JP4865994B2 - Ceramic with decorative decoration and manufacturing method thereof - Google Patents

Description

  The present invention relates to a ceramic with a decorative decoration and a method for producing the same, and more particularly to a technique for obtaining a decorative decoration having a high quality texture such as a jewel.

  One type of decoration applied to ceramics is a thick decoration that is fixed using transfer paper. As this thick decoration has a three-dimensional effect as the thickness increases, it is evaluated as a high-grade ceramic. An example of the decorative decoration with an inglaze picture described in Patent Document 1 and the thick decoration described in Patent Document 2 are examples.

JP-A-5-301696 JP 2000-7468 A

  By the way, in the conventional thick decoration as described above, a transfer paper whose thickness is increased by multi-layer printing with a decorative pattern is created, and a thick decoration is applied using the transfer paper, or high temperature baking is used. In other words, the decorative material is melted into the vitreous material of the porcelain pottery layer to give a decorative decoration, which is nothing but a white or colored opaque or translucent decorative decoration. That is, it did not provide a transparent decorative decoration with a three-dimensional and gem-like texture.

  The present invention has been made against the background of the above circumstances, and the purpose of the present invention is to provide a transparent thick decoration with a three-dimensional and transparent gem-like texture. It is to provide a ceramic or a manufacturing method thereof.

  As a result of repeating various studies to achieve the above object, the present inventor provided a colored base layer between the eaves layer and the thick decorative layer and changed the thick decorative layer from the translucent material. When it was constructed and the colored foundation layer could be seen through the thick decorative layer, it was found that a high-quality decorative decoration with a gem-like texture was obtained. In addition, when the thick decorative layer is formed from a translucent material in the same manner as described above, and a filler is added to the thick decorative layer, a high-quality decorative decoration with a pearly texture is obtained. I found out that I could get it. The present invention has been made based on such findings. In the present invention, the filler refers to a substance that is substantially insoluble in the first glass frit, such as inorganic pigments, metal oxides, and minerals.

In other words, the gist of the invention according to claim 1 is that a bubble formed by baking with painting is applied to a cloth composed of a base material which is a sintered body and a vitreous cocoon layer welded to the surface of the base material. A method for producing a ceramic with translucent or transparent vitreous embellishment without emulsion, comprising: (a) a portion of the surface of the cocoon layer of the fabric subjected to the embellishment 20 μm to 20 μm for forming a translucent thick layer having a hemispherical cross-sectional shape having a height of 0.5 to 3.0 mm after melting and capable of observing reflected light from the fabric side A build-up material layer forming step of forming a build-up material layer including a first glass frit having a particle size of 5 mm; and (b) the build-up material layer formed on the surface of the cocoon layer of the dough. a picture with baking step of melting by the urging firing, seen including, the first glass frit, 2 mol Or less (including 0 mol%) lies in comprising ZrO ₂ and 10 mol% to 30 mol% of _{B 2} O ₃ in.

Further, the gist of the invention according to claim 3 is that the thick material layer formed by the thick material layer forming step generates pearls by generating light scattering in the thick layer after melting. It is to include a light scattering filler for generating a tonal texture.

The gist of the invention according to claim 2 is that a base material layer including a second glass frit for constituting a colored base layer positioned between the cocoon layer of the fabric and the thick layer. The method further includes a base material layer forming step of forming the thick material layer on the cocoon layer of the dough before the formation of the thick material layer.

According to the first aspect of the present invention, there is no air bubbles or milky permeation welded to the fabric made of the sintered body and the vitreous cocoon layer welded to the surface of the base. The method for producing a ceramic with a light or transparent vitreous thick decoration is: (a) on the surface of the cocoon layer of the dough, on the portion to be thickly decorated, 0.5 to No. 2 having a particle diameter of 20 μm to 5 mm for constituting a translucent thick layer having a hemispherical cross-sectional shape having a height of 3.0 mm and capable of observing reflected light from the fabric side after melting. A thick material layer forming step of forming a thick material layer containing one glass frit; and (b) melting the thick material layer formed on the surface of the surface of the cocoon layer of the dough by the above-mentioned baking with painting. look including the image with the firing step of the first glass frit is less 2 mol% (provided that the 0 mol% Since comprising ZrO ₂ and 10 mol% to 30 mol% of B ₂ O ₃ free), by fluoroscopy coloration of underlying through the thickness up layer after AtsuSakari material layer is fired, three-dimensional transparent feeling Since it is possible to observe a colored or filler like a certain jewel, a ceramic having a transparent thick decoration with a texture like a jewel or a pearl can be obtained. Furthermore, since the thick layer is formed using the first glass frit having a particle size of 20 μm to 5 mm, the entrainment of bubbles is reduced during firing, and the transparency after firing is further enhanced.

Moreover, according to the invention concerning Claim 3 , the said thick material layer formed by the said thick material layer formation process produces | generates light scattering in the said thick material layer after a fusion | melting, and is a pearl-like texture. Because it contains a light-scattering filler for generating, by seeing through the light-scattering filler through the thick layer, it is possible to observe a three-dimensional and transparent pearly color tone, A ceramic with transparent thick decoration with a pearly texture can be obtained.

According to the invention of claim 2 , the base material layer including a second glass frit for constituting a colored base layer positioned between the cocoon layer and the thick layer of the fabric is the thick material. since the base material layer forming step of forming at a position where the thickness Sheng material layer on glaze of the dough is formed prior to layer formation is Ru further includes, through the thickness up layer after firing of AtsuSakari material layer By seeing through the coloring of the underlayer, it is possible to observe coloring like a jewel with transparency, so that a ceramic with a transparent embellishment with a jewel-like texture can be obtained.

  Here, preferably, the first glass frit included in the thick material layer is made of a predetermined oxide, and includes an oxide, carbonate, and nitrate containing chemical components necessary to have a desired glass composition. In addition, industrial products such as composite oxides, reagents, or natural raw materials such as kaolin, feldspar, and quartz sand are appropriately selected and prepared as starting materials. The first glass frit is preferably a transparent glass for the purpose of coloring itself within a range not losing translucency from the necessity of design, although the thick layer obtained thereby is preferably transparent. An appropriate amount of various metals, metal oxides, metal nitrates, metal halides, etc., which become colorants may be added. Such a raw material mixture is mixed in a refractory crucible such as alumina, chamotte, refractory clay, platinum after being mixed for 30 minutes to several hours so as to be sufficiently uniform with a dry mixer or the like. It is put into a furnace maintained at a temperature. In order to form a homogeneous glass, a high temperature is preferable, and a melting temperature of 1200 to 1500 ° C. is generally used. The homogeneously melted and liquefied melt is rapidly poured into water and rapidly cooled to obtain a homogeneous glass lump. The glass lump is pulverized by a pulverizer such as a ball mill over a set time so as to obtain a target particle size (particle size). The crushed glass frit is classified so as to have a desired particle size by a sieve, an airflow classifier, or the like, if necessary.

  In the thick decoration of about 0.2 to 3.0 mm after firing, it is desirable to use a first glass frit having a particle size of at least 20 μm or more in order to increase the transparency of the thick layer after firing. When the particle size is less than 20 μm, particularly 10 μm, entrainment of bubbles increases during firing, and the thick layer after firing tends to become cloudy. The upper limit value of the particle size of the first glass frit can be used up to a value that allows decoration work or painting work, for example, a particle size of about 5 mm.

The first glass frit is preferably 0 mol% to 2 mol% ZrO _2, ie 2 mol% or less ZrO _2, and 0 mol% to 30 mol% B ₂ O _3, ie 30 mol% or less B _2. In the thick layer after firing the thick material layer containing O ₃ , the amount of ZrO ₂ (zirconium oxide) that has an emulsion action and B ₂ O ₃ (boron oxide) that easily foams during firing is suppressed. Therefore, a highly transparent thick layer can be obtained.

When the ZrO ₂ component having an emulsion action is 3 mol% or more, the thick layer after baking with painting becomes milky regardless of the particle size of the first glass frit, and it becomes difficult to obtain a transparent feeling like a jewel. However, in order to improve the chemical resistance of the thick layer according to the present invention, it is desirable that about 1 mol% of ZrO ₂ is contained, and in this sense, 1 mol% to 2 mol% of ZrO ₂ is preferable. Should be included. Moreover, since tin oxide, titanium oxide, and the like also have an emulsion action, a large amount in the glass frit is not preferable.

The above-mentioned B ₂ O ₃ component, which has an easily foaming property that increases the tendency of foaming in glass, exceeds 30 mol%, and the formation of bubbles in the thick layer after baking with painting becomes noticeable and white turbidity. Thus, it is difficult to obtain the transparency as described above. Considering gray discoloration due to residual carbon after firing caused by organic substances such as vehicle added when the first glass frit is made into a paste so as to facilitate painting work, it should be 20 mol% or less. Is more desirable. However, the B ₂ O ₃ component has an effect of not increasing the thermal expansion coefficient. Therefore, the B ₂ O ₃ component is preferably contained within a range of 10 mol% to 20 mol%.

The chemical composition of the first glass frit is not particularly _{limited, SiO 2, Al 2 O 3} , B 2 O 3, P 2 O 5, CaO, MgO, BaO, ZnO, PbO, Na 2 O, K 2 O, Other oxides such as Li ₂ O and ZrO ₂ may be contained as necessary, but lead-free glass containing no lead component PbO is preferable.

The first glass frit constituting the thick layer after baking with a picture has a difference in thermal expansion of 3 × 10 with respect to the second glass frit constituting the foundation layer of the thick layer or the ceramic glaze layer. The chemical composition is adjusted to be within ⁻⁶ K ⁻¹ , more preferably within 1 × 10 ⁻⁶ K ⁻¹ . When the difference in thermal expansion becomes a value larger than that, a thermal shock is applied to the ceramics, or insertion or separation is generated in the thick decoration or the thick layer at the time of cooling after baking with painting.

  When the first glass frit is made into a paste, a small amount of the pigment, metal oxide, composite oxide, mineral powder or the like is added as a filler and mixed and kneaded within a range that does not impair the transparency of the glass itself after firing. It doesn't matter. These are preferably separated from each other and dispersed in the transparent glass as colored fine bodies after firing.

  As the second glass frit constituting the base layer after firing, a general ceramic paint, preferably a lead-free paint is used.

Further, the first glass frit included in the thick material layer and the second glass frit included in the base material layer are made of glass frit having a difference in thermal expansion coefficient of 1 × 10 ⁻⁶ K ^{−1 or} less. It should be a thing. If it does in this way, generation | occurrence | production of a fitting, peeling, etc. will be prevented suitably between the thick layer after baking and a base layer.

  As ceramics, general ceramics, porcelain, bone china, etc. are used. If the pottery is colored and the glazed layer is transparent, the color of the pottery can be seen through the transparent thick layer even if there is no colored underlayer, and it is transparent with a gem-like texture. A decorated ceramic is obtained.

  The porcelain glazing layer is a general hard or soft glazing, and if it is a colored glazing layer, the coloring of the glazing layer is seen through a transparent thick layer even if there is no colored underlayer. It is possible to obtain a ceramic with a transparent embellishment that has a gem-like texture with only a transparent thick layer.

  The above-mentioned thick layer does not necessarily have to be fixed on the eaves layer via the underlayer, and may protrude from the underlayer and partially touch the eave layer.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In the following description, a thick decoration example in the case where a bone china is used as an example of ceramics will be described. In the drawings used in the following description, the dimensional ratios such as length, width, and thickness are appropriately changed for easy understanding.

  FIG. 1 is a schematic view showing an enlarged cross section of a main part of a ceramic 10 according to an embodiment of the present invention. In FIG. 1, a bone china dough 12 is applied to a substrate 14 obtained by sintering a general material at a temperature of about 1250 ° C., for example, and to the surface of the substrate 14 by a well-known method. Then, a vitreous glazing layer 16 which is fired and welded at a temperature of about 1150 ° C. is provided.

  On the cocoon layer 16 of the dough 12, a base layer 18 that has been transferred and baked using a transfer paper generally known as a painting technique, and a paste containing a glass frit of material are applied and The fired translucent thick layer 20 is fixed. The underlayer 18 is an opaque glass material colored according to a pattern by including a ceramic paint, and is melted by baking with painting and fixed to a thickness of about 10 to 100 μm. The thick layer 20 is a transparent or transparent glassy material free from bubbles and emulsion, and is melted simultaneously with the underlayer 18 or by another painting baking, and has a thickness of about 0.2 mm to 3 mm. It is directly fixed on the base layer 18 at a height. The thick layer 20 has a semi-cylindrical or hemispherical cross-sectional shape formed by the surface tension of the glass during firing, that is, melting. The foundation layer 18 and the thick layer 20 are configured on the fabric 12 in a predetermined pattern, so that the thick decoration 22 is applied.

  In the ceramic 10 decorated thickly as described above, the translucent thick layer 20 having a thickness sufficiently larger than that of the ground layer 18 is fixed on the colored and opaque ground layer 18, so that 0 is obtained. Because the thick decoration having a height of 2 to 3.0 mm is configured, the coloring of the underlayer 18 is seen through the thick layer 20 so that it looks like a three-dimensional and transparent jewel. Therefore, it is possible to obtain the ceramic 10 with a transparent thick decoration having a three-dimensional jewel-like texture.

  FIG. 2 explains the manufacturing process of the ceramic 10. In FIG. 2, in the ceramic dough production process P <b> 1, the dough 12 is produced through a well-known production process for bone chana. In the transfer paper manufacturing process P2, the transfer paper is manufactured through a well-known transfer paper manufacturing process. The transfer paper is provided with a well-known printing paste for ceramic painting obtained by kneading the second glass frit for constituting the underlayer 18 and an organic substance such as a pigment or a vehicle (resin). A thick embellishment pattern is formed by screen printing with a pattern.

  In the base material layer forming step P3, the base material layer is formed at a predetermined position on the ceramic cloth 12 by using the transfer paper. This base material layer has the same shape as that of the base layer 18 shown in FIG. 1, and organic materials such as a vehicle and a top coat disappear during firing, and the second glass frit is melted so that the thickness is greater than that during printing. And the glassy base layer 18 colored with paint (pigment) is reduced.

On the other hand, in the glass frit manufacturing step P4, starting materials such as various oxides, industrial products such as carbonates, reagents, natural mineral materials such as quartz sand are prepared so as to contain any of the components shown in Table 1. The mixture is mixed in a refractory crucible such as chamotte after being mixed for about 1 hour by a dry mixer or the like so that the mixture is sufficiently uniform, and the mixture is placed in a furnace maintained at a temperature of about 1400 ° C. The crucible is charged, and the melted material liquefied by melting the raw material in the crucible is dropped into water and rapidly cooled to produce a homogeneous glass lump. Next, the glass lump is pulverized for several hours so that the target particle size can be obtained with a ball mill or the like, and then classified so as to have a predetermined particle size by a sieve or an airflow classifier, and is lead-free for transparent decorative decoration A first glass frit that is a glass frit is manufactured. This first glass frit contains, for example, the components shown in any of Samples 2 to 5 in Table 1 so that there is no cloudiness or bubbles after firing, and there is no space between the base layer 18 and the glazing layer 16. The transparent thick layer 20 having a thermal expansion coefficient difference of 3 × 10 ^{−6 or} less, preferably 1 × 10 ⁻⁶ K ^{−1 or} less, is formed.

(Table 1)

Composition table of lead-free glass frit for transparent decoration

Component Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
Na ₂ O 7 7 2 4.5 4.5
K ₂ O 1 1 1 1.0 1.0
Li ₂ O 6 6 10 6.0 6.0
MgO 3 3-1.5 1.5
CaO 3 3-1.5 1.5
ZnO 3 3-1.5 1.5
Al ₂ O ₃ 4 4 5 4.0 4.5
SiO ₂ 60 62 60 60.0 60.0
B ₂ O ₃ 10 11 22 18.0 16.5
ZrO ₂ 3--2.0 1.0
Total 100 100 100 100 100
Coefficient of thermal expansion 7.7 7.7 6.0 6.6 6.9
(However, the unit of the component is mol%. The thermal expansion coefficient is 25 to 400 ° C.
The unit of which is × 10 ⁻⁶ / K. )

  Next, in the paste manufacturing step P5, a paste in which the first glass frit is pasted is used for the application work for forming a thick material layer such as application by brush coating, application by a syringe, application by printing, and the like. Produced. For example, the first glass frit manufactured by the glass frit manufacturing process P4 is kneaded with a vehicle (resin) or a solvent to obtain a highly viscous fluid suitable for the coating operation.

  In the thick material layer forming step P6, the paste manufactured in the paste manufacturing step P5 is applied on the base material layer formed in the base material layer forming step P3 to form a thick material layer. This thick material layer has the same shape as the thick layer 20 shown in FIG. 1, organic matters such as a vehicle disappear during firing, and the first glass frit is melted, so that the thickness is larger than that during printing. It decreases and becomes the said thick build-up layer 20 of transparent glassy.

  In the firing step P7, the ceramic fabric 12 on which the base material layer and the thick material layer are formed is fired at a temperature of, for example, about 850 ° C. in a painting furnace such as an electric furnace or a roller hearth kiln. Thereby, the organic matter in the base material layer and the thick material layer is gasified and burned out, and the second glass frit and the first glass frit contained therein are respectively melted, so that the ceramic 10 shown in FIG. can get. The thick layer 20 in this state is formed in a semi-cylindrical or hemispherical cross-sectional shape by the surface tension of the glass at the time of melting.

Hereinafter, experimental examples in which the present inventor has changed the components and the minimum particle diameter of the first glass frit to a plurality of types and evaluated them will be described.
[Experimental Example 1]
In this experimental example, as the first glass frit, those containing the components shown in Sample 1 to Sample 5 in Table 1 are used, and the thick layer 20 obtained by performing the steps shown in FIG. 2 under the same conditions is used. It was evaluated. Table 2 shows the experimental results. In Table 2, ○ indicates a sensitivity evaluation that the thick layer 20 has good transparency or translucency, and Δ indicates a sensitivity evaluation that the thick layer 20 contains some emulsion or bubbles. X indicates a sensitivity evaluation that the thick layer 20 lacks merchantability because it contains emulsion or bubbles. In Sample 3, it was observed that the thick layer 20 was slightly gray.

(Table 2)
Firing results by frit glass particle size

Minimum particle size Hemispherical sample Sample 1 Sample 2 Sample 3 Sample 4 Sample 5
Classification 10μm Diameter mm 3.4 3.4 4.3 3.3 3.9
Height mm 0.7 0.7 0.6 0.5 0.7
Transparency × × △ × △
20μm Diameter mm 3.7 3.4 3.8 3.2 3.6
Height mm 0.7 0.6 0.7 0.6 0.6
Transparency × △ ○ △ ○
30μm Diameter mm 3.5 3.4 4.2 3.0 3.9
Height mm 0.7 0.7 0.6 0.5 0.7
Transparency × ○ ○ ○ ○
40μm Diameter mm 3.4 3.4 4.2 3.5 3.8
Over height mm 0.6 0.7 0.7 0.8 0.7
Transparency △ ○ ○ ○ ○
53μm Diameter mm 3.4 3.2 4.1 3.2 4.0
Height mm 0.7 0.6 0.6 0.7 0.6
Transparency △ ○ ○ ○ ○
No classification Diameter mm 3.0 3.4 4.2 3.6 3.4
10μm Not Height mm 0.6 0.7 0.6 0.9 0.6
Full including transparency × × × × ×
Gray discoloration None None Slight None None

As apparent from Table 2 above, when the ZrO ₂ having an emulsion action is 3 mol% or more, the thick layer 20 tends to become almost turbid although it slightly depends on the minimum particle size of the frit. Even if it is 2 mol% or less, it will become milky when the minimum particle size of glass frit is less than 20 μm, and even if it is less than 1 mol%, it will become milky if the minimum particle size is less than 10 μm. It becomes difficult to obtain a transparent feeling. In this sense, the ZrO ₂ component is desirably 2 mol% or less in order to obtain a thick transparent layer 20 having no emulsion. However, in order to ensure the chemical resistance of the thick layer, it is desirable that approximately 1 mol% or more of ZrO ₂ is contained, and it is optimal that 1 mol% to 2 mol% of ZrO ₂ is included after all.

  Further, as apparent from Table 2 above, the size of the first glass frit is also related to the entrainment of bubbles in the thick layer 20, that is, the opacification. In thick decoration of about 0.2 to 3.0 mm, when the minimum particle size of the first glass frit is less than 20 μm, particularly 10 μm, entrainment of bubbles increases. For this tendency, it is desirable to use the first glass frit having a particle size of 20 μm or more in order to increase the transparency of the thick layer after firing. The upper limit value of the particle size of the first glass frit is not limited, but can be used up to a value that can be worked by tweezers or the like, for example, about 3 to 5 mm in the decoration work or the painting work.

Further, as apparent from Table 2 above, the B ₂ O ₃ (boron oxide) component contained in the first glass frit is easily foamed during firing when contained in a large amount. In order to obtain a high thickness buildup layer 20, it is desirable that the range be 0 mol% to 30 mol%. Also, in consideration of gray discoloration after firing caused by organic substances such as vehicle added when the first glass frit is made into a paste so as to facilitate painting work, it is 25 mol% or less, preferably 20 mol% or less. Is desirable. The B ₂ O ₃ component has an action that does not increase the thermal expansion coefficient, and is preferably contained within a range of 10 mol% to 20 mol%. On the other hand, if it exceeds 30 mol%, the melting point (softening point) of the glass frit becomes low, so that it is close to the temperature range of decomposition of organic matter, generation of carbon, and disappearance of firing. Become.

[Experiment 2]
Next, in order to obtain the relationship between the height dimension H of the thick layer 20 fixed on the fabric 12 by firing and the transparency thereof, four types of samples were tested using the components of the sample 5. It was created and evaluated in a process under the same conditions as in 1. Table 3 shows the results. According to Experiment 2, when the height dimension H of the thick layer 20 exceeded 2.8 mm, entrainment of bubbles in the thick layer 20 was slightly observed. Thereby, it is desirable that the height dimension H of the thick layer 20 be 3 mm or less.

(Table 3)
Frit glass test by height

Frit glass Diameter mm Height mm Transparency
Sample 5 6.6 2.8 △
5.2 1.9 ○
4.0 1.2 ○
2.7 0.6 ○

  FIG. 3 shows an example of the ceramic 30 in which the foundation layer 18 is not formed and the thick layer 20 is directly fixed to the surface of the fabric 12. The ceramic 30 of the present embodiment is manufactured by the same processes and materials except for the transfer paper manufacturing process P2 and the base material layer forming process P3 in the manufacturing process of FIG. Since the ceramic 30 of the present embodiment can see through the coloring from the thick layer 20 when the substrate 14 or the cocoon layer 16 of the fabric 12 is colored, the same effect as the ceramic 10 of the above-described embodiment can be obtained. It is done. In the present embodiment, the substrate 14 or the eaves layer 16 is the base of the thick layer 20.

  In the ceramics 10 or 30, the first glass frit that is a material of the thick layer 20 is made of a minute light scattering filler in order to generate a pearly texture by scattering light in the thick layer 20. It can also be added to the paste containing it. In this case, by transparently seeing the light-scattering filler through the thick layer 20, a transparent pearl-like color tone can be observed, so that a transparent thick-splitting decoration with a pearl-like texture can be obtained. The applied ceramic 10 or 30 is obtained.

  As described above, according to the method of manufacturing the ceramic 10 or 30 having the light-transmitting thick layer 20 according to the present embodiment, (a) the thick decoration of the surface of the ceramic 10 or 30 is applied. A thick material layer forming step P6 for forming a thick material layer including a first glass frit constituting a light transmissive thick layer capable of observing reflected light from the ground after melting on the ground of the portion to be applied. And (b) a firing step P7 in which the thick material layer formed on the foundation layer on the surface of the ceramic is melted by firing, so that the foundation is passed through the thick layer 20 after the thick material layer is fired. By seeing through the coloring of the glass, it is possible to observe the coloring or filler like a three-dimensional and transparent jewel, so a transparent embellishment with a texture like a jewel or pearl was given. Ceramics are obtained.

  Moreover, according to the present embodiment, the base material layer forming step of forming the base material layer including the second glass frit for constituting the colored base layer 18 positioned between the ceramic fabric 12 and the thick layer 20. Since P3 is further included, by seeing through the coloring of the underlayer 18 through the thick layer 20 after firing the thick material layer, it is possible to observe the coloring like a transparent gemstone, A ceramic with a transparent decoration with a texture like this is obtained.

Moreover, according to the present example, the first glass frit contained in the thick material layer contains 2 mol% or less of ZrO ₂ and 30 mol% or less of B ₂ O ₃ , so In the thick layer 20 after the material layer layer is fired, the amount of ZrO ₂ (zirconium oxide) having an emulsion action and B ₂ O ₃ (boron oxide) which is easily foamed during firing is suppressed, and the transparency is high. A thick layer 20 is obtained.

  In addition, according to the present embodiment, the first glass frit is substantially composed of glass particles having a particle diameter of 20 μm or more, so that the thick layer after the thick material layer is fired. In 20, the entrainment of bubbles is reduced, and a highly transparent thick layer is obtained.

Further, according to this example, the difference in thermal expansion coefficient between the first glass frit included in the thick material layer and the second glass frit included in the base material layer is 1 × 10 ⁻⁶ K ^−1. Therefore, the occurrence of fitting, peeling, or the like between the thick layer 20 and the base layer 18 after firing is suitably prevented.

  In addition, although not illustrated one by one, the present invention can be variously modified without departing from the gist thereof.

It is a figure which shows typically the cross section which expands and shows the principal part of the ceramic with which thick embellishment of one Example of this invention was given. It is a figure explaining the manufacturing process of the ceramics of FIG. It is a figure which shows typically the cross section which expands and shows the principal part of the ceramic with which thick decoration of the other Example of this invention was given.

Explanation of symbols

10, 30: Ceramic 12: Fabric 18: Base layer 20: Thick layer

Claims (3)

Thickness of translucent or transparent vitreous material free from bubbles or emulsion deposited on the fabric consisting of a sintered body and a vitreous cocoon layer welded to the surface of the base. A method of manufacturing a decorated ceramic,
Reflected light from the fabric side having a hemispherical cross-sectional shape having a height of 0.5 to 3.0 mm after melting on a portion of the surface of the cocoon layer to which the thick decoration is applied. A thick material layer forming step of forming a thick material layer including a first glass frit having a particle diameter of 20 μm to 5 mm, to constitute a light transmissive thick layer capable of observing
The AtsuSakari material layer formed on the surface of glaze of the fabric, and a picture with baking step of melting by firing with the picture, seen including,
The first glass frit, 2 mol% or less (including 0 mol%) pottery AtsuSakari decoration, characterized in that it comprises a ZrO ₂ and 10 mol% to 30 mol% of _{B 2} O ₃ of is performed Manufacturing method.   Prior to the formation of the thick material layer, the base material layer including a second glass frit for forming a colored base layer positioned between the fabric layer and the thick layer is formed. The method for producing a ceramic with a decorative embellishment according to claim 1, further comprising a base material layer forming step of forming the thick material layer on the layer at a position where the thick material layer is formed. The thick material layer formed by the thick material layer forming step includes a light scattering filler for generating a pearly texture by generating light scattering in the thick layer after melting. A method for producing a ceramic with a thick decoration according to claim 1 or 2 .

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