JP2019218242A - Sanitary earthenware and manufacturing method of sanitary earthenware - Google Patents

Abstract

To provide a sanitary earthenware capable of enhancing "depth", and a manufacturing method of the sanitary earthenware.SOLUTION: There is provided a sanitary earthenware 1 having an earthenware base material 10, an upper glaze layer 30 positioned on a surface of the sanitary earthenware 10, and an intermediate layer 20 positioned between the earthenware raw material 10 and the upper glaze layer 30, and having percentage of area of air bubbles based on area of a cut surface by cutting the upper glaze layer 30 in a thickness direction of 3% or less. It is preferable that average air bubble diameter of the air bubbles at the cut surface is 50 μm or less. It is preferable that the number of air bubbles at the cut surface is 120 or less per 1 mm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to sanitary ware and a method for manufacturing the sanitary ware.

  2. Description of the Related Art Conventionally, an upper glaze layer (glaze layer) is formed on the outermost surface of sanitary ware such as a toilet bowl and a washbasin in order to suppress the adhesion of dirt or improve the design of the appearance.

In recent years, there is a need for not only hygiene but also a sense of quality and quality in the toilet space and washroom space where sanitary ware is installed. Dignity is perceived not only in design properties such as color and shape.
One of the indexes indicating the quality is image clarity. The image clarity expresses the sharpness of the image reflected on the surface of the sanitary ware, and the sharper the image reflected, the higher the image clarity is determined. Sanitary ware with high image clarity gives a high-quality impression.
For example, Patent Literature 1 proposes a sanitary ware in which a glaze layer having improved image clarity is formed on a pottery substrate surface.

JP 2012-72609 A

One of the indexes indicating quality is “depth”. "Depth" is an expression of the depth of the upper glaze layer on the surface of sanitary ware, and is recognized by human vision. Sanitary ware with a “depth” gives a high-quality impression.
However, in the invention of Patent Literature 1, "depth" of sanitary ware was not considered.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a sanitary ware and a method for manufacturing the sanitary ware, which can further improve “depth”.

  In general, sanitary ware having high image clarity has a clear image reflected on the surface of the sanitary ware, and is likely to give a high-quality impression. However, as a result of intensive studies by the present inventors, sanitary ware having high image clarity does not always have a sense of depth, and no correlation with “depth” was found. The present invention seeks a sense of quality and quality of sanitary ware from a viewpoint different from image clarity.

In order to achieve the above object, the present invention has the following aspects.
[1] A ceramic body, an upper glaze layer located on the surface of the ceramic body, and an intermediate layer located between the ceramic body and the upper glaze layer, wherein the upper glaze layer is cut in a thickness direction. A sanitary ware, wherein the ratio of the area of the bubbles to the area of the cut section is 3% or less.
[2] A ceramic body, an upper glaze layer located on the surface of the ceramic body, and an intermediate layer located between the ceramic body and the upper glaze layer, wherein the upper glaze layer is cut in a thickness direction. A sanitary ware having an average bubble diameter of 50 μm or less in the cut section.
[3] The sanitary ware according to [1] or [2], wherein the number of bubbles on the cut surface is 120 or less per 1 mm ² .
[4] The sanitary ware according to [1], wherein the average bubble diameter of the bubbles on the cut surface is 50 μm or less, and the number of bubbles on the cut surface is 120 or less per 1 mm ² .
[5] The number of air bubbles in a cut surface obtained by cutting the intermediate layer in the thickness direction is 1,000 or less per 1 mm ² , and a ratio of an area of the air bubble to an area of the cut surface of the intermediate layer is 20% or less, The sanitary ware according to any one of [1] to [4], wherein the average bubble diameter of the bubbles on the cut surface of the intermediate layer is 25 μm or less.
[6] The sanitary ware according to any one of [1] to [5], wherein the thickness of the upper glaze layer is 100 μm or more.
[7] The sanitary ware according to any one of [1] to [6], wherein the thickness of the intermediate layer is 200 μm or more.

[8] The intermediate layer composition for forming the intermediate layer is applied to the surface of the ceramic body by dipping, pouring, painting, or spraying, dried, and then the intermediate layer composition The method for producing sanitary ware according to any one of [1] to [7], wherein an upper glaze layer composition for forming the upper glaze layer is applied to a surface on which the upper glaze layer is applied.
[9] The intermediate layer composition for forming the intermediate layer is applied to the surface of the ceramic body by dipping, pouring, painting, or spraying, and then fired to obtain a primary fired body. The method for producing sanitary ware according to any one of [1] to [7], wherein an upper glaze layer composition for forming the upper glaze layer is applied to the primary fired body and fired.

  According to the sanitary ware and the method for manufacturing the sanitary ware of the present invention, the "depth" of the sanitary ware can be further improved.

1 is a sectional view of a sanitary ware according to an embodiment of the present invention. 5 is an example of a DTA curve of an upper glaze layer of sanitary ware according to an embodiment of the present invention.

[Sanitary ware]
Hereinafter, an embodiment of the present invention will be described with reference to FIG.
The sanitary ware 1 shown in FIG. 1 includes a ceramic body 10, an upper glaze layer 30 located on the surface of the ceramic body 10, and an intermediate layer 20 located between the ceramic body 10 and the upper glaze layer 30.

As used herein, "sanitary ware" refers to pottery products used around toilets and toilets. Examples of the sanitary ware 1 include a urinal, a toilet bowl, a toilet tank, a washbasin of a wash basin, and a handwasher.
In the present specification, “porcelain” means a material obtained by applying glazing to the surface using feldspar, porcelain stone, kaolin, or clay as a raw material.

The thickness _{T 1} of the sanitary ware 1 is not particularly limited, for example, preferably from 1 to 50 mm, more preferably from 2 to 30 mm, more preferably 3 to 20 mm. If the thickness T ₁ is not less than the above lower limit, the strength of the sanitary ware 1 is likely enhanced. If the thickness T ₁ is equal to or less than the above upper limit, can sanitary ware 1 lightweight, it is easy to handle.
The thickness T ₁ of the sanitary ware 1, for example, can be measured using calipers.

The image clarity of the sanitary ware 1 is preferably 80 or more, more preferably 85 or more, and even more preferably 90 or more. When the image clarity of the sanitary ware 1 is equal to or more than the lower limit, an impression of high quality is easily given. The upper limit of the image clarity of the sanitary ware 1 is not particularly limited, but is substantially 99 or less.
In the present specification, the image clarity means a DOI value measured by a wave scan DOI measuring device (BYK Gardner, Wave-Scan-DUAL).

As the pottery base 10, a pottery base composition (pottery base slurry) containing feldspar, pottery stone, kaolin, clay or the like as a raw material is formed into a predetermined shape using a plaster mold or a resin mold and fired at 1100 to 1300 ° C. The base that did.
The pottery base composition contains water. The content of water based on the total mass of the pottery base composition is preferably 30 to 50% by mass, more preferably 30 to 40% by mass.

The thickness _{T 10} of the pottery green body 10 is not particularly limited, for example, preferably from 1 to 50 mm, more preferably from 2 to 30 mm, more preferably 3 to 20 mm. If the thickness T ₁₀ is not less than the above lower limit, the strength of the ware matrix 10 is likely to be enhanced. If the thickness T ₁₀ is less than the above upper limit can pottery green body 10 to the light weight, it becomes easy to handle.
The thickness _{T 10} of the pottery green body 10, for example, can be measured using calipers.

The upper glaze layer 30 is a fired product of the upper glaze layer composition for sanitary ware of the present invention (hereinafter, also simply referred to as upper glaze layer composition). The upper glaze layer 30 is a layer made of glaze (glaze) for forming a layer located on the outermost surface of the sanitary ware 1. The upper glaze layer composition is a so-called glaze. The upper glaze layer composition is a slurry (slurry) in which silica sand, feldspar, lime, clay, and the like, which are glaze raw materials, are dispersed in water.
The content of water based on the total mass of the upper glaze layer composition is preferably from 40 to 80% by mass, and more preferably from 40 to 70% by mass.

The average particle diameter of the solid component contained in the upper glaze layer composition is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less. When the average particle size of the solid content contained in the upper glaze layer composition is equal to or less than the upper limit, the melting start temperature of the solid content contained in the upper glaze layer composition is easily reduced.
The lower limit of the average particle diameter of the solid component contained in the upper glaze layer composition is not particularly limited, but is, for example, 0.1 μm or more.
The average particle diameter of the solid component contained in the upper glaze layer composition can be adjusted, for example, by grinding the glaze raw material. As a tool for crushing the glaze raw material, for example, a ball mill can be mentioned.

In the present specification, the “average particle diameter” means a 50% average particle diameter (D50). D50 is a median diameter on a number basis, and means an average particle diameter of 50% in the cumulative distribution. The particle size can be measured, for example, using a laser diffraction type particle size distribution analyzer (“MT3300EX (model number)” manufactured by Nikkiso Co., Ltd.).
The solid content contained in the upper glaze layer composition is a dried product of the upper glaze layer composition.

Examples of the upper glaze layer composition include a composition containing 5 to 25 parts by mass of silica sand, 20 to 40 parts by mass of feldspar, 5 to 15 parts by mass of lime, and 1 to 5 parts by mass of clay.
The upper glaze layer composition preferably contains a frit in addition to the above.
The frit is obtained by melting a frit raw material at a temperature of 1300 ° C. or higher and then cooling it to obtain an amorphous glass. When the upper glaze layer composition contains a frit, the melting start temperature of the upper glaze layer composition can be easily lowered. In addition, since the upper glaze layer composition contains a frit, the upper glaze layer composition can be more uniformly melted, and bubbles in the upper glaze layer can be easily reduced.
As the frit raw material, silicon dioxide (SiO ₂ ) is 40 to 70 mass%, aluminum oxide (Al ₂ O ₃ ) is 5 to 15 mass%, and sodium oxide (Na ₂ O) is based on the total mass of the frit raw material. The sum of potassium oxide (K ₂ O), calcium oxide (CaO), magnesium oxide (MgO), zinc oxide (ZnO), strontium oxide (SrO), barium oxide (BaO), and boron oxide (B ₂ O ₃ ) A composition containing 10 to 50% by mass is exemplified.
The sum of the contents of the components of the frit raw material does not exceed 100% by mass with respect to the total mass of the frit raw material.

  When the upper glaze layer composition contains a frit, the content of the frit is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total mass of the solid content contained in the upper glaze layer composition. preferable. When the content of the frit is equal to or more than the lower limit, the melting start temperature of the upper glaze layer composition is easily reduced. In addition, the content of the frit shall not exceed 100% by mass with respect to the total mass of the solid content contained in the upper glaze layer composition.

The melting start temperature of the upper glaze layer composition can be defined by any of the first melting temperature, the second melting temperature, and the third melting temperature.
The first melting temperature is measured by the following measurement method 1-1.
<Measurement method 1-1>
DTA measurement is performed using alumina powder as a reference substance and a dried product of the upper glaze layer composition for sanitary ware as a sample powder to obtain a DTA curve. In the region above 700 ° C. of the obtained DTA curve, the potential difference ΔV indicating the value ΔT obtained by subtracting the temperature of the reference substance from the temperature of the sample powder is the temperature of the reference substance at the first inflection point at which the temperature decreases, and the first melting temperature. And In the region on the higher temperature side than the first melting temperature, the temperature of the reference substance at the first inflection point where the potential difference ΔV becomes large is defined as the second melting temperature.

The DTA curve is obtained by performing DTA measurement using a differential thermal analysis (DTA) device. The DTA measurement may be a TG-DTA measurement (thermogravimetric differential thermal analysis measurement). In the DTA measurement, alumina powder was used as a reference substance, and a dried product of the upper glaze layer composition was used as a sample powder. The dried product of the upper glaze layer composition is obtained, for example, by heating the upper glaze layer composition to 20 to 110 ° C to evaporate water. The water content based on the total mass of the dried product of the upper glaze layer composition is, for example, 0 to 1% by mass.
In the DTA measurement, a value ΔT ((sample powder temperature) − (reference material temperature) obtained by subtracting the reference material temperature from the sample powder temperature while changing the temperature of the sample powder and the temperature of the reference material by a certain program. )) Is measured as a function of temperature. In the DTA curve, among the inflection points that appear in the region where the temperature of the reference substance exceeds 700 ° C., the first inflection point at which the potential difference ΔV becomes smaller is defined as the first inflection point. The temperature of the reference material at the first inflection point is defined as a first melting temperature. The first inflection point at which the potential difference ΔV becomes large among the inflection points appearing in a region higher than the first melting temperature is defined as a second inflection point. The temperature of the reference substance at the second inflection point is defined as a second melting temperature.

FIG. 2 is a graph of TG-DTA obtained when TG-DTA measurement of the upper glaze layer composition forming the upper glaze layer 30 of the sanitary ware 1 is performed. In the TG-DTA graph, the horizontal axis represents the temperature (° C.) of the reference material. The first axis on the vertical axis represents the mass change (% by mass) of the sample powder. The second axis of the vertical axis represents a potential difference ΔV (μV) indicating a value ΔT obtained by subtracting the temperature of the reference substance from the temperature of the sample powder.
In FIG. 2, C1 represents a TG curve. C2 represents the DTA curve. In C2, the potential difference ΔV increases as the temperature of the reference material increases, and the first inflection point P1 appears in a region where the temperature of the reference material exceeds 700 ° C. At the first inflection point P1, it is considered that the upper glaze layer composition started to melt and the glass structure of the upper glaze layer composition began to loosen. The first inflection point P1 is drawn to the tangent line drawn to C2 when the slope of C2 (the amount of increase in ΔV / the amount of increase in the temperature of the reference material) is maximum, and to C2 when the slope of C2 is minimum. Given by the intersection with the tangent. The temperature of the reference material at the first inflection point P1 is the first melting temperature. The first melting temperature is determined in the same manner as the method for determining the extrapolation melting start temperature in a general TG-DTA graph (see JIS K7121-1987).
C2 has a second inflection point P2 at which ΔV decreases and ΔV increases again after the first inflection point P1 appears. At the second inflection point P2, it is considered that the upper glaze layer composition has melted and the glass structure of the upper glaze layer composition has been completely loosened. The second inflection point P2 is given by the intersection of the tangent drawn to C2 when the slope of C2 is minimum and the tangent drawn to C2 when the slope of C2 is positive. The temperature of the reference material at the second inflection point P2 is the second melting temperature. The second melting temperature is determined in the same manner as the method for determining the melting peak temperature in a general TG-DTA graph (see JIS K7121-1987).

In the DTA measurement, the mass of the reference substance is preferably, for example, 5 to 50 mg.
The mass of the sample powder is preferably, for example, 5 to 50 mg.
The heating temperature for obtaining a dried product of the upper glaze layer composition is preferably, for example, 20 to 110 ° C.
The heating rate when heating the sample powder is, for example, preferably 2 to 10 ° C./min.

  The first melting temperature of the upper glaze layer composition is preferably from 800 to 1050C, more preferably from 820 to 1000C, and still more preferably from 840 to 950C. When the first melting temperature of the upper glaze layer composition is equal to or higher than the lower limit, it is easy to suppress generation of bubbles when firing the upper glaze layer composition. When the first melting temperature of the upper glaze layer composition is equal to or lower than the upper limit, bubbles generated when firing the upper glaze layer composition are easily diffused into the atmosphere.

The second melting temperature is measured by the above measurement method 1-1.
The second melting temperature of the upper glaze layer composition is preferably 850 to 1150C, more preferably 870 to 1100C, and even more preferably 900 to 1050C. When the second melting temperature of the upper glaze layer composition is equal to or higher than the lower limit, it is easy to suppress generation of bubbles when firing the upper glaze layer composition. When the second melting temperature of the upper glaze layer composition is equal to or lower than the above upper limit, bubbles generated when firing the upper glaze layer composition are easily diffused into the atmosphere.

The difference between the second melting temperature and the first melting temperature of the upper glaze layer composition (upper glaze layer melting temperature difference) is preferably 50 to 120 ° C, more preferably 60 to 100 ° C, and even more preferably 70 to 90 ° C. . When the upper glaze layer melting temperature difference is equal to or more than the above lower limit, the average bubble diameter of bubbles generated when firing the upper glaze layer composition is easily reduced. When the upper glaze layer melting temperature difference is equal to or less than the above upper limit, it is easy to suppress generation of bubbles when firing the upper glaze layer composition.
The upper glaze layer melting temperature difference is obtained by subtracting the first melting temperature of the upper glaze layer composition from the second melting temperature of the upper glaze layer composition.

The first melting temperature of the upper glaze layer composition can be adjusted by the type of glaze raw material, the blending ratio of the glaze raw material, the average particle diameter of the solid content of the upper glaze layer composition, and a combination thereof.
The second melting temperature of the upper glaze layer composition can be adjusted similarly to the first melting temperature of the upper glaze layer composition.

The third melting temperature is measured by the following measurement method 1-2.
<Measurement method 1-2>
A dried product of the upper glaze layer composition for sanitary ware is pressure-formed to obtain a cylindrical sample. Light is irradiated while heating the obtained cylindrical sample. The amount of light reflected by the surface of the cylindrical sample is measured. The first temperature at which the amount of reflected light becomes 10 times or more the amount of reflected light detected at the beginning of light emission is defined as a third melting temperature.

In the measurement method 1-2, the columnar sample is obtained by pressure-forming a dried product of the upper glaze layer composition for sanitary ware.
The diameter of the cylindrical sample is preferably, for example, 2 to 10 mm. The height of the columnar sample is preferably, for example, 5 to 20 mm. The mass of the columnar sample is preferably, for example, 100 to 500 mg. The pressure at the time of press-molding the dried product of the upper glaze layer composition is preferably, for example, 10 to 50 MPa.
The amount of reflected light is taken as a value converted into the number of pixels by an image processing system by photographing with a digital camera with a telephoto lens.
The amount of reflected light when heating the cylindrical sample is measured every 1 ° C. "Begins to shine" means that the amount of reflected light reflected by the surface of the cylindrical sample is no longer zero.
The heating rate when heating the cylindrical sample is preferably, for example, 1 to 10 ° C./min.
The amount of light applied to the cylindrical sample is preferably, for example, 500 to 2000 lumens.
At the third melting temperature, it is considered that the upper glaze layer composition starts melting and the glass structure of the upper glaze layer composition is completely loosened.

  The third melting temperature of the upper glaze layer composition is preferably 850 to 1150C, more preferably 870 to 1100C, and even more preferably 900 to 1050C. When the third melting temperature of the upper glaze layer composition is equal to or higher than the lower limit, it is easy to suppress the generation of bubbles when firing the upper glaze layer composition. When the third melting temperature of the upper glaze layer composition is equal to or lower than the upper limit, bubbles generated when firing the upper glaze layer composition are easily diffused into the atmosphere.

  The third melting temperature of the upper glaze layer composition can be adjusted similarly to the first melting temperature of the upper glaze layer composition.

When determining the melting start temperature of the upper glaze layer 30 from the sanitary ware 1 having the upper glaze layer 30, the first melting temperature and the second melting temperature are measured by the following measuring method 2-1.
<Measurement method 2-1>
DTA measurement is performed using alumina powder as a reference material and the powder of the upper glaze layer 30 as a sample powder to obtain a DTA curve. In the region above 700 ° C. of the obtained DTA curve, the potential difference ΔV (μV) indicating the value ΔT obtained by subtracting the temperature of the reference substance from the temperature of the sample powder becomes the first inflection point at which the temperature of the reference substance becomes smaller. One melting temperature. In the region on the higher temperature side than the first melting temperature, the temperature of the reference substance at the first inflection point where the potential difference ΔV becomes large is defined as the second melting temperature.

The powder of the upper glaze layer 30 is obtained by appropriately cutting out the upper glaze layer 30 and polishing the same. The conditions for the DTA measurement are the same as the conditions for the DTA measurement in the above measurement method 1-1.
The first melting temperature of the upper glaze layer 30 is the same as the first melting temperature of the upper glaze layer composition.
The second melting temperature of the upper glaze layer 30 is the same as the second melting temperature of the upper glaze layer composition.
The difference between the second melting temperature and the first melting temperature of the upper glaze layer 30 is the same as the difference between the second melting temperature and the first melting temperature of the upper glaze layer composition (upper glaze layer melting temperature difference).

When obtaining the third melting temperature of the upper glaze layer 30 from the sanitary ware 1 having the upper glaze layer 30, it is measured by the following measuring method 2-2.
<Measurement method 2-2>
The powder of the upper glaze layer 30 is pressure-formed to obtain a cylindrical sample. Light is irradiated while heating the obtained cylindrical sample. The amount of light reflected by the surface of the cylindrical sample is measured. The first temperature at which the amount of reflected light becomes 10 times or more the amount of reflected light detected at the beginning of light emission is defined as a third melting temperature.

The powder of the upper glaze layer 30 is obtained by appropriately cutting out the upper glaze layer 30 and polishing the same. The conditions for obtaining a columnar sample are the same as the conditions for obtaining a columnar sample in the above measurement method 1-2.
The third melting temperature of the upper glaze layer 30 is the same as the third melting temperature of the upper glaze layer composition.

  In this specification, “bubbles” means bubbles actually contained in the upper glaze layer 30 or the intermediate layer 20. The air bubbles are generated by, for example, an oxidation reaction and a decomposition reaction of the components contained in the upper glaze layer 30, the ceramic body 10, and the intermediate layer composition, and voids contained in the upper glaze layer 30, the ceramic body 10, and the intermediate layer composition. . The bubbles are counted by binarizing the brightness of the image using image processing software and judging relatively dark portions as bubbles in an image obtained by observing the cut surface of the upper glaze layer 30 with a microscope or the like. . The size of the bubbles to be counted is 2 μm or more in terms of a perfect circle converted from the bubbles on the cut surface.

The bubbles to be counted are obtained, for example, by the following procedure.
The sanitary ware 1 is cut in the thickness direction of the upper glaze layer 30 using a small sample cutter. The cut surface is observed with a microscope (DSX510, manufactured by Olympus Corporation) at a magnification of 125 times. In the observed image, the brightness of the image is binarized using image processing software, and an area having a size of π μm ² (equivalent area of a bubble having a diameter of 2 μm) or more in each relatively dark area is detected as a bubble.

The ratio of the area of the bubbles to the area of the cut surface obtained by cutting the upper glaze layer 30 in the thickness direction (hereinafter, also referred to as “bubble area ratio of the upper glaze layer 30”) is 3% or less, and 2% or less. preferable. When the bubble area ratio of the upper glaze layer 30 is equal to or less than the upper limit, it is easy to suppress light incident on the upper glaze layer 30 from being irregularly reflected by bubbles in the upper glaze layer 30. For this reason, the "depth" of the sanitary ware 1 is more easily improved. Although the lower limit of the cell area ratio of the upper glaze layer 30 is not particularly limited, it is usually 0.01% or more.
The bubble area ratio (%) of the upper glaze layer 30 is obtained by calculating the total area (mm ² ) of bubbles detected in the image observed using the above-described microscope or the like by the visual field area (mm ² ) in the observed image. It is obtained by dividing by

The average bubble diameter of the bubbles on the cut surface obtained by cutting the upper glaze layer 30 in the thickness direction (hereinafter, also referred to as “the average bubble diameter of the bubbles on the cut surface of the upper glaze layer 30”) is 50 μm or less, and 40 μm or less. Is preferable, and 30 μm or less is more preferable. When the average bubble diameter of the bubbles on the cut surface of the upper glaze layer 30 is equal to or less than the upper limit, light incident on the upper glaze layer 30 is easily suppressed from being irregularly reflected by the bubbles in the upper glaze layer 30. For this reason, the "depth" of the sanitary ware 1 is more easily improved. The lower limit value of the average bubble diameter of the bubbles on the cut surface of the upper glaze layer 30 is 2 μm.
The average bubble diameter (μm) of the bubbles on the cut surface of the upper glaze layer 30 is calculated from the area of each of the portions detected as bubbles in the image observed using the above-described microscope or the like in terms of a perfect circle in terms of the bubble diameter ( Diameter) is calculated, and the average value is obtained by dividing the total bubble diameter by the number of detected bubbles.

The number of air bubbles in the cut surface obtained by cutting the upper glaze layer 30 in the thickness direction (hereinafter, also referred to as “the number of air bubbles in the cut surface of the upper glaze layer 30”) is preferably 120 or less per 1 mm ² , and more preferably 100 or less. The number is more preferably 80 or less. When the number of bubbles in the cut surface of the upper glaze layer 30 is equal to or less than the upper limit, light incident on the upper glaze layer 30 is easily suppressed from being irregularly reflected by the bubbles in the upper glaze layer 30. For this reason, the "depth" of the sanitary ware 1 is more easily improved. The lower limit of the number of bubbles on the cut surface of the upper glaze layer 30 is not particularly limited, but is usually one or more.
The number of bubbles (pieces / mm ² ) on the cut surface of the upper glaze layer 30 is determined by the number of bubbles detected in the image observed using the above-described microscope or the like, and the visual field area (mm ² ) in the observed image. It is obtained by dividing by

The thickness T30 of the upper glaze layer ₃₀ is, for example, preferably 100 μm or more, more preferably 100 to 1000 μm, further preferably 150 to 800 μm, and particularly preferably 200 to 600 μm. If the thickness T ₃₀ is not less than the above lower limit, tends surface of the upper glaze 30 is formed flat. If the thickness T ₃₀ is less than the above upper limit, it is easy to release the air bubbles above glaze composition outside the top glaze 30.

The thickness T30 of the upper glaze layer ₃₀ is determined, for example, by the following procedure.
The sanitary ware 1 is cut in the thickness direction of the upper glaze layer 30 using a small sample cutter. The cut surface is observed with a microscope (DSX510, manufactured by Olympus Corporation) at a magnification of 125 times. In the observed image, the distance between the surface of the upper glaze layer 30 and the boundary (upper-middle boundary) between the upper glaze layer 30 and the intermediate layer 20 is measured at arbitrary 20 points. The arithmetic average value of the measured distance is defined as the thickness T30 of the upper glaze layer ₃₀ .
The site | part which cuts the sanitary ware 1 is not specifically limited, The site | part which a human eye can easily touch is preferable. Examples of the part that can be easily touched by human eyes include a bowl surface of a basin, a ceiling surface of a basin, a ceiling surface of a urinal, a rim portion of a toilet, a bowl surface of a toilet, and a side surface of a toilet.

And the maximum value _{T 30MAX} thickness _{T 30} of the upper glaze 30, the difference between _{T 30Deruta} between the minimum value _{T 30MIN} thickness _{T 30} of the upper glaze 30 is 50μm or less, preferably 40μm or less, is 30μm or less More preferred. When the difference _T30Δ is equal to or less than the upper limit, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 is easily suppressed. As a result, the “depth” of the sanitary ware 1 is more easily improved. The lower limit of the difference _T30Δ is not particularly limited, but is usually 0.1 μm or more.

The ratio of the difference T _{30Δ to} the thickness T ₃₀ (hereinafter, also referred to as “T _30Δ / T ₃₀ ratio”) is preferably 25% or less, more preferably 20% or less, and even more preferably 10% or less. When the T _30Δ / T ₃₀ ratio is equal to or less than the upper limit, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 is easily suppressed. As a result, the “depth” of the sanitary ware 1 is more easily improved. The lower limit of the T _30Δ / T ₃₀ ratio is not particularly limited, but is usually 0.01% or more.

And the maximum value _{T 30MAX} thickness _{T 30,} the minimum value _{T 30MIN} thickness _{T 30,} for example, be determined by the following procedure.
Similar to the procedure for obtaining the thickness T ₃₀ of the upper glaze 30, measures the distance between the surface and the top, middle border of the upper glaze 30 for any 20 or plants. Of the 20 measured locations, the one having the largest distance between the surface of the upper glaze layer 30 and the upper middle boundary line is defined as a maximum value _T30MAX . Of the 20 places were measured, and what distance between the surface and the top, middle border of the upper glaze 30 is minimized and the minimum value T _30MIN.

The difference _T30Δ can be controlled by forming the interface between the upper glaze layer 30 and the intermediate layer 20 flat. The melting start temperature of the intermediate layer composition described below, the average bubble diameter in the cut surface obtained by cutting the intermediate layer 20 in the thickness direction, the ratio of the area of the bubbles to the area of the cut surface obtained by cutting the intermediate layer 20 in the thickness direction, and By these combinations, the smoothness of the interface between the upper glaze layer 30 and the intermediate layer 20 can be controlled.

The intermediate layer 20 is a fired product of the intermediate layer composition. The middle layer 20 is a layer including a glaze located between the ceramic body 10 and the upper glaze layer 30. The intermediate layer composition is a slurry (slurry) in which a raw material (intermediate layer raw material) for forming the intermediate layer 20 is dispersed in water.
The content of water with respect to the total mass of the intermediate layer composition is preferably 40 to 60% by mass, and more preferably 40 to 50% by mass.

The average particle diameter of the solid component contained in the intermediate layer composition is preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less. When the average particle diameter of the solids contained in the intermediate layer composition is equal to or less than the upper limit, the melting start temperature of the solids contained in the intermediate layer composition is easily lowered.
The lower limit of the average particle diameter of the solid component contained in the intermediate layer composition is not particularly limited, but is, for example, 0.05 μm or more.
The average particle diameter of the solid content contained in the intermediate layer composition can be adjusted, for example, by pulverizing the intermediate layer raw material. As a tool for pulverizing the intermediate layer raw material, for example, a ball mill can be used.

The average particle diameter of the solid content contained in the intermediate layer composition can be measured by the same method as the average particle diameter of the solid content contained in the upper glaze layer composition.
The solid content contained in the intermediate layer composition is a dried product of the intermediate layer composition.

As the intermediate layer composition, 50 to 80% by mass of SiO ₂ , 5 to 40% by mass of Al ₂ O ₃ , Na ₂ O and K ₂ O are used based on the total mass of the solid content contained in the intermediate layer composition. And a composition containing a total of 5 to 30% by mass of CaO, MgO and ZnO.
The total content of each component of the solid content contained in the intermediate layer composition shall not exceed 100% by mass based on the total mass of the solid content contained in the intermediate layer composition.

The composition of the intermediate layer composition is such that the molar ratio of the total of Na ₂ O, K ₂ O, CaO, MgO, and ZnO to 1 is 1 to 16 mol of SiO ₂ , Al ₂ O ₃ Is preferably 0 to 5 mol.

  The intermediate layer composition may contain a frit. The content of the frit is preferably from 0 to 30% by mass, more preferably from 0 to 20% by mass, based on the total mass of the solid content contained in the intermediate layer composition.

The dried product of the intermediate layer composition (hereinafter also referred to as “intermediate layer raw material”) is a dried product of the ceramic base material composition (hereinafter also referred to as “porcelain base material”) and a dried product of the upper glaze layer composition (hereinafter referred to as “glaze raw material”). ).
When the intermediate layer raw material is a mixture of the ceramic base material and the glaze raw material, the mass ratio represented by the ceramic base material / glaze raw material (hereinafter, also referred to as “base / glaze ratio”) is 20/80 to 80 /. 20 is preferable, 30/70 to 70/30 is more preferable, and 40/60 to 60/40 is further preferable. When the base / glaze ratio is equal to or more than the lower limit, the binding property between the pottery base 10 and the intermediate layer 20 is easily increased. When the substrate / glaze ratio is equal to or less than the upper limit, the interface between the intermediate layer 20 and the upper glaze layer 30 is easily flattened.
From the viewpoint of further improving the "depth" of the sanitary ware 1, the intermediate layer raw material is preferably a mixture of a ceramic base material and a glaze material.
Further, the intermediate layer composition may be a mixture obtained by mixing the pottery base composition and the upper glaze layer composition so as to have the above-described base / glaze ratio.

The intermediate layer composition preferably contains a pigment. When the intermediate layer composition contains a pigment, the intermediate layer 20 can be colored. By coloring the intermediate layer 20, the color of the pottery substrate 10 can be hidden.
Examples of the pigment include zirconium silicate and aluminum oxide.
When the intermediate layer composition contains a pigment, the content of the pigment is preferably from 3 to 15% by mass, more preferably from 6 to 15% by mass, based on the total mass of the solid content contained in the intermediate layer composition.

The melting start temperature of the intermediate layer composition can be defined by the first melting temperature.
The first melting temperature of the intermediate layer composition is preferably 850 to 960 ° C, more preferably 910 to 950 ° C, and even more preferably 930 to 950 ° C. When the first melting temperature of the intermediate layer composition is equal to or higher than the lower limit, it is easy to suppress generation of bubbles when firing the intermediate layer composition. When the first melting temperature of the intermediate layer composition is equal to or lower than the upper limit, the interface between the upper glaze layer 30 and the intermediate layer 20 is easily flattened.
The first melting temperature of the intermediate layer composition can be measured in the same manner as the first melting temperature of the upper glaze layer composition.

  The temperature difference (first temperature difference) between the first melting temperature of the upper glaze layer composition and the first melting temperature of the intermediate layer composition is preferably 10 to 120 ° C, more preferably 30 to 115 ° C, and 60 to 110 ° C. C is more preferred. When the first temperature difference is within the above numerical range, the interface between the upper glaze layer 30 and the intermediate layer 20 is easily flattened. As a result, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 can be suppressed, and the “depth” of the sanitary ware 1 can be more easily improved.

The second melting temperature of the intermediate layer composition is preferably from 1900 to 1230 ° C, more preferably from 1095 to 1225 ° C, and still more preferably from 1100 to 1220 ° C. When the second melting temperature of the intermediate layer composition is equal to or higher than the lower limit, it is easy to suppress generation of bubbles when firing the intermediate layer composition. When the second melting temperature of the intermediate layer composition is equal to or lower than the upper limit, the interface between the upper glaze layer 30 and the intermediate layer 20 is easily flattened.
The second melting temperature of the intermediate layer composition can be measured in the same manner as the second melting temperature of the upper glaze layer composition.

  The temperature difference (second temperature difference) between the second melting temperature of the upper glaze layer composition and the second melting temperature of the intermediate layer composition is preferably from 10 to 330 ° C, more preferably from 100 to 325 ° C, and from 200 to 320 ° C. C is more preferred. When the second temperature difference is within the above numerical range, the interface between the upper glaze layer 30 and the intermediate layer 20 is easily flattened. As a result, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 can be suppressed, and the “depth” of the sanitary ware 1 can be more easily improved.

The difference (intermediate layer melting temperature difference) between the second melting temperature and the first melting temperature of the intermediate layer composition is preferably 50 to 300 ° C, more preferably 100 to 300 ° C, and even more preferably 230 to 300 ° C. When the intermediate layer melting temperature difference is equal to or more than the lower limit, the average bubble diameter of the bubbles generated when the intermediate layer composition is fired is easily reduced. When the intermediate layer melting temperature difference is equal to or less than the above upper limit, it is easy to suppress generation of bubbles when firing the intermediate layer composition.
The intermediate layer melting temperature difference is determined by subtracting the first melting temperature of the intermediate layer composition from the second melting temperature of the intermediate layer composition.

The first melting temperature of the intermediate layer composition can be adjusted by the type of the intermediate layer raw material, the mixing ratio of the intermediate layer raw material, the average particle diameter of the solid content of the intermediate layer composition, and a combination thereof.
The second melting temperature of the intermediate layer composition can be adjusted similarly to the first melting temperature of the intermediate layer composition.

When obtaining the melting start temperature of the intermediate layer 20 from the sanitary ware 1 including the intermediate layer 20, the first melting temperature and the second melting temperature are the same as those in the above-described measurement method 2-1 using the powder of the intermediate layer 20 as the sample powder. Measured by the method.
The powder of the intermediate layer 20 is obtained by appropriately cutting out the intermediate layer 20 and polishing the same.
The first melting temperature of the intermediate layer 20 is the same as the first melting temperature of the intermediate layer composition.
The second melting temperature of the intermediate layer 20 is the same as the second melting temperature of the intermediate layer composition.
The difference between the second melting temperature and the first melting temperature of the intermediate layer 20 is the same as the difference between the second melting temperature and the first melting temperature of the intermediate layer composition (intermediate layer melting temperature difference).

The ratio of the area of the bubbles to the area of the cut surface obtained by cutting the intermediate layer 20 in the thickness direction (hereinafter, also referred to as “the bubble area ratio of the intermediate layer 20”) is preferably 20% or less, more preferably 15% or less. , 12% or less is more preferable. When the bubble area ratio of the intermediate layer 20 is equal to or less than the upper limit, light incident on the upper glaze layer 30 is easily suppressed from being irregularly reflected by bubbles in the intermediate layer 20. As a result, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 can be suppressed, and the “depth” of the sanitary ware 1 can be more easily improved. The lower limit of the bubble area ratio of the intermediate layer 20 is not particularly limited, but is usually 1.0% or more.
The bubble area ratio of the intermediate layer 20 is obtained by the same method as the bubble area ratio of the upper glaze layer 30.

The average bubble diameter of the bubbles on the cut surface obtained by cutting the intermediate layer 20 in the thickness direction (hereinafter, also referred to as the “average bubble diameter of the bubbles on the cut surface of the intermediate layer 20”) is preferably 25 μm or less, more preferably 20 μm or less. It is more preferably 15 μm or less. When the average bubble diameter of the bubbles on the cut surface of the intermediate layer 20 is equal to or less than the upper limit, light incident on the upper glaze layer 30 is easily suppressed from being irregularly reflected by the bubbles in the intermediate layer 20. As a result, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 can be suppressed, and the “depth” of the sanitary ware 1 can be more easily improved. The lower limit of the average bubble diameter of the bubbles on the cut surface of the intermediate layer 20 is 2 μm.
The average bubble diameter of the bubbles on the cut surface of the intermediate layer 20 is determined by the same method as the average bubble diameter of the bubbles on the cut surface of the upper glaze layer 30.

The number of bubbles on the cut surface obtained by cutting the intermediate layer 20 in the thickness direction (hereinafter, also referred to as “the number of bubbles on the cut surface of the intermediate layer 20”) is preferably 1,000 or less per mm ² , more preferably 700 or less. , 500 or less is more preferable. When the number of bubbles on the cut surface of the intermediate layer 20 is equal to or less than the upper limit, light incident on the upper glaze layer 30 is easily suppressed from being irregularly reflected by the bubbles in the intermediate layer 20. As a result, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 can be suppressed, and the “depth” of the sanitary ware 1 can be more easily improved. The lower limit of the number of bubbles on the cut surface of the intermediate layer 20 is not particularly limited, but is usually one or more.
The number of bubbles on the cut surface of the intermediate layer 20 can be counted by the same method as the number of bubbles on the cut surface of the upper glaze layer 30.

The thickness _{T 20} of the intermediate layer 20 is, for example, is preferably at least 200 [mu] m, more preferably 200 to 1,000, more preferably 250~800μm, 300~600μm is particularly preferred. If the thickness T ₂₀ is not less than the above lower limit, tends to flatten the interface between the intermediate layer 20 and the upper glaze 30. If the thickness T ₂₀ is less than the above upper limit, it is easy to release the air bubbles in the intermediate layer composition to the outside of the intermediate layer 20.

The thickness _{T 20} of the intermediate layer 20, for example, be determined by the following procedure.
The sanitary ware 1 is cut in the thickness direction of the intermediate layer 20 using a small sample cutting machine. The cut surface is observed with a microscope (DSX510, manufactured by Olympus Corporation) at a magnification of 125 times. In the observed image, the distance between the boundary line between the upper glaze layer 30 and the intermediate layer 20 (upper middle boundary line) and the boundary line between the intermediate layer 20 and the pottery base material 10 (center boundary line) is an arbitrary distance. Measure the location. The arithmetic mean value of the measured distance and the thickness T ₂₀ of the intermediate layer 20.

And the maximum value _{T 20MAX} thickness _{T 20} of the intermediate layer 20, the difference _{T 20Deruta} minimum value of the _{T 20min} thickness _{T 20} of the intermediate layer 20 is preferably 50μm or less, more preferably 40μm or less, still is 30μm or less preferable. When the difference _T20Δ is equal to or less than the upper limit, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 is easily suppressed. As a result, the “depth” of the sanitary ware 1 is more easily improved. The lower limit of the difference _T20Δ is not particularly limited, but is usually 0.1 μm or more.

The ratio of the difference T _{20Δ to} the thickness T ₂₀ (hereinafter, also referred to as “T _20Δ / T ₂₀ ratio”) is preferably 25% or less, more preferably 20% or less, and even more preferably 10% or less. When the T _20Δ / T ₂₀ ratio is equal to or less than the upper limit, irregular reflection of light at the interface between the upper glaze layer 30 and the intermediate layer 20 is easily suppressed. As a result, the “depth” of the sanitary ware 1 is more easily improved. The lower limit of the T _20Δ / T ₂₀ ratio is not particularly limited, but is usually 0.01% or more.

And the maximum value _{T 20MAX} thickness _{T 20,} the minimum value _{T 20min} thickness _{T 20,} for example, be determined by the following procedure.
Similar to the procedure for obtaining the thickness T ₂₀ of the intermediate layer 20, to measure the distance between the upper, middle border and Chumoto boundaries for any 20 or plants. Of the 20 measured locations, the one having the largest distance between the upper middle boundary line and the middle element boundary line is defined as the maximum value _T20MAX . Of the 20 locations measured, the one that minimizes the distance between the upper middle boundary line and the middle boundary line is defined as the minimum value _T20MIN .

[Manufacturing method of sanitary ware]
Next, a method for manufacturing the sanitary ware 1 of the present embodiment will be described.
First, the pottery substrate 10 is prepared. The pottery substrate 10 may be a product obtained by firing and molding other than the product obtained by molding the pottery substrate composition, or may be a pre-formed or molded and fired commercial product.
When firing the ceramic body composition, the firing temperature is preferably, for example, 1100 to 1300C, and more preferably 1150 to 1250C. When the firing temperature is equal to or higher than the lower limit, the strength of the ceramic body 10 is easily increased. When the firing temperature is equal to or lower than the upper limit, the deformation of the ceramic body 10 is easily suppressed.

Next, the intermediate layer composition is applied to the surface of the ceramic body 10. The method of applying the intermediate layer composition to the surface of the pottery substrate 10 is not particularly limited, and a general method such as dipping, pouring, spraying, or painting can be appropriately selected. From the viewpoint of ensuring the thickness of the intermediate layer 20, the method of applying the intermediate layer composition to the surface of the ceramic body 10 is preferably one of dipping, pouring, painting, or spraying. From the viewpoint of making the thickness of the intermediate layer 20 uniform, it is preferable to spray the intermediate layer composition on the surface of the ceramic body 10.
The dip coating method includes a dip coating method. Spraying includes a spray coating method.

The application amount of the intermediate layer composition is not particularly limited, and is preferably adjusted so that the thickness of the intermediate layer 20 after firing can be 200 μm or more. The application amount of the intermediate layer composition can be adjusted by appropriately adjusting the water content of the intermediate layer composition, the viscosity of the intermediate layer composition, the average particle diameter of the solid content contained in the intermediate layer composition, and the like.
By applying the intermediate layer composition to the surface of the pottery substrate 10, a primary coated body is obtained.

By drying the primary coating, the upper glaze layer composition can be easily applied to the surface of the primary coating. For this reason, it is preferable that the primary application body is dried.
The temperature at the time of drying the primary coating body is preferably from 20 to 110 ° C, more preferably from 30 to 100 ° C, and still more preferably from 40 to 90 ° C. When the temperature at which the primary coated body is dried is equal to or higher than the lower limit, the water content of the intermediate layer composition is easily reduced. When the temperature at the time of drying the primary coated body is equal to or lower than the upper limit, the surface of the intermediate layer 20 is easily flattened.
The time for drying the primary coated body is preferably 0.5 to 48 hours. When the time for drying the primary coated body is not less than the above lower limit, the intermediate layer composition is easily dried sufficiently. When the time for drying the primary application body is equal to or less than the upper limit, the productivity of the sanitary ware 1 is easily improved.

  Next, the upper glaze layer composition is applied to the surface of the primary application body. The method of applying the upper glaze layer composition is preferably spraying (spraying) from the viewpoint of easily adjusting the thickness of the upper glaze layer 30.

The application amount of the upper glaze layer composition is not particularly limited, and is preferably adjusted so that the thickness of the upper glaze layer 30 after firing can be made 100 μm or more. The coating amount of the upper glaze layer composition is determined by appropriately adjusting the water content of the upper glaze layer composition, the viscosity of the upper glaze layer composition, the average particle diameter of the solid content contained in the upper glaze layer composition, and the like. Can be adjusted.
By applying the upper glaze layer composition to the surface of the primary coating, a secondary coating is obtained.

  Next, the secondary coated body is fired. The firing temperature at the time of firing the secondary coated body is preferably a temperature at which the ceramic body 10 is sintered and the intermediate layer composition and the upper glaze layer composition are softened. The firing temperature at the time of firing the secondary coating body is, for example, preferably from 1100 to 1300 ° C, and more preferably from 1150 to 1250 ° C. When the firing temperature at the time of firing the secondary coating body is equal to or higher than the lower limit, the upper glaze layer composition is easily melted sufficiently. In addition, when the firing temperature at the time of firing the secondary coating body is equal to or higher than the lower limit, the intermediate layer composition is easily melted sufficiently. When the firing temperature at the time of firing the secondary coating body is equal to or lower than the upper limit, the surface of the upper glaze layer 30 is easily formed flat. In addition, if the firing temperature at the time of firing the secondary coated body is equal to or lower than the upper limit, the interface between the intermediate layer 20 and the upper glaze layer 30 is easily flattened.

  The firing time for firing the secondary coating body is preferably 1 to 168 hours, more preferably 2 to 72 hours, and still more preferably 3 to 24 hours. If the baking time for baking the secondary coating body is equal to or longer than the lower limit, the surface of the upper glaze layer 30 is easily formed flat. In addition, when the firing time for firing the secondary coating body is equal to or longer than the lower limit, the interface between the intermediate layer 20 and the upper glaze layer 30 is easily flattened. When the sintering time for sintering the secondary application body is equal to or less than the above upper limit, the productivity of the sanitary ware 1 is easily improved.

By firing the secondary coating, a fired product is obtained. The fired product becomes the sanitary ware 1 by cooling. The sanitary ware 1 may be obtained by naturally cooling a fired product, or may be obtained by cooling such as blowing.
The temperature range for cooling the calcined product is preferably from 800 to 1300C, more preferably from 900 to 1250C. When the temperature range for cooling the fired product is equal to or higher than the lower limit, bubbles are easily released to the outside of the upper glaze layer 30. When the temperature range for cooling the fired product is equal to or less than the upper limit, the surface of the upper glaze layer 30 is easily formed flat.
The cooling rate when cooling the fired product is preferably 30 ° C./min or less, more preferably 10 ° C./min or less, and even more preferably 0.1 ° C./min or less. When the temperature decreasing rate at the time of cooling the fired product is equal to or lower than the upper limit, bubbles are easily released to the outside of the upper glaze layer 30. In addition, when the rate of temperature decrease when cooling the fired product is equal to or lower than the upper limit, the surface of the upper glaze layer 30 is easily formed flat.

  The sanitary ware 1 is applied with any of the intermediate layer composition on the surface of the pottery substrate 10 by dipping, pouring, painting, or spraying, and then fired to obtain a primary fired body (first firing step). Alternatively, it may be obtained by applying an upper glaze layer composition to the primary fired body and firing it (second firing step).

The firing temperature in the first firing step is preferably from 800 to 1000C, more preferably from 850 to 950C. When the firing temperature in the first firing step is equal to or higher than the above lower limit, the intermediate layer composition is easily melted sufficiently. In addition, the ceramic body 10 and the middle layer 20 are degassed, and it is easy to suppress air bubbles from entering the upper glaze layer 30. When the firing temperature in the first firing step is equal to or lower than the upper limit, the surface of the intermediate layer 20 is easily formed flat, and the adhesion to the upper glaze layer composition is easily improved.
The firing time in the first firing step is preferably 1 to 168 hours, more preferably 2 to 72 hours, and still more preferably 3 to 24 hours. When the firing time of the first firing step is equal to or longer than the lower limit, the surface of the intermediate layer 20 is easily formed flat. In addition, the ceramic body 10 and the middle layer 20 are degassed, and it is easy to suppress air bubbles from entering the upper glaze layer 30. When the firing time of the first firing step is equal to or less than the upper limit, the productivity of the sanitary ware 1 is easily improved.
By firing the primary applied body, a primary fired body is obtained.

The primary fired body is preferably cooled before applying the upper glaze layer composition. The temperature at the time of cooling the primary fired body is preferably from 800 to 1000C, more preferably from 850 to 950C. When the temperature at which the primary fired body is cooled is equal to or higher than the lower limit, bubbles are easily released to the outside of the intermediate layer 20. When the temperature at which the primary fired body is cooled is equal to or lower than the upper limit, the surface of the intermediate layer 20 is easily formed flat.
The cooling rate of the primary fired body is preferably 30 ° C./min or less, more preferably 10 ° C./min or less. When the rate of temperature decrease when cooling the primary fired body is equal to or lower than the upper limit, bubbles are easily released to the outside of the intermediate layer 20. In addition, when the rate of temperature decrease when cooling the primary fired body is equal to or lower than the upper limit, the surface of the intermediate layer 20 is easily formed flat.

Next, the upper glaze layer composition is applied to the surface of the primary fired body. As a method of applying the upper glaze layer composition to the surface of the primary fired body, spraying (spraying) is preferable from the viewpoint of easily adjusting the thickness of the upper glaze layer 30.
The application amount when applying the upper glaze layer composition to the surface of the primary fired body is the same as the application amount when applying the upper glaze layer composition to the surface of the primary application body.
By applying the upper glaze layer composition to the surface of the primary fired body, a secondary coated body is obtained.

Next, the secondary coated body is fired (second firing step). The firing temperature in the second firing step is preferably from 1100 to 1300 ° C, more preferably from 1150 to 1250 ° C. When the firing temperature in the second firing step is equal to or higher than the above lower limit, the upper glaze layer composition is easily melted sufficiently. When the firing temperature in the second firing step is equal to or lower than the upper limit, the surface of the upper glaze layer 30 is easily formed flat.
The firing time in the second firing step is preferably 1 to 168 hours, more preferably 2 to 72 hours, and still more preferably 3 to 24 hours. When the baking time of the second baking step is equal to or longer than the lower limit, the surface of the upper glaze layer 30 is easily formed flat. When the firing time of the second firing step is equal to or less than the upper limit, the productivity of the sanitary ware 1 is easily improved.
A fired product is obtained by the second firing step. The fired product becomes the sanitary ware 1 by cooling. The temperature for cooling the fired product is the same as the temperature for cooling the fired product described above. The temperature lowering rate when cooling the fired product is the same as the above-described temperature lowering rate when cooling the fired product.

By obtaining the sanitary ware 1 via the primary fired body, the interface between the intermediate layer 20 and the upper glaze layer 30 can be more easily formed. Further, the number of bubbles contained in the intermediate layer 20 and the upper glaze layer 30 can be easily reduced. For this reason, the "depth" of the sanitary ware 1 is more easily improved.
From the viewpoint that the "depth" of the sanitary ware 1 is more easily improved, it is preferable that the sanitary ware manufacturing method of the present invention obtain the sanitary ware 1 via a primary fired body.

  As described above, the embodiments of the present invention have been described in detail with reference to the drawings. However, the present invention is not limited to the above embodiments, and can be appropriately changed without departing from the spirit of the present invention. . Further, it is possible to appropriately replace the components in the above-described embodiment with known components.

In the embodiment described above, the sanitary ware 1 includes the pottery base material 10, the intermediate layer 20, and the upper glaze layer 30. However, the present invention is not limited to the embodiments described above. For example, sanitary ware may not have an intermediate layer. That is, the sanitary ware may have a form in which an upper glaze layer (glaze layer) is provided on the surface of the ceramic body. Further, another glaze layer may be provided between the upper glaze layer 30 and the intermediate layer 20, and the glaze layer may be a plurality of layers. That is, the sanitary ware may have a form in which an intermediate layer, a single-layer or multiple-layer glaze layer, and a further upper glaze layer (glaze layer) are further provided on the surface of the ceramic body.
From the viewpoint that the “depth” of the sanitary ware is more easily improved, the sanitary ware preferably includes an intermediate layer.
When the sanitary ware does not have an intermediate layer, the thickness of the upper glaze layer (glaze layer) can be determined by, for example, the following procedure.
The sanitary ware is cut in the thickness direction of the upper glaze layer using a small sample cutter. The cut surface is observed with a microscope (DSX510, manufactured by Olympus Corporation) at a magnification of 125 times. In the observed image, the distance between the surface of the upper glaze layer and the boundary line between the upper glaze layer and the ceramic body (upper boundary line) is measured at any 20 places. The arithmetic average value of the measured distance is defined as the thickness of the upper glaze layer.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
The raw materials used in this example are as shown in [Used raw materials] below.

[Raw materials]
<Pottery base material>
A-1: 10 parts by mass of pottery stone, 40 parts by mass of feldspar, 50 parts by mass of clay (70% by mass of SiO _2, 25% by mass of Al ₂ O _3, total of Na ₂ O, K ₂ O, CaO, MgO, and ZnO) 5% by mass).
A-2: 30 parts by mass of porcelain stone, 70 parts by mass of clay (65% by mass of SiO _2, 30% by mass of Al ₂ O ₃ , total of 5% by mass of Na ₂ O, K ₂ O, CaO, MgO, and ZnO).

<Middle layer material>
B-1: _SiO 2 65 _wt%, Al _{2 O} 3 20 wt%, a total of 12 mass% of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, other 3% by weight.
B-2: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 80/20.
B-3: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 70/30.
B-4: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 60/40.
B-5: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 50/50.
B-6: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 40/60.
B-7: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 30/70.
B-8: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 20/80.
B-9: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 10/90.
B-10: A mixture obtained by mixing the ceramic raw material A-2 and the following glaze raw material C-9 at a mass ratio (base / glaze ratio) of 0/100.

<Glass raw material>
C-1: _SiO 2 63 _wt%, Al _{2 O} 3 12 wt%, total 24% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 1 mass %.
C-2: _SiO 2 62 _wt%, Al _{2 O} 3 13 wt%, total 24% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 1 mass %.
C-3: _SiO 2 62 _wt%, Al _{2 O} 3 13 wt%, total 24% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 1 mass %.
C-4: _SiO 2 64 _wt%, Al _{2 O} 3 12 wt%, total 24% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3.}
C-5: _SiO 2 57 _wt%, Al _{2 O} 3 10 wt%, total 32% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 1 mass %.
C-6: _SiO 2 63 _wt%, Al _{2 O} 3 12 wt%, total 24% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 1 mass %.
C-7: _SiO 2 66 _wt%, Al _{2 O} 3 12 wt%, a total of 22 mass% of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3.}
C-8: _SiO 2 70 _wt%, Al _{2 O} 3 11 wt%, total 19% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3.}
C-9: _SiO 2 63 _wt%, Al _{2 O} 3 10 wt%, a total of 20 mass% of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 7 mass %.
C-10: _SiO 2 61 _wt%, Al _{2 O} 3 12 wt%, total 27% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3.}
C-11: _SiO 2 57 _wt%, Al _{2 O} 3 11 wt%, total 25% by weight of Na ₂ O and _{K 2} O, CaO and MgO and ZnO, SrO, BaO and _B 2 _{O 3,} other 7 mass %.

[Preparation of ceramic body]
1 kg of the pottery base material A-1 and 0.4 kg of water were mixed to obtain a mixture. The mixture was pulverized by a ball mill for 20 hours to obtain a ceramic base composition. Using a laser diffraction particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., “MT3300EX (model number)”), the particle diameter of the solid matter of the ceramic body composition was measured and found to be 12 μm.

  Next, the pottery base composition was poured into a gypsum mold having a length of 100 mm, a width of 100 mm, and a thickness of 10 mm to obtain a pottery base.

[Preparation of frit]
Glaze raw materials C-1 to C-11 were melted at 1500 ° C. as frit raw materials to obtain frit F-1 to F-11.

[Preparation of intermediate layer composition]
1 kg of the intermediate layer raw material B-1 and 0.4 kg of water were mixed to obtain a mixture. The mixture was pulverized by a ball mill for 20 hours to obtain an intermediate layer composition M-1. When the particle size of the solid component of the intermediate layer composition M-1 was measured using the laser diffraction type particle size distribution analyzer, D50 was 8 μm.

Except that the intermediate layer raw materials B-2 to B-10 were used instead of the intermediate layer raw material B-1, the intermediate layer compositions M-2 to M-10 were prepared in the same manner as the intermediate layer composition M-1. Obtained. The intermediate layer composition M-11 was prepared by mixing 1 kg of the glaze raw material C-11 as the intermediate layer raw material and 0.6 kg of water to obtain a mixture.
In Tables 1 and 2, "kind" of the intermediate layer composition indicates any of the above-described intermediate layer compositions M-1 to M-11. “D50 (μm)” of the intermediate layer composition represents a 50% average particle diameter (D50) of any of the above-described intermediate layer compositions M-1 to M-11.

[Preparation of upper glaze layer composition]
1 kg of frit F-1 and 0.6 kg of water were mixed to obtain a mixture. The mixture was pulverized with a ball mill for 30 hours, and a viscosity modifier such as carboxymethylcellulose was added for viscosity control, thereby obtaining an upper glaze layer composition G-1. When the particle diameter of the solid component of the upper glaze layer composition G-1 was measured using the laser diffraction particle size distribution analyzer, D50 was 15 μm.

Except that frit F-2 to F-10 was used instead of frit F-1, upper glaze layer compositions G-2 to G-10 were obtained in the same manner as upper glaze layer composition G-1. .
In Tables 1 and 2, the “type” of the upper glaze layer composition indicates any of the above upper glaze layer compositions G-1 to G-10. “D50 (μm)” of the upper glaze layer composition represents the 50% average particle diameter (D50) of any of the above upper glaze layer compositions G-1 to G-10.

[Examples 1 to 18, Comparative Examples 1 and 2]
[Preparation of sanitary ware]
The intermediate layer compositions described in Tables 1 and 2 are applied to the ceramic body by a spray coating method, dried at 60 ° C. for 1 hour, and then the upper glaze layer composition described in Tables 1 and 2 is spray coated. To obtain a secondary coated body. The secondary coated body was fired at 1220 ° C. for 20 hours to obtain a rectangular parallelepiped sanitary ware sample.

<Measurement of thickness of upper glaze layer>
Using a small sample cutter, each sample was cut in the thickness direction on a plane passing through the midpoint of one side in the length direction of the sample and parallel to the width direction of the sample. The cut surface was observed with a microscope (DSX510, manufactured by Olympus Corporation) at a magnification of 125 times. The observed image was divided into ten equal parts in the width direction from one end to the other end in the width direction, and the distance (L ₃₀ ) between the surface of the two upper glaze layers and the upper middle boundary line was measured. The distance (L ₃₀ ) was measured at a total of 20 places for one sample, and the maximum value, the minimum value, the difference between the maximum value and the minimum value, and the average value of the thickness of the upper glaze layer were determined. The average value of the distance (L ₃₀ ) was defined as the thickness of the upper glaze layer. The results are shown in Tables 1 and 2. In the table, “difference” represents a difference between the maximum value and the minimum value of the thickness of the upper glaze layer.

<Measurement of thickness of intermediate layer>
Using the image observed with the thickness of the upper glaze layer, one end to the other end in the width direction of the observed image is divided into 10 equal parts in the width direction, and two upper and middle boundary lines and two elementary boundary lines, respectively. (L ₂₀ ) was measured. The distance (L ₂₀ ) was measured at a total of 20 points for one sample, and the average value was determined to be the thickness of the intermediate layer. The results are shown in Tables 1 and 2.

<Measurement of average cell diameter, cell area ratio, and cell number>
Using the image observed by the above microscope, the image was binarized by device processing software (Mitani Shoji Co., Ltd., WinROOF2015), and the average cell diameter and cell area ratio at the cut surface of the upper glaze layer were analyzed by image analysis. And the number of air bubbles was determined. In addition, the average cell diameter, cell area ratio, and cell number on the cut surface of the intermediate layer were determined. The results are shown in Tables 1 and 2.

<Measurement of image clarity>
The sample of each example was prepared, and the DOI value was measured by a wave scan DOI measuring device (BYK Gardner, Wave-Scan-DUAL). The results are shown in Tables 1 and 2.

<Evaluation of "depth">
The sample of each example was prepared, held over a fluorescent lamp in a room, and evaluated for appearance sensitivity from the viewpoint of feeling the depth of light and the cleanness of the surface as “depth”. The appearance response evaluation was performed by 10 subjects, and "depth" was evaluated based on the following evaluation criteria. The results are shown in Tables 1 and 2.
"Evaluation criteria"
：: The number of subjects who felt “depth” was 5 or more.
×: The number of subjects who felt “depth” was 4 or less.

As shown in Tables 1 and 2, in Examples 1 to 18 to which the present invention was applied, the evaluation of “depth” was “○”, and it was found that “depth” could be further improved.
On the other hand, in Comparative Examples 1 and 2 in which any of the average cell diameter, cell area ratio, and cell number on the cut surface of the upper glaze layer was out of the applicable range of the present invention, the evaluation of “depth” was “x”.

  According to the sanitary ware of the present invention, it was found that the "depth" of the sanitary ware can be further improved.

DESCRIPTION OF SYMBOLS 1 Sanitary ware 10 Pottery base material 20 Intermediate layer 30 Upper glaze layer C1 TG curve C2 DTA curve P1 First inflection point P2 Second inflection point

Claims (9)

Pottery substrate, an upper glaze layer located on the surface of the pottery substrate, and an intermediate layer located between the pottery substrate and the upper glaze layer,
A sanitary ware, wherein a ratio of a bubble area to an area of a cut surface obtained by cutting the upper glaze layer in a thickness direction is 3% or less. Pottery substrate, an upper glaze layer located on the surface of the pottery substrate, and an intermediate layer located between the pottery substrate and the upper glaze layer,
A sanitary ware, wherein an average bubble diameter of bubbles in a cut surface obtained by cutting the upper glaze layer in a thickness direction is 50 μm or less. The sanitary ware according to claim 1, wherein the number of bubbles in the cut surface is 120 or less per 1 mm ² . The average bubble diameter of the bubbles on the cut surface is 50 μm or less,
The cell count in the cut surface is not more than 120 per 1 mm ^2, sanitary ware according to claim 1. The number of bubbles on a cut surface obtained by cutting the intermediate layer in the thickness direction is 1,000 or less per 1 mm ² ,
The ratio of the area of the bubbles to the area of the cut surface of the intermediate layer is 20% or less,
The sanitary ware according to any one of claims 1 to 4, wherein the average bubble diameter of the bubbles on the cut surface of the intermediate layer is 25 µm or less.   The sanitary ware according to any one of claims 1 to 5, wherein the thickness of the upper glaze layer is 100 µm or more.   The sanitary ware according to any one of claims 1 to 6, wherein the thickness of the intermediate layer is 200 µm or more.   The intermediate layer composition for forming the intermediate layer was applied to the surface of the ceramic body by dipping, pouring, coating, or spraying, dried, and then the intermediate layer composition was applied. The method for manufacturing sanitary ware according to any one of claims 1 to 7, wherein an upper glaze layer composition for forming the upper glaze layer is applied to a surface.   The intermediate layer composition for forming the intermediate layer is applied to the surface of the ceramic body by dipping, pouring, painting, or spraying, and then fired to obtain a primary fired body, and the primary fired body is obtained. The method for producing sanitary ware according to any one of claims 1 to 7, wherein a composition of the upper glaze layer for forming the upper glaze layer is applied and baked.

Images