JP2001158679A - Paint with afterglow property, and ceramic ware by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To beautifully decorate an article by making the color of the afterglow of the baked painted surface red. SOLUTION: This paint with afterglow properties contains an afterglow fluorescent substance represented by the formula Ln2O2S:Eux, My (wherein, 0.00001<=x<=0.5; 0.00001<=y<=0.3; Ln is at least one kind selected from Y, La, Gd and Lu; M is a coactivator and at least one kind selected from a group of Mg, Ti, Nb, Ga and Ta) and nonlead frit containing 0.1-5 wt.% MgO and <=5 wt.% CaO. The paint with afterglow properties contains 1-100 pts.wt. afterglow fluorescent substance based on 100 pts.wt. nonlead frit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an afterglow paint which is baked and painted on a ceramic product, and a ceramic product which is painted with the afterglow paint.

[0002]

2. Description of the Related Art Conventionally, various white paints have been used to beautifully decorate the surface of ceramic products. However, these products are intended for use and appreciation in the daytime, and cannot be used at night, and their uses are limited. As a paint that solves this drawback, an afterglow paint that can be seen at night has been developed. The afterglow contains an aluminate phosphor substituted with boron. By using a paint in which this phosphor is mixed with a lead-free frit, a ceramic product having afterglow can be realized. This technique is disclosed in Japanese Patent Application Laid-Open No. 10-194871.

[0003]

With this technology, ceramic products which develop color at night have been put to practical use. However, this ceramic product has a drawback that the afterglow color of the afterglow paint is limited to bluish green, so that it cannot be changed to other emission colors.

The present invention has been developed to solve this drawback, and an important object of the present invention is to provide a ceramic product which can be beautifully decorated by making the afterglow color of a baked painted surface red. Is to do.

[0005]

According to the present invention, there is provided an afterglow paint comprising:
It contains an afterglow phosphor and a lead-free frit and is used for painting and painting on ceramic products, and has the following composition. (A) The afterglow phosphor contained in the afterglow paint is represented by the following general formula. _{Ln 2 O 2 S: Eu x} , M y 0.00001 ≦ x ≦ 0.5 0.00001 ≦ y ≦ 0.3 , however, Ln in the composition formula Y, La, at least one selected from the group consisting of Gd and Lu, M Is a co-activator and is at least one selected from the group consisting of Mg, Ti, Nb, Ga and Ta. When the value of X is less than 0.00001, the light absorption of the afterglow phosphor is deteriorated, and as a result, the phosphorescent luminance is lowered, and the value of 0.
If it is larger than 5, the concentration disappears, and the phosphorescent luminance decreases. When the value of Y is less than 0.00001, the light absorption of the afterglow phosphor deteriorates, and as a result, the phosphorescent luminance decreases. When the value of Y is more than 0.3, the concentration disappears and the phosphorescent luminance decreases. descend.

(B) The lead-free frit contains at least both MgO and CaO, and the content of MgO is 0.1
% By weight or more and 5% by weight or less, and the CaO content is 5% by weight or less.
% By weight or less. When the content of MgO is less than 0.1% by weight, the afterglow phosphor is easily decomposed, and when it is more than 5% by weight, the afterglow phosphor is easily decomposed. When the content of CaO exceeds 5% by weight, the afterglow phosphor is easily decomposed.

(C) The afterglow paint contains 1 to 100 parts by weight of the afterglow phosphor based on 100 parts by weight of the lead-free frit. The content of the afterglow phosphor is determined to be an optimum value in consideration of the color depth of the ceramic product.

In the afterglow paint used for painting the ceramic product of the present invention, the composition of the lead-free frit preferably has the following composition. 60% when SiO ₂ is more than 20% by weight
10% by weight when the content of Al ₂ O ₃ is 5% by weight or more
Hereinafter, CaO is more than 0 and 5% by weight or less, and MgO is 0% or less.
More than 3% by weight, more than 2% by weight of K ₂ O and less than 5% by weight, more than 4% by weight of Na ₂ O and less than 10% by weight,
B ₂ O ₃ is 10% by weight or more and 30% by weight or less. The lead-free frit of the afterglow paint of the present invention is composed of MgO and C
It contains both aO and preferably neither BaO nor ZnO. Furthermore, the afterglow of the present invention preferably contains 10% by weight or less of an inorganic pigment.

Further, the ceramic product of the present invention is obtained by baking and painting the above-mentioned afterglow paint.
For example, ceramic products, enamel products, glass products, fine ceramic products, and the like.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. However, the following examples illustrate afterglow paints and ceramic products for embodying the technical idea of the present invention, and the present invention converts the afterglow paints and ceramic products to the following. Do not specify.

Further, in this specification, in order to make it easier to understand the claims, the numbers corresponding to the members shown in the embodiments are set forth in the “claims” and “ In the column of “means”. However, the members described in the claims are not limited to the members of the embodiments.

The afterglow paint of the present invention contains an afterglow phosphor excellent in heat resistance and weather resistance, and further contains a lead-free frit suitable for this phosphor. The afterglow phosphor and the lead-free frit were subjected to extensive tests and intensive studies, and as a result, the following afterglow paints were completed.

The afterglow paint contains at least a phosphor and a lead-free frit, and the phosphor is represented by the following general formula. _{Ln 2 O 2 S: Eu x} , M y 0.00001 ≦ x ≦ 0.5 0.00001 ≦ y ≦ 0.3 , however, Ln in the composition formula is at least one selected from the group consisting of Y, La, Gd and Lu. M is a co-activator, and is at least one selected from the group consisting of Mg, Ti, Nb, Ga, and Ta. Lead-free frit is
The composition contains at least CaO and MgO. The afterglow phosphor is 1 part by weight or more and 100 parts by weight or less based on 100 parts by weight of the lead-free frit.

A lead-free frit is prepared as follows. The lead-free frit can be obtained by weighing and mixing and melting the oxide and carbonate compounds having the composition ranges described above. In this case, it is a necessary condition to include at least CaO and MgO. However, the lead-free frit preferably does not contain any of BaO and ZnO. This is because a lead-free frit containing BaO and ZnO reacts with the afterglow phosphor to form a sulfide compound when baked on a ceramic product, and turns black to deteriorate the afterglow property and the light emission property.

The lead-free frit and the afterglow phosphor are mixed as follows. An afterglow paint containing only a lead frit and an afterglow phosphor and containing no pigment has a lead-free frit of 10%.
The amount of the afterglow phosphor is preferably in the range of 2 to 100 parts by weight with respect to 0 parts by weight. When the amount of the afterglow phosphor is 40 parts by weight or more with respect to 100 parts by weight of the lead-free frit, the state of the painted surface becomes mat-like (matte). Semi-matte is used when the afterglow phosphor is in the range of 25 to 40 parts by weight, and gloss is obtained when the afterglow phosphor is 25 parts by weight or less with respect to 100 parts by weight of the lead-free frit. When adding an inorganic pigment to the afterglow paint, the inorganic pigment is mixed in an amount of 5% by weight or less based on the whole.

The following are used as the inorganic pigment added to the afterglow paint. In the present specification, the term "inorganic pigment" means a pigment generally used particularly in the ceramic industry, and includes pigments such as Turkish blue, lemon yellow, malon, peacock, navy blue, red tea, and neodymium oxide, Metal oxides such as erbium oxide and prasedium oxide can be used.

The paint is prepared as follows. The lead frit is mixed with an inorganic pigment, if necessary, finely pulverized using a porcelain pot mill or the like, and finally, an afterglow phosphor is added and mixed to obtain a paint powder. It can be obtained by adding and mixing a binder and a solvent to the paint powder thus obtained. The mixing with the binder is performed using a raikai machine or the like so that the solid content of the powder is uniformly suspended. The binder is added in an amount of 1 to 50 parts by weight based on 100 parts by weight of the solid content.

The following are used as the binder.
As the binder used for the afterglow paint, carboxymethylcellulose (CMC), gum arabic glue, bracken glue, squeegee oil, and the like which are usually used for paints can be used. The binder causes the afterglow phosphor and the lead-free frit to adhere to the surface of the ceramic product, and is burned off when fired. For this reason, the binder does not necessarily need to be added to the afterglow paint. For example, the afterglow phosphor and the lead-free frit can be kneaded in water and applied to the surface of the ceramic product.

The afterglow paint is applied to a ceramic product as follows. The afterglow paint may be a commonly used general painting method. For example, there are a silk screen printing method, a spraying method, a brush / brush coating method, and the like.

The ceramic products to which the afterglow paint can be printed are as follows. Afterglow paints are applicable throughout ceramics, ceramic products including tiles,
It can be used for enamel products, glass products, fine ceramic products, etc.

The painted ceramic product is 700 ° C.
Bake at a temperature of ８850 ° C. for about 5 to 8 hours to burn the afterglow paint.

The afterglow phosphor contained in the afterglow paint is as follows.
Prepare as follows. As a raw material of the afterglow phosphor,
For example, Y₂O₃, Eu₂O₃, MgO, TiO ₂As
Metal oxide or carbonate, sulfate, oxalic acid
Easily oxidized by baking at high temperature such as salt and hydroxide
Select the compound that will be the product. Luminescent properties are pure raw material
The purity of these raw materials is 99.9% or less
The upper is suitable, more preferably 99.99% or more
Preferably, there is. These raw materials are adjusted to a predetermined molar ratio.
After mixing and mixing, add
And a suitable flux (such as an alkali metal carbonate),
After calcination, an afterglow phosphor that emits red light is obtained.

[0023]

EXAMPLE A lead-free frit a, b, c having the following composition is fired. The lead-free frit a is used for the afterglow paint of the embodiment of the present invention. The lead-free frit b and c are made of Mg
Since it does not contain both O and CaO, it is not used for the afterglow of Examples of the present invention.

<Frit a> SiO ₂ 52.6 wt% Al ₂ O ₃ 7.7 wt% CaO 0.7 wt% MgO MgO 1.6 wt% · _{K 2} O .................. 2.0 wt% · Na ₂ O ............... 9.3 wt% _· B 2 _{O 3} ............ 26.1 wt%

<Frit b> SiO ₂ 39.4% by weight Al ₂ O ₃ 4.5% by weight CaO 12.3% by weight BaO 3% by weight 14.2 wt% · _{K 2} O .................. 0.7 wt% · Na ₂ O ............... 7.7 wt% _· B ₂ O 3 ............... 21.2 wt%

<Frit c> SiO ₂ 49.2% by weight Al ₂ O ₃ 4.7% by weight CaO 3.2% by weight ZnO ............... 2.5 wt% · _{K 2} O .................. 1.3 wt% · Na ₂ O ............ 12.5 _{wt% · B 2 O 3 ............... 26} . 6% by weight

The lead-free frit b is made of Mg of the lead-free frit a.
BaO is used in place of O, and the lead-free frit c is Zn
O is used and does not contain both MgO and CaO,
It is not used for the afterglow of the present invention. Furthermore, since the lead-free frits b and c contain BaO or ZnO, when the afterglow paint is baked on a ceramic product, it reacts with the afterglow phosphor to form a sulfide compound,
Decreases light emission characteristics and afterglow characteristics.

As an afterglow phosphor, Y ₂ O ₂ S: Eu, M
g, 20 wt% of Ti phosphor and 80 wt% of each of a, b, and c as lead-free frit were prepared to produce a solid specimen of an afterglow paint, which was baked at 800 ° C. to afterglow. The time change of luminance was obtained. This is plotted in FIG. 1 (frit c did not emit light). However, this figure
It shows the afterglow luminance when irradiated with black light having a light energy of 0.5 mW / cm ² . As shown in this figure, the afterglow paint using the lead-free frit b (Comparative Example 1) had a significantly lower afterglow luminance than that using the lead-free frit a (Example 1).

The afterglow phosphor used in the present invention exhibits strong luminescence due to trivalent Eu as an activator,
u absorbs an extremely wide range of light energy from visible light to ultraviolet region and emits light for a long afterglow time. Therefore, the ceramic product painted using the afterglow paint of the present invention emits light with high efficiency when excited in a wide wavelength range such as natural light. In addition, it emits light by being excited by artificial lighting such as incandescent lamps and fluorescent lamps as well as sunlight, and exhibits afterglow.

[0030]

[Example 1] The following raw materials were weighed and mixed as raw materials, then put into a flask, and melted in an electric furnace heated to 1400 ° C to obtain a lead-free frit.・ SiO ₂ ...... 52.6% by weight ・ Al ₂ O ₃ 7.7% by weight ・ CaO 0.7% by weight ・ MgO 1.6% by weight ・ K ₂ O 2.0% by weight ・ Na ₂ O 9.3% by weight ・ B ₂ O ₃ 26.1% by weight

The composition was Y ₂ O ₂ S: Eu _0.082, Mg
_The following are weighed as raw materials of the afterglow phosphor to be _{0.086 and} Ti _0.030 . _{· Y 2 O 3 .................. 46.5g ·} Eu 2 O 3 .................. 3.0g · MgCO 3 ............... 1.5g · TiO 2 .................. 0. 5g ・ Sulfur (S) 22.7g ・ Na ₂ CO ₃ 22.0g

After mixing the above raw materials, the mixture is filled in an alumina crucible and fired at 1100 ° C. for 6 hours. After the baking, washing is performed several times, the flux is washed, and then dried at 120 ° C. for 10 hours to obtain the afterglow phosphor having the above-described composition.

20 g of the afterglow phosphor and 80 g of the above-mentioned lead-free frit were sufficiently mixed to obtain an afterglow paint.

Example 2 To the afterglow paint obtained in Example 1 was added 1% by weight of erbium oxide as a pigment.
In order to suspend the pigment, the afterglow phosphor, and the lead-free frit, 30% by weight of a 1% CMC aqueous solution is mixed with 100 parts by weight of the powder solid content to prepare an afterglow paint slurry.
The obtained afterglow paint slurry is applied to a ceramic tile with a brush. Thereafter, the ceramic style is placed in a firing furnace and fired at 800 ° C. for several hours to obtain a ceramic product painted with an afterglow paint in which the afterglow color is red.

Example 3 To the afterglow paint obtained in Example 1, 1% by weight of Turkish blue was added as a pigment. To suspend the pigment, the afterglow phosphor and the lead-free frit,
% CMC aqueous solution is mixed in an amount of 30 parts by weight with respect to 100 parts by weight of the solid content of the powder to obtain an afterglow paint slurry. The obtained afterglow paint slurry is applied to a ceramic tile with a brush. Thereafter, the ceramic style is placed in a firing furnace and fired at 800 ° C. for several hours to obtain a ceramic product painted with an afterglow paint having a red afterglow color.

Example 4 The paint obtained in Example 1
As a pigment, 1% by weight of yellow-green is added. In order to suspend the pigment, the afterglow phosphor, and the lead-free frit, 30 parts by weight of a 1% CMC aqueous solution is mixed with 100 parts by weight of the powder solid content to prepare an afterglow paint slurry. The obtained afterglow paint slurry is applied to a ceramic tile with a brush and fired at 800 ° C. for several hours to obtain a ceramic product having a red afterglow color.

Comparative Example 1 The following raw materials were weighed as lead-free frit raw materials. · SiO ₂ ··· 39.4% by weight · Al ₂ O ₃ ··· 4.5% by weight · CaO ··· 12.3% by weight · BaO ··· 14.2% by weight · K ₂ O ··· ...... 0.7 wt% _· Na 2 O ............ 7.7 wt% _· B 2 _{O 3} ......... 21.2 wt%

These raw materials are placed in a jar, and
It was melted in an electric furnace heated to 400 ° C. to form a lead-free frit.

80 g of the obtained lead-free frit and 20 g of an afterglow phosphor were sufficiently mixed, and 30 g of a 1% CMC aqueous solution was mixed in order to suspend them into paint.
Make it an afterglow paint slurry. This afterglow paint slurry was applied to a ceramic tile with a brush and baked at 800 ° C. for several hours.

Comparative Example 2 The following raw materials were weighed as lead-free frit raw materials. · SiO ₂ ··· 49.2 wt% · Al ₂ O ₃ · · · 4.7 wt% · CaO · · · 3.2 wt% · ZnO · · · 2.5 wt% · K ₂ O ............... 1.3 wt% _· Na 2 O ......... 12.5 wt% _· B 2 _{O 3} ......... 26.6 wt%

These materials were placed in a jar, and
The frit was melted in an electric furnace heated to 00 ° C. In order to sufficiently mix the obtained lead-free frit (80 g) and the afterglow phosphor (20 g) and suspend them in a paint,
30 g of a 1% CMC aqueous solution is mixed to make a slurpable paint slurry. The afterglow paint slurry was applied to the ceramic tile with a brush and baked at 800 ° C. for several hours.

The ceramic tiles obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were illuminated by a white fluorescent lamp at an illuminance of 300.
The afterglow phosphor was excited to be lux. After the lighting was stopped, the afterglow color of each tile was visually recognized in the dark. In addition, the appearance of the picture (gloss, mat, firing color) is also compared, and the results are summarized in Table 1.

[0043]

[Table 1]

As shown in Table 1, Examples 1 to 4 of the present invention
The ceramic products described above had a beautiful red color afterglow, and had a glossy appearance with a picture, and a high-quality picture was obtained. On the other hand, Comparative Examples 1 to
The ceramic product of No. 2 had no afterglow and did not develop a beautiful color even in a painted state.

[0045]

The afterglow paint of the present invention and the ceramic product painted with the afterglow paint give a beautiful red color with high afterglow luminance, and give the ceramic a new and unique painting. There are features that can be.

In addition, afterglow paint and ceramic products are
Since inorganic pigments can be mixed and used, multicoloring is possible, and diversification in design can be achieved, such as different coloring at daytime and at night.

Further, the lead-free frit contained in the afterglow paint is safe for the human body, and there is no fear of harming the health of ceramic products using the same.

[Brief description of the drawings]

FIG. 1 is a graph showing the afterglow characteristics of the afterglow paint of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 7/12 C09D 7/12 Z 201/00 201/00 // C01F 17/00 C01F 17/00 EF Terms (Reference) 4D075 CB09 CB11 DB14 EC01 EC03 EC11 4G076 AA03 AB06 AB08 AB09 AB12 BA38 BB01 CA21 DA15 DA30 4J038 BA011 BA041 BA201 HA016 HA066 HA176 HA196 HA206 HA216 HA356 HA446 KA06 KA07 KA12 NA01 NA19 PA19 PB14 PC03

Claims (9)

[Claims] 1. An afterglow paint for painting, which comprises at least a phosphor and a lead-free frit, and is baked on a ceramic product, having the following composition. (A) The afterglow phosphor contained in the afterglow paint is represented by the following general formula. _{Ln 2 O 2 S: Eu x} , M y 0.00001 ≦ x ≦ 0.5 0.00001 ≦ y ≦ 0.3 , however, Ln in the composition formula Y, La, at least one selected from the group consisting of Gd and Lu, M Is a co-activator and is at least one selected from the group consisting of Mg, Ti, Nb, Ga and Ta. (B) The lead-free frit comprises at least MgO and Ca
It contains both O and the content of MgO is 0.1% by weight or more and 5% by weight or less, and the content of CaO is 5% by weight or less. (C) The afterglow paint contains 1 to 100 parts by weight of the afterglow phosphor based on 100 parts by weight of the lead-free frit. 2. The composition of the lead-free frit includes 20% by weight or more and 60% by weight or less of SiO ₂ , 5% by weight or more and 10% by weight or less of Al ₂ O ₃ , and CaO more than 0% and 5% by weight. Below, MgO is more than 0 and 3% by weight or less, K ₂ O
Is 2% by weight or more and 5% by weight or less, Na ₂ O is 4% by weight or more and 10% by weight or less, and B ₂ O ₃ is 10% by weight or more and 30% by weight.
The afterglow paint according to claim 1, wherein the content is not more than% by weight. 3. The afterglow paint according to claim 1, wherein the lead-free frit contains both MgO and CaO and does not contain any of BaO and ZnO. 4. The afterglow paint according to claim 1, which contains 10% by weight or less of an inorganic pigment. 5. A ceramic product obtained by baking an afterglow paint containing at least an afterglow phosphor and a lead-free frit, wherein the afterglow paint has the following composition. (A) The afterglow phosphor contained in the afterglow paint is represented by the following general formula. _{Ln 2 O 2 S: Eu x} , M y 0.00001 ≦ x ≦ 0.5 0.00001 ≦ y ≦ 0.3 , however, Ln in the composition formula Y, La, at least one selected from the group consisting of Gd and Lu, M Is a co-activator and is at least one selected from the group consisting of Mg, Ti, Nb, Ga and Ta. (B) The lead-free frit comprises at least MgO and Ca
It contains both O and the content of MgO is 0.1% by weight or more and 5% by weight or less, and the content of CaO is 5% by weight or less. (C) The afterglow paint contains 1 to 100 parts by weight of the afterglow phosphor based on 100 parts by weight of the lead-free frit. 6. The composition of the lead-free frit includes 20% by weight or more and 60% by weight or less of SiO ₂ , 5% by weight or more and 10% by weight or less of Al ₂ O ₃ , and CaO more than 0% and 5% by weight. Below, MgO is more than 0 and 3% by weight or less, K ₂ O
Is 2% by weight or more and 5% by weight or less, Na ₂ O is 4% by weight or more and 10% by weight or less, and B ₂ O ₃ is 10% by weight or more and 30% by weight.
The ceramic product using the afterglow phosphor according to claim 5, wherein the content is not more than weight%. 7. The ceramic product using the afterglow phosphor according to claim 5, wherein the lead-free frit contains both MgO and CaO and does not contain any of BaO and ZnO. 8. The ceramic product using the afterglow phosphor according to claim 5, wherein the afterglow paint contains 10% by weight or less of an inorganic pigment. 9. The ceramic product using the afterglow phosphor according to claim 5, wherein the ceramic product is any one of a ceramic product, an enamel product, a glass product, and a fine ceramic product.