting, showed vivid afterglow in the dark and emerged. The phosphorescent decorative article 52 of this example had sufficient heat resistance as a lighting device, and was excellent in water resistance, surface smoothness, and decorativeness. In this embodiment, the surface of the base 100 is milky white, but may be colored.

(Experimental Example 1) In this example, as shown in Table 1, the luminous action of the luminous decorative article was evaluated. By changing the mixing ratio between the luminous powder and the lead-free glass frit, a luminous layer was formed on the substrate surface, and the surface was covered with the lead-free glass layer. Other configurations are the same as those of the first embodiment. The obtained phosphorescent decorative articles were designated as Samples 1 to 10.

The luminous action was evaluated visually. The evaluation method is as follows.
After leaving for 0 minutes, the lights were turned off and left for 30 minutes. Regarding the luminous action at that time, ◎ indicates a bright afterglow, ○ indicates a clear outline, Δ indicates a faint outline, and × indicates no afterglow.
And Table 1 shows the obtained evaluation results. As can be seen from the table, the luminous effect was recognized for all luminous ornaments. Samples 3 to 8 had a particularly excellent light storage effect.

[0050]

[Table 1]

(Experimental Example 2) In this example, a test was conducted on the content ratio of the luminous powder in the luminous layer and the luminous action. A luminous layer comprising 30 parts by weight of luminous powder and 70 parts by weight of lead-free glass frit was formed on a substrate, and this was
And Further, a luminous layer composed of 40 parts by weight of the luminous powder and 60 parts by weight of the lead-free glass frit was formed on the substrate, and this was used as Sample 13. The phosphorescent layers of Samples 11 and 13 in this example have the same composition as the phosphorescent layers of Samples 1 and 3 in Experimental Example 1 described above.

First, the luminous layer of the sample 11 has a thickness of 300 μm.
When the thickness was increased to about m, the phosphorescent property was exhibited. Further, when the thickness was increased to about 500 μm, the phosphorescent property was exhibited to the same extent as a commercially available plastic phosphorescent material. Further, the luminous layer is formed by the firing conditions of the first embodiment (at 840 ° C. for 10 minutes).
And the surface of the luminous layer became smooth.

Next, the phosphorescent layer of the sample 13 has a thickness of 150 μm.
When the thickness was increased to about m, the phosphorescent property was exhibited. This sample 1
It was found that the light-storing layer of No. 3 exhibited light-storing properties at a thickness smaller than that of the light-storing layer of the sample 11. Further, the luminous layer of the sample 13 did not vitrify but had a rough and rough surface under the firing conditions of the first embodiment.

From the above, the composition of the sample 3 (the luminous powder 40
(% By weight, 60% by weight of lead-free glass frit), it is possible to obtain excellent luminous properties by producing the luminous layer, but since it is a rough surface, it is necessary to cover the surface with a glass layer to make it smooth. You can see that there is.

(Experimental Example 3) In this example, the water resistance of the phosphorescent decorative article was evaluated. The phosphorescent decorative article of Embodiment 1 was left in water at 25 ° C. for 24 hours. For comparison, a phosphorescent decorative article was manufactured without exposing the phosphorescent layer without forming a lead-free glass layer, and this was used as a comparative example. This comparative example was similarly left in water.

As a result, in the case of the first embodiment, the color of the luminous layer remained yellow-green, there was no change, and excellent luminous performance was exhibited as before the underwater test. In addition, the phosphorescent powder was not dissolved in water. On the other hand, in the case of the comparative example, the surface of the luminous layer changed its color from yellow-green to white, and it was confirmed that the luminous powder was dissolved in water.

(Experimental Example 4) In this example, as shown in Table 2, a test was conducted on the water resistance of the phosphorescent decorative article. By changing the mixing ratio of the luminous powder contained in the luminous layer and the lead-free glass frit, each of the luminous layers was coated with a lead-free glass layer, and one with no lead-free glass layer was produced. Other configurations are the same as those of the first embodiment.

The obtained luminous decorative article was subjected to a water boiling test. That is, the phosphorescent decoration was put into boiling water at 100 ° C. and boiled for 1 to 4 hours. During that time, the surface condition of the phosphorescent decoration was visually observed. Then, the case where the surface state of the luminous layer did not change was evaluated as ○, the color changed to white but no peeling occurred, and the Δ was determined when the luminous layer peeled. Table 2 shows the results.

According to the table, no change was observed on the surface of any of the phosphorescent decorative articles in which the phosphorescent layer was covered with the lead-free glass layer. On the other hand, when the lead-free glass layer is not formed, adverse effects such as discoloration of the luminous layer to white and peeling of the luminous layer occurred.

[0060]

[Table 2]

(Experimental example 5) In this example, as shown in Table 3, the stain resistance of the phosphorescent decorative article was evaluated. That is,
The thickness of the lead-free glass layer was changed between 0 and 300 μm. The phosphorescent powder used had an average particle size of 10 μm.
Other than the above, a phosphorescent decorative article was manufactured in the same manner as in the first embodiment.

The surface of the obtained phosphorescent decorative article was rubbed with a pencil (pencil hardness 2B) to evenly adhere the dirt, and the surface of the phosphorescent decorative article was wiped off with a wet cloth. After that, the condition of dirt on the surface of the phosphorescent decorative article was visually observed.
When the trace of the pencil was completely wiped off without any trace of dirt, 残 was determined when the trace was almost completely wiped off, Δ was determined when a little dirt remained, and X was determined when the pencil trace remained black. Table 3 shows the evaluation results.

As can be seen from the table, by coating the luminous layer with the lead-free glass layer, dirt hardly adhered to the surface of the luminous decorative article. In addition, when the thickness of the lead-free glass layer was 20 μm or more, dirt could be particularly wiped off.

[0064]

[Table 3]

(Experimental Example 6) In this example, as shown in Table 4, the afterglow luminance of the phosphorescent decorative article was measured. The luminous layer is
It is composed of 70 parts by weight of the phosphorescent powder and 30 parts by weight of the lead-free glass frit, and is the same as Sample 6 in Experimental Example 1 described above. The luminous layer was formed on the surface of the substrate in the same manner as in Example 1, and the surface was covered with a lead-free glass layer.

The obtained phosphorescent ornament was left overnight in a dark place in a light-shielded state to completely remove the afterglow, and then placed under a brightness of 200 lux for 4 minutes. 60
After storage for one minute, the afterglow luminance was measured.

On the other hand, for comparison, a similar test was performed using a commercially available plastic panel containing zinc sulfide as a luminous powder. The phosphorescent phosphor of commercially available plastic panels is zinc sulfide. Table 4 shows the results of these measurements. As can be seen from the table, the luminous layer of sample 6 has 1
It had excellent afterglow brightness for 0-60 minutes. On the other hand, in the light storage layer of the comparative example, the afterglow luminance after 20 minutes was reduced.

[0068]

[Table 4]

(Experimental Example 7) In this example, the luminous performance of the luminous powder when fired in a neutral atmosphere was examined. First, as in Embodiment 1, a luminous layer was formed on the surface of the substrate, and the surface was covered with a lead-free glass layer. Then, these are placed in an oxidizing atmosphere at about 400 to 50.
By heating at 0 ° C., all organic binders contained in the luminous layer and the lead-free glass layer were decomposed or burned. Then, it was fired at about 830 ° C. for 10 minutes in a neutral atmosphere in a nitrogen furnace to obtain a phosphorescent decorative article.

Further, the luminous powder was taken out of the luminous decorative article manufactured in this example. The luminous powder after calcination was compared with the luminous powder before calcination, and the luminous performance was comparatively measured. This comparative measurement is the same as in Experimental Example 6. As a result, residual luminance was observed for about 4 hours after standing in a dark room.

As a result, assuming that the luminous performance of unused luminous powder is 100%, the luminous performance of the luminous powder used in the luminous decorative article of this example is 95%, and both are almost the same. Luminescent performance was shown. Therefore, it can be seen that the luminous performance of the luminous layer of this example does not decrease even when firing in a neutral atmosphere.

(Experimental Example 8) In this example, the luminous performance of the luminous powder when fired in a reducing atmosphere was examined. First, as in Embodiment 1, a luminous layer was formed on the surface of the substrate, and the surface was covered with a lead-free glass layer. Next, these were fired at 800 ° C. for 10 minutes in a tunnel-type hydrogen furnace in which the dew point was controlled by steam to obtain a phosphorescent decorative article.

The light-storing effect of the light-storing layer after firing was compared with that of the light-storing layer before firing. This comparative measurement
This is the same as in Experimental Example 6 above. As a result, residual luminance was observed for about 6 hours after standing in a dark room.

The luminous performance of unused luminous powder was 1
When it was set to 00%, the luminous performance of the luminous powder used in the luminous decorative article of this example was 100%. Therefore, it can be seen that the luminous performance of the luminous layer of this example does not decrease even by firing in a reducing atmosphere.

[0075]

According to the present invention, it can be used indoors and outdoors,
It is possible to provide a luminous decorative article excellent in luminous properties, heat resistance, water resistance, surface smoothness, stain resistance, and decorativeness.

[Brief description of the drawings]

FIG. 1 is a sectional view of a phosphorescent decorative article according to a first embodiment.

FIG. 2 is a perspective view of a phosphorescent decorative article according to a second embodiment.

FIG. 3 is a cross-sectional view of a substrate on which a paint layer is printed according to a second embodiment.

FIG. 4 is a sectional view of the substrate on which the luminous layer is printed, following FIG. 3;

FIG. 5 is a sectional view of the substrate on which the lead-free glass layer is printed, following FIG. 4;

FIG. 6 is a perspective view of a phosphorescent decorative article according to a third embodiment.

FIG. 7 is a sectional view of a phosphorescent decorative article according to a third embodiment.

[Explanation of symbols]

 1,10,100. . . Substrate, 11. . . Pattern, 110. . . Decorative pattern, 12,120. . . Margins, 2, 20, 200. . . Luminous layer, 3, 30, 300. . . Inorganic glass layers, 40,. . . Paint layer, 5, 51, 52. . . Luminous decorations,

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 11/08 C09K 11/08 G

Claims (6)

[Claims] 1. A luminous layer containing luminous powder and lead-free glass frit is formed on the surface of a substrate,
A luminous decorative article, wherein the surface of the luminous layer is covered with a lead-free glass layer. 2. The luminous layer according to claim 1, wherein the luminous layer comprises 35 to 95 parts by weight of a luminous powder and 65% by weight of a lead-free glass frit.
Luminescent decoration characterized by comprising up to 5 parts by weight. 3. The phosphorescent decorative article according to claim 1, wherein the thickness of the lead-free glass layer is equal to or larger than the particle diameter of the phosphorescent powder. 4. The method according to claim 1, wherein:
The phosphorescent decorative article, wherein the phosphorescent layer has a thickness of 30 to 800 μm. 5. The method according to claim 1, wherein:
The phosphorescent decorative article, wherein the thickness of the lead-free glass layer is 10 to 300 μm. 6. The method according to claim 1, wherein:
The phosphorescent decorative article, wherein the substrate is any one of pottery, porcelain, enamel, glass and crystallized glass.