SANITARY WARE

Abstract

Disclosed is a sanitary ware compatibly satisfying both low water absorption and weight reduction. The sanitary ware has a pottery substrate of a vitreous body and a glaze layer, in which part of the substrate is exposed to outside thereof without the glaze layer; the substrate has (A) an anorthite and (B) an alkali metal component; and an amount of the alkali metal component is in the range of 5 to 10% by weight in terms of an oxide conversion (A.sub.2O) relative to the substrate. This sanitary ware has the properties of low water absorption and light weight.

Claims

1. A sanitary ware comprising a pottery substrate of a vitreous body and a glaze layer, wherein a part of the substrate is exposed to outside thereof without the glaze layer; the substrate comprising: (A) an anorthite and (B) an alkali metal component; and where an amount of the alkali metal component is in the range of 5 to 10% by weight in terms of an oxide conversion (A.sub.2O) relative to the substrate.

2. The sanitary ware according to claim 1, wherein the substrate further comprises (C) at least one selected from the group consisting of corundum, chamotte, quartz, hollow silica, hollow alumina, zirconia, zircon, cordierite, and mullite.

3. The sanitary ware according to claim 2, wherein the (C) component is corundum.

4. The sanitary ware according to claim 1, wherein the glaze layer comprises SiO.sub.2 in the range of 55 to 80 parts by weight, Al.sub.2O.sub.3 in the range of 5 to 13 parts by weight, Fe.sub.2O.sub.3 in the range of 0.1 to 0.4 parts by weight, MgO in the range of 0.8 to 3.0 parts by weight, CaO in the range of 8 to 17 parts by weight, ZnO in the range of 3 to 8 parts by weight, K.sub.2O in the range of 1 to 4 parts by weight, and Na.sub.2O in the range of 0.5 to 2.5 parts by weight.

5. The sanitary ware according to claim 4, wherein the glaze layer further comprises ZrO.sub.2 in the range of 0 to 15 parts by weight and a pigment in the range of 0 to 20 parts by weight.

6. The sanitary ware according to claim 1, wherein a closed pore rate in the substrate is 15% or greater by volume.

7. The sanitary ware according to claim 1, wherein a water absorption rate of the substrate is less than 2%.

8. The sanitary ware according to claim 1, wherein the substrate comprises calcium in the range of 3 to 10% by weight in terms of an oxide conversion thereof (CaO).

Description

DESCRIPTION OF THE EMBODIMENTS

[0042] Sanitary Ware and Substrate

[0043] In this disclosure, a “sanitary ware” means a toilet and a washbowl, as well as pottery products that are used around them, specifically, a closet bowl, a urinal, a tank, a perforate plate, a washbowl, a hand washer, and the like. The sanitary ware according to the present invention is the pottery whose material is described in “7.1 Kinds of Materials” of JIS A5207:2019, and is preferably the one that satisfies the properties described in “7.2 Quality of Pottery”.

[0044] In the sanitary ware according to the present invention, the substrate thereof is basically a pottery substrate of a vitreous body. In this disclosure, the term “pottery substrate of a vitreous body” means usual meaning that is understood by those skilled in the art with regard to the sanitary ware; thus, “pottery substrate of a vitreous body” as the substrate of the sanitary ware according to the present invention can be understood with a usual meaning except for the characteristics given by the present invention to be described later.

[0045] The “pottery substrate of a vitreous body” in the sanitary ware according to the present invention includes (A) an anorthite and (B) an alkali metal component, in which an amount of the alkali metal component is in the range of 5 to 10% by weight in terms of an oxide conversion (A.sub.2O) relative to the substrate, preferably in the range of 6 to 10% by weight. Here, the alkali metal component is preferably Li, Na, and K. Therefore, the oxides thereof are Li.sub.2O, Na.sub.2O, and K.sub.2O.

[0046] According to heretofore knowledge, in a large pottery product such as the sanitary ware, the alkali metal component within the range described above is disadvantageous in view of the product's strength, deformation thereof during firing, and the like; therefore, this amount is usually understood to be improper. However, the substrate containing the alkali metal component whose amount is considered to be too much as described above could bring about, upon coexisting with (A) the anorthite therein, a low water-absorption and a high strength, so that reduction of the product's weight could be accomplished.

[0047] According to a preferred embodiment of the present invention, the substrate of the sanitary ware according to the present invention is further characterized by the closed pore therein. In this specification, the term “closed pore” means a pore present inside the substrate that is not connected to an outside air. In addition, according to a preferred embodiment of the present invention, the closed pore rate that is obtained by the measurement method of the “closed pore rate” to be described later is determined 15% or greater by volume.

[0048] According to a preferred embodiment of the present invention, the substrate of the sanitary ware according to the present invention is characterized also by water absorption rate thereof. In this specification, this water absorption rate that is obtained by the measurement method of the “water absorption rate” to be described later is determined less than 2%.

[0049] In the present invention, the reason for realization of low water absorption and weight reduction in the sanitary ware is not clear yet; but the following theory may be presumed. However, this theory is a hypothesis; thus, the present invention is not limited by this theory.

[0050] One theory is that the pore generated in the substrate upon forming the anorthite at 900 to 1000° C. is kept until the maximum firing temperature; then, this open pore could be closed, as described below.

[0051] As the temperature of the vitreous body including a kaolin is raised, firstly a metakaolin is formed by dehydration reaction of the kaolin. When a limestone is blended as one raw material of the substrate, the reaction between the metakaolin and the limestone takes place at 900 to 1000° C. to generate an anorthite (CaAl.sub.2Si.sub.2O.sub.8).

Al.sub.2O.sub.3.2SiO.sub.2+CaCO.sub.3.fwdarw.CaAl.sub.2Si.sub.2O.sub.8+CO.sub.2  (1)

[0052] In this reaction, the portion where the limestone is consumed turns to a pore; then, the anorthite is formed around the pore.

[0053] In the case of a usual sanitary ware substrate, the metakaolin decomposes at 1000° C. or higher to generate a mullite and a SiO.sub.2 glass. There is a possibility that the amount of the closed pore is decreased by this amount and that a flux component at the maximum temperature increases.

3(Al.sub.2O.sub.3.2SiO.sub.2).fwdarw.3Al.sub.2O.sub.3.2SiO.sub.2+4SiO.sub.2  (2)

[0054] However, the reaction formula (2) does not occur, because the metakaolin is consumed by the anorthite-forming reaction (reaction formula (1)) that takes place at lower temperature during temperature rising. Therefore, it is presumed that the mullite and the SiO.sub.2 glass does not formed, and that the pores formed by the anorthite-forming reaction can readily remain as they are.

[0055] Then, the pore amount may be maximized until the maximum firing temperature of 1100 to 1200° C. at which the viterification reaction takes place; then, the viscosity of a small amount of the glass is lowered owing to the higher content of the alkali metal component, thereby leading to increase of the fluidity thereof resulting in the enclosure of the open pores. As a result, not only the open pores are closed but also many closed pores remain, so that excellent low water absorption and weight reduction are realized.

[0056] In place of limestone, a calcium (Ca)-containing raw material such as wollastonite may be used as the raw material capable of contributing to formation of anorthite. In the present invention, the raw material containing calcium is at least one selected from the group consisting of limestone, wollastonite, dolomite, and apatite, while this is preferably any one of limestone and wollastonite, or both. These calcium-containing raw materials react with metakaolin (Al.sub.2O.sub.3.2SiO.sub.2) at 900 to 1000° C. to form anorthite.

[0057] When wollastonite is used as the calcium-containing raw material, it is presumed that anorthite is formed according to the following reaction (reaction formula (3)).

Al.sub.2O.sub.3.2SiO.sub.2+CaSiO.sub.3.fwdarw.CaAl.sub.2Si.sub.2O.sub.8+SiO.sub.2  (3)

[0058] Because a CO.sub.2 gas is not generated in the reaction of the anorthite-forming reaction formula (3), pores are not increased; thus, the density change in the firing process is small. In addition, because the SiO.sub.2 glass is formed excessively in the reaction according to the reaction formula (3), this excess SiO.sub.2 glass, together with the glass that is going to be formed by the viterification reaction thereafter, contributes to enclosure of the open pores. That is, when wollastonite is used as the calcium-containing raw material, the amount of the closed pore in the substrate after firing decreases as compared with the case that limestone is used; but this has a merit in that the deformation due to firing can be lowered.

[0059] According to a preferred embodiment of the present invention, the amount of anorthite in the substrate is preferably in the range of 10 to 45% by weight, while more preferably in the range of 13 to 31% by weight. The amount of the anorthite can be obtained in such a way that the Rietveld analysis is done to the X-ray diffraction pattern obtained by the powder analysis method to determine the scale coefficient, from which the existing amounts of each crystal phase can be estimated. The detailed quantification method of anorthite is described in Example to be described later.

[0060] According to a preferred embodiment of the present invention, the amount of the alkali metal component in terms of the oxide conversion relative to the substrate is in the range of 5 to 10% by weight, while more preferably in the range of 6 to 9% by weight. The closed pore rate is preferably in the range of 20% to 31% by volume, and the water absorption rate is preferably less than 1%.

[0061] According to a preferred embodiment of the present invention, the sanitary ware substrate contains calcium, in terms of the oxide conversion (CaO), in the range of 3 to 10% by weight, while preferably in the range of 4 to 9% by weight.

[0062] (C) Component: Aggregate

[0063] The sanitary ware substrate according to the present invention may contain an aggregate component in view of the strength thereof. The aggregate component usable herein may be usually the one that is added to the pottery substrate of the vitreous body, and that does not undergo the reaction during firing, and that can suppress shrinkage during firing or deformation due to softening or can have an effect to the strength of the fired body.

[0064] According to a preferred embodiment of the present invention, the aggregate component, namely the (C) component, contains preferably at least one aggregate selected from the group consisting of corundum, chamotte, quartz, hollow silica, hollow alumina, zirconia, zircon, cordierite, and mullite.

[0065] In the present invention, the use of the aggregate component may bring about following merits. That is, when metakaolin is consumed in the anorthite-forming reaction (reaction formula (1)) thereby producing comparatively large amount of anorthite, there is a possibility to cause significant shrinkage within this reaction temperature range. This shrinkage impairs matching with the glaze. Then, it was found that these aggregates described above did not involve in the reaction formula (1) and that they were the materials that suppress the increase in the flux component in the viterification reaction. Therefore, the use of these aggregates is advantageous from a viewpoint to lower water-absorption and weight. In addition, according to a preferred embodiment of the present invention, the use of these aggregates can bring about the sanitary ware that is excellent in the thermal shock resistance.

[0066] In the present invention, the shape and composition of the aggregate component can be identified by the reflection electron image of the polished surface of the sanitary ware obtained by the scanning electron microscope (SEM) and by the element mapping of the energy-dispersion type X-ray analysis (EDX).

[0067] Raw Materials and Composition of Sanitary Ware Substrate

[0068] The raw materials of the sanitary ware substrate may be prepared from heretofore known raw materials with considering the composition thereof. Specifically, illustrative examples of the raw material include silica sand, feldspar, limestone, wollastonite, clay, alumina, and chamotte. The composition of the sanitary ware substrate according to the present invention is preferably as those described below; thus, raw materials of the pottery substrate are blended so as to give the following composition.

TABLE-US-00001 SiO.sub.2 40 to 65 parts by weight Al.sub.2O.sub.3 20 to 50 parts by weight CaO 3 to 10 parts by weight MgO 0.1 to 1 parts by weight K.sub.2O 3 to 6 parts by weight Na.sub.2O 0.5 to 5 parts by weight Li.sub.2O 0 to 2 parts by weight

[0069] Glaze Layer

[0070] The glaze layer of the sanitary ware according to the present invention is not particularly restricted; although according to a preferred embodiment of the present invention, the composition of the glaze layer is preferably those described below in terms of the oxide conversion.

TABLE-US-00002 SiO.sub.2 55 to 80 parts by weight Al.sub.2O.sub.3 5 to 13 parts by weight Fe.sub.2O.sub.3 0.1 to 0.4 parts by weight CaO 8 to 17 parts by weight MgO 0.8 to 3.0 parts by weight ZnO 3 to 8 parts by weight K.sub.2O 1 to 4 parts by weight Na.sub.2O 0.5 to 2.5 parts by weight ZrO.sub.2 0 to 15 parts by weight Pigment 0 to 20 parts by weight

[0071] The raw materials of the glaze layer may be prepared from heretofore known raw materials with considering the composition thereof. Illustrative examples thereof include silica sand, feldspar, limestone, dolomite, alumina, zinc oxide, and zircon.

[0072] According to a preferred embodiment of the present invention, the sanitary ware substrate and the glaze layer are preferably the combination that does not show a big difference in the deformation amount between the substrate and the glaze layer after firing, and that does not adversely affect the shape or the surface state of the sanitary ware after firing.

[0073] In the combination, for example, matching with the glaze in Example to be described later is preferably within 5 mm in terms of deformation amount. According to another embodiment of the present invention, the linear thermal expansion coefficient of the substrate is preferably about 5×10.sup.−7/K to 10×10.sup.−7/K higher than that of the graze.

[0074] Production of Sanitary Ware

[0075] The sanitary ware according to the present invention may be produced in such a way that the slip prepared from the afore-mentioned substrate raw materials is molded in a mold made of plaster or the like by slip casting to obtain a molded article, followed by drying, applied with the glaze, and then firing. In the present invention, as described above, the pore formed during formation of the anorthite is kept until the maximum firing temperature; then, the open pore is closed thereby realizing superior low water absorption, strength, and weight reduction. Accordingly, it is preferable to determine the firing condition such that the reaction and phenomena mentioned above can be surely realized. According to one aspect of the present invention, preferably the firing is carried out with the temperature raising rate of about 200° C./hour; then, the temperature is kept at the maximum temperature of 1180 to 1200° C. for 2 hours.

[0076] “Closed pore rate” and “water absorption rate” defined in the present invention are measured by the methods described below.

[0077] Water Absorption Rate

[0078] The fired body that is molded or cut out to the size of 7 mm×8 mm×70 mm is prepared as the measurement sample. This sample is dried at 110° C. for 24 hours; then, the weight of the sample is measured to obtain the dry weight thereof. Then, the sample is placed in a vessel; then, this is degassed by a vacuum pump for 20 minutes. With keeping the vacuum condition, distilled water is charged into the vessel in which the sample is placed; then, this is degassed for further 60 minutes. The vessel is opened to an atmospheric air; then, the sample is dipped into water and pulled up from water. The water on the surface is wiped off with a cloth or the like to measure the weight thereof. This is taken as the weight at the time of water absorption. The water absorption rate is calculated by the following calculation formula.

[00001]$\mathrm{Water}\mathrm{absorption}\mathrm{rate}=\frac{\mathrm{absorbed}\mathrm{water}\mathrm{weight}-\mathrm{dry}\mathrm{weight}}{\mathrm{dry}\mathrm{weight}}\times 100$

[0079] Closed Pore Rate

[0080] By using the values to obtain the water absorption rate, the apparent density is obtained from the following formula.

[00002]$\mathrm{Apparent}\mathrm{density}=\mathrm{Specific}\mathrm{gravity}\mathrm{of}\mathrm{water}\times \frac{\mathrm{dry}\mathrm{weight}}{\mathrm{dry}\mathrm{weight}-\mathrm{absorbed}\mathrm{water}\mathrm{weight}}$

[0081] Further, “true density” was measured as follows. Namely, the fired substrate body was crushed to the degree not including the closed pore; then, the density of the powder thereby obtained was measured by using a specific gravity vial using water as the solvent. This is defined as “true density” of the substrate.

[0082] From the apparent density and the true density, the closed pore rate can be defined by the following formula.

[00003]$\mathrm{Closed}\mathrm{pore}\mathrm{rate}=\left(1-\frac{\mathrm{apparent}\mathrm{density}}{\mathrm{true}\mathrm{density}}\right)\times 100$

EXAMPLES

[0083] The present invention will be explained in more detail by Examples described below; but the present invention is not limited to these Examples.

[0084] Production of Sanitary Ware

[0085] Raw Material

[0086] The raw materials described in Table 1 below were prepared; then, they were mixed in accordance with the combination described in Table 2 so as to give the composition described in Table 3. Then, they were crushed if necessary with a ball mill or the like to obtain the raw material of the sanitary ware substrate.

TABLE-US-00003 TABLE 1 Raw material SiO.sub.2 Al.sub.2O.sub.3 TiO.sub.2 Fe.sub.2O.sub.3 CaO MgO K.sub.2O Na.sub.2O Li.sub.2O ZrO.sub.2 China stone 75 18.1 0.13 0.38 0.17 0.02 0.17 — — — Kaolin 48.1 36.4 0.2  0.8 0.2 0.3 2.2 0.1 — — Sericite 46.69 37.56 0.63 0.35 0.31 0.18 8.3 1.14 — — Feldspar A 56.1 25.2 0.2  0.1 1.1 — 8.8 7.7 — — Feldspar B 67.51 17.82 — 0.13 0.18 0.02 10.95 3.03 — — Feldspar C 60.4 23.31 — 0.07 0.34 — 5.03 10.36 — — Petalite 75.49 17.52 0   0.09 0.16 0.03 0.64 0.47 4.24 — Limestone 0.03 — — 0.01 55.89 0.31 — — — — Wollastonite 51.19 0.66 — 0.31 45.07 0.62 — — — — Dolomite 2.5 — — 0.1 32.3 19.5 — — — — Silica sand A 96.5 1.5 0.04 0.08 0.15 0.04 1.04 — — — Silica sand B 98.94 0.34 — 0.03 0.01 0.01 0.3 0.09 — — Silica sand C 99.11 0.47 — 0.02 0.04 0.03 0.12 0.06 — — Chamotte A 52.24 43.2 2.09 1.61 0.21 0.38 0.48 0.06 — — Chamotte B 53.95 42.13 0.04 1.25 0.05 0.3 2.03 0.06 — — Chamotte C 53.95 42.13 0.04 1.25 0.05 0.3 2.03 0.06 — — Clay A 53.5 29.9 1.2  1 0.3 0.4 2.1 0.2 — — Clay B 48.78 34.93 0.87 1.37 0.21 0.24 0.59 0.07 — — Clay C 54.02 28.84 1.17 1.03 0.14 0.35 2.09 0.31 — — Alumina A 0.03 99.6 — 0.02 — — — 0.34 — — Alumina B 0.03 99.9 — 0.03 — — — 0.07 — — Alumina C 0.02 99.6 — 0.03 — — — — — — Alumina D 0.02 99.7 — 0.01 — — — — — — Zirconia — — — — — — — — — 100 Zircon 33 0.6 0.1  0.1 — — — — —  66 Cordierite 49.5 36 0.3  0.3 0.2 0.2 13 — — —

TABLE-US-00004 TABLE 2 Example Substrate 1 2 3 4 5 6 7 8 9 10 11 12 Used raw China stone material Kaolin Sericite FeldsparA FeldsparB ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ FeldsparC ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Petalite ◯ ◯ Limestone ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Wollastonite ◯ Dolomite ◯ Alumina A ◯ ◯ ◯ Alumina B ◯ Alumina C ◯ Alumina D SilicasandA SilicasandB ◯ SilicasandC ◯ ChamotteA ChamotteB ◯ ◯ ChamotteC ◯ Zirconia Zircon Cordierite ClayA ◯ ClayB ◯ ◯ ◯ ◯ ◯ ClayC ◯ ◯ ◯ ◯ ◯ ◯ Main Corundu — — 10.2 20.3 — — — — 10.2 10.2 — 15 aggregate Chamott — — — — — — 10.2 20.4 — — 10.2 — in Quartz 4.5 10 3.9 2.2 8.7 19.4 3.1 2.8 8.5 9.5 8.5 — substrate Zirconia — — — — — — — — — — — — raw Zircon — — — — — — — — — — — — material Cordierit — — — — — — — — — — — — (wt %) Total 4.5 10 14.1 22.5 8.7 19.4 13.3 23.2 18.7 19.7 18.7 15 firing temperature (° C.) 1180 1180  1180 1180 1180 1180 1180 1180 1180 1180 1180 1180  Example Comparative Example Substrate 13 14 15 16 17 18 1 2 3 4 5 Used raw China stone ◯ ◯ material Kaolin ◯ ◯ ◯ Sericite ◯ ◯ FeldsparA ◯ ◯ FeldsparB ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ FeldsparC ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Petalite Limestone ◯ ◯ ◯ ◯ ◯ ◯ Wollastonite ◯ ◯ Dolomite ◯ ◯ Alumina A Alumina B Alumina C ◯ ◯ Alumina D ∘ SilicasandA ◯ SilicasandB SilicasandC ◯ ◯ ChamotteA ◯ ChamotteB ChamotteC ◯ ◯ ◯ Zirconia ◯ Zircon ◯ Cordierite ◯ ClayA ◯ ◯ ◯ ClayB ClayC ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Main Corundum — 17 — 20 — — — — — 15.8 5.9 aggregate Chamotte — — 10 — — — — 23.2 — — — in Quartz —  3  5 — — — 35.6 23.5 34.9 11 6.6 substrate Zirconia 14.6 — — — — — — — — — — raw Zircon — — — — 10.2 — — — — — — material Cordierite — — — — — 5.7 — — — — — (wt %) Total 14.6 20 15 20 10.2 5.7 35.6 46.7 34.9 26.8 12.5 firing temperature (° C.) 1180 1180  1180  1180  1180 1180 1200 1200 1180 1180 1180

TABLE-US-00005 TABLE 3 Example 1 2 3 4 5 6 7 8 9 10 11 12 Substrate SiO.sub.2 54.8 58.5 50.2 44.7 57.4 63 53.5 54.2 52.5 55.3 58.5 48.8 Composition Al.sub.2O.sub.3 27.1 24.4 34.8 42.3 25.4 21.8 30.1 30.7 32.5 30.9 26.1 33.4 (wt %) Na.sub.2O 3.3 3.51 3.09 2.02 3.27 3.02 2.65 2.33 3.44 1.39 3.41 1.45 K.sub.2O 4.33 5.03 4.34 5.02 4.28 4.37 4.05 3.83 4.73 5.23 4.96 3.5 Li.sub.2O 0 0 0 0 0 0 0 0 0 0.41 0 0.06 MgO 0.17 0.22 0.14 0.13 0.16 0.2 0.2 0.27 0.17 0.17 0.21 0.35 CaO 9.22 7.24 6.5 5.22 8.39 6.62 8.58 7.5 5.81 5.81 5.81 5.39 ZrO.sub.2 0 0 0 0 0 0 0 0 0 0 0 0 Others 1.08 1.1 0.93 0.61 1.1 0.99 0.92 1.17 0.85 0.79 1.01 7.12 Example Comparative Example 13 14 15 16 17 18 1 2 3 4 5 Substrate SiO.sub.2 44.3 52.4 60.8 49 55.7 57.78 72.5 64.1 73.5 45.1 57.6 Composition Al.sub.2O.sub.3 18.7 35.6 24.7 38.7 21.7 25.26 19.8 32.1 18.8 39.9 27.3 (wt %) Na.sub.2O 2.53 3.15 3.22 2.96 3.16 3.2 1.15 0.03 2.66 1.38 4.88 K.sub.2O 3.7 4.26 4.69 4.06 4.5 5.45 3.32 1.22 3.58 2.67 6.18 Li.sub.2O 0 0 0 0 0 0 0 0 0 0 0 MgO 0.17 0.16 0.19 0.17 0.19 0.22 0.75 0.29 0.31 0.28 0.1 CaO 5.81 3.77 5.46 4.34 6.34 6.97 1.1 0.22 0.57 9.29 3.37 ZrO.sub.2 0 0 0 0 0 0 0 0 0 0 0 Others 24.8 0.72 1 0.76 8.42 1.12 1.38 2.04 0.58 1.38 0.57

[0087] In Tables, the substrate compositions were measured by a glass bead method of a fluorescence X-ray analysis instrument (XRF) after the fired substrate was crushed. Here, the Li.sub.2O amount in the substrate composition was calculated from Li.sub.2O amount in the used raw material (petalite) and the blended amount thereof.

[0088] The glaze having the following composition was prepared; then, this was applied onto the sanitary ware substrate and fired at the firing temperature described in Table 2 as the maximum temperature.

[0089] SiO.sub.2 56.8 parts by weight

TABLE-US-00006 Al.sub.2O.sub.3 8.3 parts by weight Fe.sub.2O.sub.3 0.1 parts by weight CaO 10.1 parts by weight MgO 1.1 parts by weight ZnO 5.1 parts by weight K.sub.2O 1.9 parts by weight Na.sub.2O 1.4 parts by weight ZrO.sub.2 5.6 parts by weight Pigment 0.01 parts by weight

[0090] Physical properties of the sanitary ware obtained by firing are summarized in Table 4 below.

TABLE-US-00007 TABLE 4 Example 1 2 3 4 5 6 7 8 9 10 11 12 Total amount of alkali 7.63 8.54 7.43 7.04 7.55 7.39 6.7 6.16 8.17 7.03 8.37 5.01 metal oxides (wt %) CaO amount (wt %) 9.22 7.24 6.5 5.22 8.39 6.62 8.58 7.5 5.81 5.81 5.81 5.39 Minerals Anorthite ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ contained Corundum — — ◯ ◯ — — — — ◯ ◯ — ◯ * Qualitative Mullite — — — — — — ◯ ◯ — — ◯ — analysis by Quartz — ◯ — — ◯ ◯ — — ◯ ◯ ◯ ◯ XRD Zirconia — — — — — — — — — — — — Zircon — — — — — — — — — — — — Cordierite — — — — — — — — — — — — Anorthite amount (wt %) 29.4 — — — — — 30.3 — — — — — Bulk density (g/cm.sup.3) 1.79 1.93 1.85 2.04 1.79 1.97 1.95 2.11 1.93 2.03 1.95 2.08 Water absorption rate (%) 0.31 0.14 0.34 0.11 0.4 0.2 0.16 0.11 0.3 0.04 0.2 1.44 Closed pore rate (%) 30.2 25.8 30.5 26.4 30.2 23.6 25 19.2 27 23.7 25 24.1  Shrinkage rate by firing (%) 2.2 2.1 1.5 1.99 1.8 1.9 4.7 6.5 1.5 3.2 1.9 1.7  Deformation amount by 1.9 7.6 3.6 6.4 1.9 10 2.8 5.5 5.8 13.6 6 1.14 softening (mm) Flexural Rod — — 63 73 — — — — 69 — — — strength Rectangular 55 51 57 69 53 47 53 62 58 67 46 47.4  (Mpa) Matching with glaze 6.2 2.6 3.8 4.8 4.3 1.8 — — 1.1 — 1.9 — (deformation amount (mm)) Thermal shock resistance — 130 — — — 140 — — 130 — 150 —  T(° C.) Example Comparative Example 13 14 15 16 17 18 1 2 3 4 5 Total amount of alkali 6.23 7.41 7.91 7.02 7.66 8.65 4.47 1.25 6.24 4.05 11.06 metal oxides (wt %) CaO amount (wt %) 5.81 3.77 5.46 4.34 6.34 6.97 1.1 0.22 0.57 9.29 3.37 Minerals Anorthite ◯ ◯ ◯ ◯ ◯ ◯ — — — ◯ ◯ contained Corundum — ◯ — ◯ — — — — — ◯ ◯ * Qualitative Mullite — — ◯ — — — ◯ ◯ ◯ — — analysis by Quartz ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ XRD Zirconia ◯ — — — — — — — — — — Zircon — — — — ◯ — — — — — — Cordierite — — — — — ◯ — — — — — Anorthite amount (wt %) — 14.1  — 15.1 — — — — — — 12.7 Bulk density (g/cm.sup.3) 2.14 2.13 1.97 2.18 2.04 1.99 2.39 1.91 2.35 1.84 3.27 Water absorption rate (%) 0.22 0.18 0.2  0.21 0.14 0.14 0.1 13.8 0.06 16.6 0.02 Closed pore rate (%) 23.2 26.9  23.9  24 24.9  23.2  9.1 0 12 1.8 2.3 Shrinkage rate by firing (%) 1.73 2.23 2.12 1.5 1.64 2.4  9.8 2.4 12.3 1.1 7.1 Deformation amount by 8.1 9.7  8.4  10.7 7.7  11.3  32 2.8 102 0.4 155 softening (mm) Flexural Rod — — — — — — 82 39 — — — strength Rectangular 50.6 61.5  47.4  68 50.7  44.6  — — 74 48 — (Mpa) Matching with glaze — — — — — — 1.0 — — 2.7 — (deformation amount (mm)) Thermal shock resistance 120 — — 140 — — 150 — — — —  T(° C.)

[0091] In the table, the total amount of the alkali metal oxides is the total amount of Li.sub.2O, Na.sub.2O, and K.sub.2O components in the substrate composition in Table 3.

[0092] Identification of the minerals contained therein was done as follows. Namely, the fired substrate was crushed; then, the crushed powders thereby obtained were press-molded to a disk-like shape. By using this as the measurement sample, the qualitative analysis thereof was carried out by an X-ray diffraction apparatus (XRD).

[0093] Quantification of Anorthite

[0094] The anorthite amount the was obtained in such a way that the Rietveld analysis was carried out to the X-ray diffraction pattern obtained by the powder analysis method to determine the scale coefficient, from which the existing amounts of each crystal phase were estimated. Specifically, this was done by the procedure described below.

[0095] Here, the pretreatment was done as follows. Namely, the substrate obtained was crushed until the average particle diameter thereof reached 10 μm or less to obtain the powders. In this example, the mortar and pestle made of tungsten carbide (WC) were used for this treatment. There is no restriction in the crushing method; a general crushing tool such as a ball mill or a mortar may be used.

[0096] The average particle diameter was measured in accordance with the following procedure.

[0097] The water-dispersed body of the substrate powders was prepared by using the ultrasonic dispersion apparatus HYDRO LV (manufactured by Malvern Panalytical Ltd.). The dispersion conditions described below were used. [0098] Dispersant: not used [0099] Frequency: 40 kHz [0100] Irradiation period: 15 seconds [0101] Down-time before start of measurement: 10 seconds [0102] Pump speed: 3500 rpm

[0103] By using the water-dispersed body thereby obtained, the average particle diameter was measured. For the measurement, the laser diffraction type particle measurement instrument MASTERSIZER 3000 and the software MASTERSIZER ver. 3.72 (both manufactured by Malvern Panalytical Ltd.) were used. With the laser diffraction/scattering method based on the Mie theory, the volume-average value was obtained. The refractive index of the dispersion medium was assumed 1.33.

[0104] Next, the X-ray diffraction pattern was obtained by using the powders mentioned above. By using X'Pert (manufactured by Malvern Panalytical Ltd.), the X-ray diffraction pattern was obtained with the X-ray source of CuKα beam (wavelength: λ=0.15406 nm), the diffraction angle (20) of 10 to 60°, and the step size of 0.02°, as the measurement condition. Because it had been known that the larger the obtained X-ray diffraction peak of the crystal phase is, the higher is the accuracy of the quantification, the measurement was done in such a way that the strength of the highest peak in the X-ray diffraction peaks might be 10,000 counts or greater. The X-ray diffraction peak thereby obtained was analyzed by using the software High Score Plus (ver. 4.9).

[0105] The crystal phase included in the substrate was identified by selecting the crystal phase that coincided with the PDF (Powder Diffraction File) data of ICDD (International Centre for Diffraction Data) upon comparing the X-ray diffraction pattern obtained under the conditions described above with these data.

[0106] With regard to the crystal phase thus identified, the Rietveld analysis was done by the external standard method. Al.sub.2O.sub.3 was used as the substance for the outside standard sample. From this outside standard sample, the X-ray diffraction pattern was obtained; then, by comparing with the area of the obtained X-ray diffraction with referring to the COD (Crystallography Open Database) file, the existing amount thereof (% by weight) was calculated to set the standard.

[0107] Next, the X-ray diffraction data were obtained in each substrate of Examples and Comparative Examples: then, the diffraction pattern of only the identified crystal phase was quantitatively evaluated with referring to the COD file corresponding to each crystal phase. Because the total amount (% by weight) of the obtained crystal phases did not reach 100%, the amount obtained by subtracting the total amount of the crystal phases from 100% was taken as the quantitative value (% by weight) of the glass phase (amorphous phase).

[0108] Among others, the treatment of the background and the treatment of the X-ray diffraction pattern necessary for quantification such as the diffraction peaks by Kα2 and Kβ, smoothing, or the like were done by the software “High Score Plus”.

[0109] The “water absorption rate” and “closed pore rate” in the tables were measured by the measurement methods described above. Further, “bulk density”, “shrinkage rate by firing”, “deformation amount by softening”, “flexural strength”, and “thermal shock resistance” were measured as follows.

[0110] Bulk Density

[0111] This was measured in accordance with the measurement method of the density and open pore rate of a sintered body of fine ceramics in JIS R1634:1988.

[0112] Shrinkage Rate by Firing

[0113] The substrate before firing was cut out to the size of 7 mm×8 mm×70 mm to prepare the molded article sample. The length of the center portion of this molded article sample was measured. Next, this sample was fired; then, the length of the center portion of this sample after firing was measured. The shrinkage rate was calculated from the difference of the shrinkage amount.

[0114] Deformation Amount by Softening

[0115] The test piece of the molded article having the width of 30 mm, the thickness of 10 mm, and the length of 250 mm was fired under the state of this being held with the span of 200 mm. The hang-down amount in the center portion of the test piece after firing was measured to determine the measurement value of the deformation by softening. Because the amount of the deformation by softening is inversely proportional to the square of the thickness, the value converted to the thickness of 10 mm was taken as the deformation amount by softening.

[00004]$\mathrm{Deformation}\mathrm{amount}\mathrm{by}\mathrm{softening}=\begin{array}{c}\mathrm{Measurement}\mathrm{value}\mathrm{of}\\ \mathrm{deformation}\mathrm{by}\mathrm{softening}\end{array}\times \frac{{\left(\mathrm{Measurement}\mathrm{value}\mathrm{of}\mathrm{thickness}\right)}^2}{10^2}$

[0116] Flexural Strength

[0117] This was measured in accordance with JIS A1509-4: 2014. Specifically, this was measured as follows. The fired body molded to or cut out to the size of 7 mm×8 mm×70 mm was prepared as the rectangular sample. The 3-ponts flexural strength of this sample was measured. The measurement condition with the span of 50 mm and the cross head speed of 0.5 mm/minute was used.

[0118] The fired body having the diameter of 14 mm×150 mm was prepared as the rod sample. The 3-ponts flexural strength of this sample was measured. The measurement condition with the span of 100 mm and the cross head speed of 2.5 mm/minute was used.

[0119] Matching with Glaze

[0120] The substrate raw material of the sanitary ware was molded to prepare the test piece having the size of 20 mm×8 mm×150 mm. A glaze was applied onto one surface of this test piece with the thickness of 0.6 to 0.7 mm; then, this was fired by placing the side of the 8 mm thickness and the 150 mm length (side surface) as the down side. After firing, the warp in the center portion in the non-blazed side thereof was measured with the longitude direction as the standard to obtain the warp amount as the deformation amount.

[0121] Thermal Shock Resistance

[0122] The fired body having the width of 25 mm, the thickness of 10 mm, and the length of 110 mm was used as the test piece. The test piece was heated to a prescribed temperature, and then, after this was kept at this temperature for 1 hour or longer, this was dropped into water so as to be rapidly cooled; then, the generated crack was confirmed by the ink check. The temperature difference at the rapid cooling (difference between the prescribed heating temperature and the water temperature) was gradually increased; and this operation was repeated until the crack was formed in the test piece. The temperature difference to generate the crack upon rapid cooling in 50% of the samples in number was taken as the thermal shock resistance of the test substrate.