JP2003206189A - Luminous ceramic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminous ceramic material which is obtained by using a lead glass frit wherein a luminous layer of which ceramic material is advantageously prevented from being blackened, and which has excellent weatherability and resistance to chemicals. <P>SOLUTION: In the luminous ceramic material in which the luminous layer is formed by coating the surface of a ceramic base material with a composition containing an aluminate-based luminous pigment and lead glass frit and baking, the content ratio (x) of an oxide of a tetravalent element and the content ratio (y) of an oxide of a trivalent element, constituting the lead glass frit, are each set to a value within either of predetermined areas A and B. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phosphorescent ceramic material,
In particular, the present invention relates to a phosphorescent ceramic material that does not turn black in the phosphorescent layer even when it contains lead glass frit as a component that constitutes the phosphorescent layer, and that has excellent weather resistance.

[0002]

BACKGROUND ART Conventionally, by utilizing the characteristic of a phosphorescent pigment that is excited by the irradiation of daytime light or artificial light and emits light at night or in the dark after the irradiation of such light is stopped. It has been considered to guide the eyes at night such as sidewalks, guide the eyes at tunnels, etc., and further guide the evacuation of hospitals, public facilities, etc., and products using such a phosphorescent pigment, for example, , Phosphorescent paints and phosphorescent plastics are now on the market. However,
Such phosphorescent paints and phosphorescent plastics have problems in weather resistance, durability, abrasion resistance, etc., because they use an organic binder or have a phosphorescent pigment dispersed in an organic resin. It could not be used outdoors or under harsh environmental conditions.

On the other hand, there has been proposed an inorganic light-storing material in which a mixture of a light-storing pigment and glass frit is heated and melted to disperse and retain the light-storing pigment in the glass. The properties such as weather resistance, durability, and wear resistance are improved as compared with those of the luminous materials. In particular, in recent years, when lead glass is used as a glass frit, lead and cadmium are considered in consideration of problems such as adverse reaction to human body and environmental pollution in addition to the problem of blackening by reacting with phosphorescent pigment. The use of a lead-free glass frit containing no harmful metal element such as, for example, has been studied. For example, in Japanese Patent No. 2951902, an inorganic-based light-storing paint ( Glaze) has been proposed, and is also disclosed in JP-A-10-27.
In 3657 and Japanese Patent Laid-Open No. 8-165140,
By fusing a glaze containing a phosphorescent pigment and a lead-free glass frit etc. on the surface of a base material such as ceramics,
A phosphorescent ceramic product in which a phosphorescent layer is formed has been proposed.

However, even such an inorganic phosphorescent product retains the lead-free phosphorescent pigment that retains the phosphorescent pigment when it is exposed to rain including exhaust gas or water leak from a tunnel for a long period of time. The glass frit is eroded by acids, alkalis, etc. contained in rain, water leakage, etc., and when the light-accumulating pigment exposed on the surface comes into contact with water, the light-accumulating pigment is decomposed, and the desired light-accumulating performance is obtained. It was difficult to say that the weather resistance was still sufficient because the problem of loss was caused. Moreover, it was revealed that the gloss of the phosphorescent layer was inferior and the formability thereof was deteriorated as compared with the case of using the lead glass frit containing lead.

[0005]

The present invention has been made in view of such circumstances, and a problem to be solved by the present invention is that in a phosphorescent ceramic material using lead glass frit, a black phosphorescent layer is used. It is an object of the present invention to provide a phosphorescent ceramic material which can be prevented from being changed extremely advantageously and which is also excellent in weather resistance and chemical resistance.

[0006]

SOLUTION: The present inventors have conducted extensive studies to solve such a problem, and as a result, as a phosphorescent pigment,
It has been found that the blackening of the phosphorescent layer can be extremely advantageously prevented by using an aluminate-based phosphorescent pigment and selecting and using a lead glass frit having a specific composition.

Therefore, the present invention is based on such findings.
It is a completed work, and the gist of it is
On the surface of the Ramix base material, phosphorescent pigment and lead glass
And applying a composition containing
A phosphorescent ceramic in which a phosphorescent layer is formed.
As a phosphorescent material, and as the phosphorescent pigment, an aluminate-based storage material.
The lead glass frit is constructed with the use of a light pigment.
The content ratio of oxides of tetravalent element and trivalent element
Storage characterized by being present in one of the two areas A and B
It is in a photoceramic material. Area A: y ≧ 0 (1) y ≧ 0.64x−25.71 (2) y ≦ −0.39x + 30 (3) y ≦ 0.5x−2 (4) y ≧ −x + 28 (5) Area B: y ≧ −0.56x + 50.67 (6) y ≧ 0.7x−32.2 (7) y ≦ −0.5x + 59 (8) y ≦ 0.42x + 4 (9) [However, in the above formulas (1) to (9), x is a tetravalent element.
Elementary (M) oxide: MO ₂Indicates the content ratio (% by weight) of
On the other hand, y is an oxide of trivalent element (M '): M'₂O₃of
Indicates the content ratio (% by weight)]

That is, in the phosphorescent ceramic material according to the present invention, an aluminate-based phosphorescent pigment is used as the phosphorescent pigment, and the lead glass frit is a tetravalent element among the constituent elements. As shown in FIG. 1, the content ratio (x, y) of the oxides of (M) and the trivalent element (M ′) is (x, y) = (28, 0),
(40,0), (54,9), (36,16) and (2
0,8) in the pentagonal area A, or (x,
y) = (48,24), (66,14), (76,2)
1) and (60, 29) are present in the rectangular B region, the blackening of the luminous layer, which is likely to occur when lead glass frit is used, is extremely advantageously prevented. As a result, the luminous performance of the luminous pigment can be exhibited to a high degree. Moreover, erosion due to acids and alkalis contained in rain and water leakage is effectively suppressed, and even when exposed to harsh environmental conditions for a long period of time, it is possible to realize weather resistance that can sufficiently withstand it. Of.

Further, since the luminous layer is basically a fired body made of glass and has a structure in which a predetermined luminous pigment is distributed inside the layer, it has excellent resistance. Needless to say, it has abrasion resistance and stain resistance, and has features such as excellent luster of the light-storing layer and excellent formability of the light-storing layer as compared with the case of using a lead-free glass frit.

According to one of the preferred embodiments of the phosphorescent ceramic material according to the present invention, the tetravalent element (M) is silicon, while the trivalent element (M ') is aluminum and / or Alternatively, boron is desirable.

According to another preferred embodiment of the present invention, the lead glass frit is 0.1 to 70.
It is desirable to contain PbO by weight.

Further, according to another preferred embodiment of the phosphorescent ceramic material according to the present invention, the phosphorescent layer comprises:
It is desirable that the composition is composed of 20 to 95% by weight of the luminous pigment and 5 to 80% by weight of the lead glass frit so that the object of the present invention can be more effectively realized. Become.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION By the way, such a phosphorescent ceramic material according to the present invention has, for example, a structure as shown in FIG. 2, and a phosphorescent material having a phosphorescent property is formed on the surface of a base material 12 made of ceramics. The layer (glaze layer) 14 is formed. There, the light-storing layer 14 constituting such a light-storing ceramic material 10 is
It is formed by applying a composition (glaze) containing a specific phosphorescent pigment and a lead glass frit having a specific composition and baking it.
The great feature of the present invention exists.

More specifically, the luminous layer 14 as described above.
The phosphorescent pigment constituting the is excited by irradiation of light,
Not only emits fluorescence when irradiated with such light, but also emits afterglow (phosphorescence) even after the irradiation of light is stopped, and has such characteristics from the past. As the sulfide-based phosphorescent inorganic phosphors such as zinc sulfide, and the aluminate-based phosphorescent inorganic phosphors such as strontium aluminate, etc. are known as the phosphorescent layer 14 in the present invention. In order to prevent the above blackening, among the conventionally known phosphorescent pigments, aluminate-based phosphorescent inorganic phosphors such as strontium aluminate, calcium aluminate and barium aluminate are used. As is well known, such a phosphorescent pigment is obtained by adding Eu ₂ O ₃ or the like as an activator to a raw material such as SrCO ₃ , Al ₂ O ₃ or H ₃ BO ₃ and further adding an activator. As a mixture of Dy ₂ O _{3 and the} like and firing,
It is manufactured. Further, as such a phosphorescent pigment, one having a melting temperature of about 1400 ° C. or higher can be appropriately selected from commercially available products and can be advantageously used, and specifically, Chemitec Powder products such as Picarico CP-05, 10, 20, 30 manufactured by Co., Ltd. are preferably used.

On the other hand, the lead glass frit as another constituent component for providing the luminous layer 14 is a glass frit containing the lead element: Pb, and is fired at a temperature equal to or higher than its melting point to obtain such a luminous property. This is for fixing the pigment to the surface of the ceramic substrate 12 and for holding and protecting the light-accumulating pigment. In the lead glass frit used in the present invention, in order to prevent blackening of the phosphorescent layer 14 and to realize excellent weather resistance and chemical resistance, among the lead glass frits known in the related art, particularly, , An oxide of tetravalent element (M) and 3
As shown in FIG. 1, the content ratios (x, y) of the oxides of the valent element (M ′), that is, MO ₂ and M ′ ₂ O ₃ , respectively, are as follows: , B, whichever is present, is required. Area A: y ≧ 0 (1) y ≧ 0.64x−25.71 (2) y ≦ −0.39x + 30 (3) y ≦ 0.5x−2 (( 4) y ≧ −x + 28 (5) B area: y ≧ −0.56x + 50.67 (6) y ≧ 0.7x−32.2 (7) y ≦ −0.5x + 59・ ・ ・ (8) y ≦ 0.42x + 4 ・ ・ ・ (9)

However, the above (1) to (5); (6) to
In each formula of (9), x represents the content ratio (wt%) of the oxide of the tetravalent element (M): MO ₂ , while y represents 3
'Oxides: M valence element (M)' indicates the total content of the ₂ O ₃ (wt%).

However, as is clear from FIG. 1, the area A satisfying the above equations (1) to (5) is (x, y) =
(28,0), (40,0), (54,9), (36,
16) and (20, 8) are pentagonal regions (including the boundary line) connecting the five points, and similarly, the B region that satisfies the above formulas (6) to (9) is (x, y) = (48,2
4), (66, 14), (76, 21), and (60,
29) Square area connecting the four points (including the boundary line)
Is.

The tetravalent element (M) as described above includes, for example, silicon and zirconium, while the trivalent element (M ') includes, for example, aluminum, boron and phosphorus. is there. Therefore, a plurality of tetravalent elements (M) are contained in the lead glass frit used.
And a trivalent element (M ′) are contained, x and y as described above are respectively the sum of oxides of tetravalent elements contained in the lead glass frit: SiO ₂ and ZrO ₂ . Content ratio (% by weight) Trivalent oxide: Al
The total content (% by weight) of ₂ O ₃ , B ₂ O ₃ , P ₂ O _{3 and the} like is shown.

When the content ratio (% by weight) of the oxide of the trivalent element and the oxide of the tetravalent element does not exist in the area A or the area B as described above, the phosphorescent pigment is Even when the above-mentioned aluminate-based phosphorescent pigment is used, the phosphorescent layer 14 is not baked during baking.
Is blackened, and further, the weather resistance cannot be improved, and it becomes impossible to impart desired characteristics to the phosphorescent ceramic material.

The content ratio of lead, which is an essential component of the lead glass frit as described above, in the form of its oxide: PbO is preferably 0.1 to 70.
It is desirable that the content is wt%. If the content is less than 0.1% by weight, the desired weather resistance and chemical resistance cannot be obtained. On the contrary, if the content exceeds 70% by weight, the phosphorescent pigment is decomposed by PbO. This is because it becomes difficult to form an effective glassy material.

In the lead glass frit used in the present invention, in addition to PbO, the oxides of trivalent elements such as boron and aluminum, and the oxides of tetravalent elements such as silicon, as described above, Na ₂ O, K ₂ O, CaO, MgO, Zn
Components such as O and BaO that have been conventionally contained in lead glass are
It will be appropriately contained.

Then, such a lead glass frit is
The composition (glaze) for forming the phosphorescent layer 14 is prepared in combination with the phosphorescent pigment described above. At the time of preparation, the phosphorescent pigment and the lead glass frit are mixed with each other in a predetermined amount. In the present invention, the luminous layer 14 after baking (baking) is generally composed of 20 to 95% by weight of a luminous pigment and 5 to 80% by weight of lead glass frit. Their usage rates will be selected and used so that they can be configured. At this time, if the amount of the phosphorescent pigment used is too small, the phosphorescent performance cannot be sufficiently exhibited, and if it is too large, not only the effect commensurate with the amount used cannot be expected, but also expensive phosphorescent In addition to increasing the amount of the organic pigment used, the amount of lead glass frit used becomes too small, which adversely affects the glaze properties and makes it difficult to form the phosphorescent layer 14 after firing. This is because there is a possibility that the phosphorescent pigment cannot be protected and held in the lead glass.

Furthermore, since the above-mentioned phosphorescent pigment and lead glass frit are solid at room temperature and are generally used in the form of powder, the composition for forming the phosphorescent layer contains acrylic resin, methyl cellulose, Suitable known binders such as ethyl cellulose, carboxymethyl cellulose, squeegee oil, etc., and solvents such as water and toluene are appropriately blended to form, for example, a slurry form or a paste form, whereby a ceramic substrate The application of 12 surfaces can be realized very advantageously. The organic binder and solvent added to these compositions are decomposed and burned off by baking (baking) performed after such a coating step.

The composition for forming the phosphorescent layer also includes
Further, if necessary, it is possible to add an inorganic pigment or the like other than the luminous pigment to color the luminous layer 14.
However, by adding such an inorganic pigment, the light to be applied to the phosphorescent pigment is blocked, and the phosphorescent performance may be deteriorated. It goes without saying that the amount that does not impair the characteristics is appropriately set.

By the way, in manufacturing the phosphorescent ceramic material 10 according to the present invention, various conventionally known methods can be adopted. For example, first, the above-mentioned components are uniformly mixed at room temperature. A composition (glaze) for forming a light-storing layer is prepared. Then, the composition thus prepared is applied to the surface of the ceramic base material 12. In addition, such coating on the base material 12 can be performed by various conventionally known methods,
For example, it can be carried out by appropriately adopting a method such as brush coating, spraying method, dip coating, screen printing or transfer. Further, the film thickness of the composition applied to the surface of the substrate 12 is not particularly limited, either.
Although it can be appropriately set according to the application of the phosphorescent ceramic material 10, the thickness of the phosphorescent layer 14 is generally 100 to
It will be applied so as to have a thickness of 1000 μm.

Then, the composition for forming a phosphorescent layer thus coated on the surface of the substrate 12 is dried at room temperature or by heating if necessary, and then the composition is heated at a temperature higher than the melting point of the lead glass frit. The lead glass frit in the inside is melted and baked (fired) to produce the phosphorescent ceramic material 10 in which the phosphorescent layer 14 having the desired characteristics such as phosphorescence resistance, weather resistance, and chemical resistance is formed. Of.

In the baking process as described above,
As the heating temperature (firing temperature), since it is necessary to melt the lead glass frit, a temperature equal to or higher than the melting point is adopted, but generally a temperature of 500 ° C. or higher is adopted, and The upper limit of the above will be appropriately determined so as not to adversely affect the light storage characteristics and the like of the light storing pigment, but generally a temperature of about 1100 ° C. will be the upper limit.

The phosphorescent ceramic material 10 obtained by firing in this manner uses the aluminate-based phosphorescent pigment and the lead glass frit having a specific composition. No blackening is caused in the phosphorescent layer 14, and the phosphorescent pigment existing in the phosphorescent layer 14 is excited by the irradiation light, and as a result, the phosphorescent performance of the phosphorescent pigment can be sufficiently exhibited.

In addition, the light-storing layer 14 is less likely to be eroded by acids or alkalis contained in rain, water leakage, etc., so that even if it is exposed to harsh environmental conditions for a long period of time, it is sufficient. It has weather resistance that can withstand.

The phosphorescent ceramic material thus obtained can be advantageously used in various applications by utilizing its excellent properties such as phosphorescence and weather resistance. By emitting light at night or in the dark, it can be used as a tile or the like for guiding the line of sight at night such as a sidewalk, guiding the line of sight at a tunnel or the like, and guiding the evacuation of a hospital or public facility.

As the ceramic base material 12 of the phosphorescent ceramic material 10, an appropriate shape and size can be adopted according to its application and the like.
The material is not limited as long as it can be classified into ceramics.

[0032]

EXAMPLES In order to clarify the present invention more specifically, representative examples of the present invention will be shown below.
It goes without saying that the present invention is not limited by the description of such embodiments. In addition to the following embodiments, the present invention further includes various changes and modifications based on the knowledge of those skilled in the art, in addition to the above specific description, without departing from the spirit of the present invention. It should be understood that improvements and the like can be added.

First, a strontium aluminate-based fluorescent pigment (C
P-10: manufactured by Chemtech Co., Ltd., and as a lead glass frit or a lead-free glass frit, the following Table 1 is used.
Or Example 1 having the content ratio (composition) shown in Table 2.
5 and Comparative Examples 1 to 4 and squeegee oil (manufactured by Kure Chemical Industry Co., Ltd.) as an organic binder.

[0034]

[Table 1]

[0035]

[Table 2]

Then, these three kinds of raw materials were used in a ratio of 25 parts by weight of a phosphorescent pigment, 75 parts by weight of a lead glass frit or a lead-free glass frit, and 60 parts by weight of an organic binder, and these were mixed to carry out. The paste-like composition for forming a phosphorescent layer (glaze) according to Examples 1 to 5 and Comparative Examples 1 to 4 was prepared.

Next, the composition for forming a phosphorescent layer is applied on the surface of an alumina substrate having a size of 40 mm × 80 mm × 1 mm (thickness) to a thickness of 700 μm, and baked at a maximum temperature of 750 ° C. According to Examples 1 to 5 and Comparative Examples 1 to 4 in which the phosphorescent layer was formed.
The phosphorescent ceramics plate according to 1. was produced. In addition, about the thing that the phosphorescent layer turned black by baking (firing),
For the ones that did not turn black, mark a ○, and
The results are shown in Tables 3 and 4 below.

The phosphorescent ceramic plates (samples) according to Examples 1 to 5 and Comparative Examples 1 to 4 thus obtained were subjected to the following evaluation tests, and the results are shown in Tables 3 and 4 below. It was shown to.

-Evaluation of luminous efficiency-A white fluorescent lamp was used as a light source and irradiation time was 20 minutes.
Each phosphorescent ceramic material was irradiated with light, and afterglow 0.5 minutes after the irradiation was stopped,
It was visually confirmed and objectively evaluated by the following judgment method. ◯: Afterglow can be clearly confirmed, Δ: Afterglow can be confirmed slightly, ×: Afterglow cannot be confirmed.

-Evaluation of chemical resistance-In addition, in order to examine the weather resistance of the phosphorescent ceramic plates according to Examples 1 to 5 and Comparative Examples 1 to 4, the following resistance was examined using acid and alkali. The chemical properties were evaluated. First, prepare 1 wt% hydrochloric acid and 3 wt% sodium hydroxide aqueous solution, and add these chemicals to
Each phosphorescent ceramic plate was dipped for 1 week and then dried to measure the weight reduction amount of the phosphorescent layer, and the reduction rate was calculated by the following formula (1). The results are shown in Tables 3 and 4 below. Decrease rate [%] = (W ₀ −W ₁ ) / W ₀ × 100 (1) [where W ₀ represents the weight (g) of the phosphorescent layer before being immersed in the chemical, while W ₁ Indicates the weight (g) of the phosphorescent layer after immersion]

[0041]

[Table 3]

[0042]

[Table 4]

As is clear from the results of Tables 3 and 4, the content ratios of the oxides of the tetravalent element and the trivalent element constituting the lead glass frit are present in any of the regions A and B as described above. In the phosphorescent ceramic materials according to Examples 1 to 5, although the lead element is contained, the phosphorescent ceramic material according to Comparative Example 4 using lead-free glass frit without blackening during baking. The same level of light storage performance was observed. On the other hand, the content ratio of oxides of tetravalent element and trivalent element constituting the lead glass frit is
In the phosphorescent ceramic materials according to Comparative Examples 1 to 3 which do not exist in any of the regions A and B as described above, the phosphorescent layer turned black during baking, and afterglow could not be confirmed.

Regarding the chemical resistance, in the phosphorescent ceramic materials according to Examples 1 to 5, the reduction ratio of the phosphorescent layer when 1 wt% hydrochloric acid was used was smaller than that in the comparative example. It can be seen that the chemical resistance is improved, and it can be seen that the weather resistance is also excellent.

[0045]

As is clear from the above description, in the phosphorescent ceramic material according to the present invention, the lead glass frit containing the lead element is used. The content ratio of the oxide of the valent element is selected to exist in a specific region, and as the phosphorescent pigment, an aluminate-based phosphorescent pigment is used. The blackening of the light-storing layer, which is likely to be caused by the above, can be very advantageously prevented, and the light-storing performance of the light-storing pigment can be highly exhibited. Moreover, by using such a lead glass frit,
Chemical resistance against chemicals such as acids and alkalis is also improved, which effectively suppresses erosion by acids and alkalis contained in rain and water leaks, and protects from harsh environmental conditions for a long period of time. Even if it is exposed, it is possible to realize weather resistance enough to endure it.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing regions (A, B) of a content ratio (x, y) of oxides of a tetravalent element and a trivalent element constituting a lead glass frit used in the present invention.

FIG. 2 is an explanatory diagram showing a specific example of the phosphorescent ceramic material according to the present invention.

[Explanation of symbols]

10 Luminescent ceramic material 12 Ceramic base material 14 phosphorescent layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masato Takagi             Gifu Prefecture Ogaki City Asaani 1-4, Inc.             Within the tilement technology development center (72) Inventor Toshichika Hirano             230 Akadochi, Minamiharayama Town, Owariasahi City, Aichi Prefecture             Company C day F-term (reference) 4G062 AA08 AA09 BB01 BB04 CC08                       DA04 DA05 DA06 DB03 DC01                       DC03 DC04 DD01 DE03 DF03                       DF04 DF05 DF06 EA01 EB03                       EC03 ED01 EE02 EF01 EG01                       FA01 FB01 FC01 FD01 FE01                       FF01 FG01 FH01 FJ01 FK01                       FL01 GA01 GB01 GC01 GD01                       GE01 HH01 HH03 HH05 HH07                       HH09 HH11 HH13 HH15 HH17                       HH20 JJ01 JJ03 JJ05 JJ07                       JJ10 KK01 KK03 KK05 KK07                       KK10 MM12 MM13 MM27 NN32                       NN34                 4H001 XA08 XA13 XA20 XA38 XA56                       YA63 YA66

Claims (4)

[Claims] 1. A phosphorescent face is formed on the surface of a ceramic base material.
Coating composition containing lead and glass frit,
By baking it, a phosphorescent layer is formed.
As a phosphorescent ceramic material, as the phosphorescent pigment,
In addition to using an aluminate-based phosphorescent pigment,
Containing oxides of tetravalent and trivalent elements that make up the slit
A certain proportion must exist in either of the following two areas A and B.
A phosphorescent ceramic material characterized by: Area A: y ≧ 0 (1) y ≧ 0.64x−25.71 (2) y ≦ −0.39x + 30 (3) y ≦ 0.5x−2 (4) y ≧ −x + 28 (5) Area B: y ≧ −0.56x + 50.67 (6) y ≧ 0.7x−32.2 (7) y ≦ −0.5x + 59 (8) y ≦ 0.42x + 4 (9) [However, in the above formulas (1) to (9), x is a tetravalent element.
Elementary (M) oxide: MO ₂Indicates the content ratio (% by weight) of
On the other hand, y is an oxide of trivalent element (M '): M'₂O₃of
Indicates the content ratio (% by weight)] 2. The phosphorescent ceramic material according to claim 1, wherein the tetravalent element (M) is silicon, and the trivalent element (M ′) is aluminum and / or boron. 3. The lead glass frit is 0.1 to 70.
The phosphorescent ceramic material according to claim 1 or 2, which contains PbO in a weight percentage. 4. The phosphorescent layer comprises 20 to 20 of the phosphorescent pigment.
95% by weight and 5 to 80% by weight of the lead glass frit
The phosphorescent ceramic material according to any one of claims 1 to 3, which is composed of