Shaped body, shaped body having glaze layer, and method for manufacturing shaped body

Abstract

To provide: a shaped body capable of preventing defects from occurring in a glaze layer to be formed on a shaped body having excellent dimensional accuracy; a shaped body having the glaze layer; and a method for manufacturing the shaped body.SOLUTION: A shaped body has a main body thereof comprising an aggregate and a binder for bonding the aggregate, and a surface heterogeneous layer provided on at least a part of a surface of the main body. In a first embodiment, the surface heterogeneous layer has: a pore median diameter Du of 0.1 μm to 15.0 μm; and a product of an open pore rate Pu of the surface heterogeneous layer and an average thickness Tu of the surface heterogeneous layer of 0.01 mm to 0.30 mm, wherein Du is smaller than the pore median diameter Dm of the shaped body. In a second embodiment, a parameter Am represented by formula (1) is smaller than a parameter Au represented by formula (2). Explanations of formulae (1) and (2) are omitted.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a shaped body, a shaped body with a glaze layer, and a method for manufacturing a shaped body.

Background Art

[0002] In recent years, the shaping technology of ceramics using 3D printers has advanced and has been widely put into practical use. Shaping ceramics with a 3D printer can handle complex shapes that are difficult with ordinary shaping methods using a plaster mold, and is also suitable for multi-variety production and small-lot production. Therefore, it is expected to be applied to high-value-added products such as artworks. In Non-Patent Document 1, basic technology for directly shaping ceramic products using clay as a raw material with a 3D printer was studied, and a cylindrical shape was realized. In addition, in Non-Patent Document 2, for the purpose of shaping more complex shapes with higher precision, a shaping material made of a mixture of heat-resistant spherical particles and alumina cement was used instead of clay, and the shaping of an inorganic shaped body was realized by a powder lamination type 3D printer. The inorganic shaped body using this shaping material (hereinafter referred to as "powder lamination shaped body") has characteristics such as being able to realize excellent surface properties and being able to realize high dimensional accuracy because it hardly shrinks thermally unlike ordinary clay. Non-Patent Document 2 introduces a case of utilization as a mold.

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Generally, for ceramics, the texture is improved by applying glaze to the surface of a bisque fired product made of clay, and design properties are imparted by coloring. Similarly, in the case of a powder laminated compact, glazing is required from the viewpoint of design properties. However, unlike general bisque firing, depending on the type of glaze, an intended surface cannot be obtained with a single glazing, and it has been found that color unevenness may occur or a rough surface may result without forming a smooth glassy surface. In order to solve such problems and approach the surface properties of general bisque firing, it is conceivable to apply glaze thickly by combining methods such as applying glaze multiple times, changing the concentration of the glaze, and changing the glazing method. However, changing the glazing conditions only for some colors not only poses problems in terms of cost and mass productivity, but may also result in the loss of fine design properties on the surface of the compact. In addition, there are also problems such as the limitation of the available glaze and the loss of the advantages of the powder laminated compact. Furthermore, the problem that the glaze layer adheres poorly to the powder laminated compact is also cited.

[0005] Therefore, an object of the present invention is to provide a compact capable of suppressing the occurrence of defects in a glaze layer when forming the glaze layer on a compact having excellent dimensional accuracy, a compact with a glaze layer using this compact, and a method for manufacturing this compact.

Means for Solving the Problems

[0006] Specific means for achieving the above object are as follows. <1> A compact body including an aggregate and a binder that binds the aggregate, and a surface heterogeneous layer provided on at least a part of the surface of the compact body, wherein a pore median diameter D of the surface heterogeneous layer u is 0.1 μm to 15.0 μm, and a product of an open porosity P of the surface heterogeneous layer u and an average thickness T of the surface heterogeneous layer u [mm] is 0.01 mm to 0.30 mm, wherein the pore median diameter D of the surface heterogeneous layeru is a shaped body with a pore median diameter D of the shaped body main body m smaller than that. <2> The shaped body according to <1>, wherein the average thickness T u is 0.01 mm to 0.55 mm. <3> The difference D m between the D u and the D m -D u is 5.0 μm to 49.0 μm, which is the shaped body according to <1> or <2>. <4> The parameter A represented by the following formula (1) for the shaped body main body m is smaller than the parameter A represented by the following formula (2) for the surface heterogeneous layer u which is the shaped body according to any one of <1> to <3>. A m = 0.5[SiO 2 m - 0.2[ZrO 2 m - 5[TiO 2 m + 5[R 2 O] m + 2[ReO] m - 0.2[Al 2 O 3 m ··· Formula (1) A u = 0.5[SiO 2 u - 0.2[ZrO 2 u - 5[TiO 2 u + 5[R 2 O] u + 2[ReO] u - 0.2[Al 2 O 3 u ··· Formula (2) Here, [SiO 2 , [ZrO 2 , [TiO 2 and [Al 2 O 3 are SiO 2 , ZrO 2 ​​​​​​​​, TiO 2 , and Al 2 O 3 is a number representing the amount, and [R 2 O] is a number representing the total amount of Li 2 O, Na 2 O, and K 2 O in mass percentage based on oxides. [ReO] is a number representing the total amount of MgO, CaO, SrO, and BaO in mass percentage based on oxides. Each subscript m represents a number representing the amount contained in the formed body main body, and each subscript u represents a number representing the amount contained in the surface heterogeneous layer. <5> A formed body main body including an aggregate and a binder that binds the aggregate, and a surface heterogeneous layer provided on at least a part of the surface of the formed body main body, The parameter A represented by the following formula (1) for the formed body main body m is smaller than the parameter A represented by the following formula (2) for the surface heterogeneous layer. u A formed body. A m = 0.5[SiO 2 m - 0.2[ZrO 2 m - 5[TiO 2 m + 5[R 2 O] m + 2[RO] m - 0.2[Al 2 O 3 m ··· Formula (1) A u = 0.5[SiO 2 u - 0.2[ZrO 2 u - 5[TiO 2 u + 5[R 2 O] u + 2[ReO] u - 0.2[Al 2 O 3 u ··· Formula (2) Here, [SiO 2 , [ZrO 2 ​​​​​​​​, [TiO 2 , and [Al 2 O 3 are numbers representing the amounts of SiO 2 , ZrO 2 , TiO 2 , and Al 2 O 3 respectively in terms of mass percentage based on oxides. [R 2 O] is a number representing the total amount of Li 2 O, Na 2 O, and K 2 O in terms of mass percentage based on oxides. [ReO] is a number representing the total amount of MgO, CaO, SrO, and BaO in terms of mass percentage based on oxides. Each with subscript m represents the amount contained in the shaped body main body, and each with subscript u represents the amount contained in the surface heterogeneous layer. <6> The parameter T represented by the following formula (3) using the A m , the A u , and the open porosity P m of the shaped body main body is 0.0 to 50.0, which is the shaped body according to <4> or <5>. T = (1 - P m ) × A m + P m × A u ··· Formula (3) <7> The surface heterogeneous layer contains, based on oxides, 65 to 85 mass% of SiO 2 , 15 to 35 mass% of Al 2 O 3 , a total of 1 to 20 mass% of Li 2 O, Na 2 O, and K 2 O, and a total of 0.1 to 5 mass% of MgO, CaO, SrO, and BaO. The shaped body main body contains, based on oxides, 1 to 30 mass% of SiO 2 , 40 to 95 mass% of Al 2 O 3 , and 0 to 30 mass% of ZrO 2 , which is the shaped body according to any one of <1> to <6>. <8> The volume V 2 of the surface heterogeneous layer with respect to the volume V 1Volume ratio: V 1 / V 2 is 10 -9 ~1, being the shaped body according to any one of <1> to <7>. <9> The shaped body according to any one of <1> to <8>, wherein the binder contains an inorganic binder. <10> The shaped body according to any one of <1> to <9>, and a glaze layer provided on at least a part of the surface heterogeneous layer in the shaped body, being a shaped body with a glaze layer. <11> The shaped body with a glaze layer according to <10>, used as tableware. <12> The shaped body with a glaze layer according to <10>, used as a work of art. <13> Forming a surface heterogeneous layer on at least a part of the surface of a shaped body main body including an aggregate and a binder that binds the aggregate, wherein the surface heterogeneous layer has a pore median diameter D u of 0.1 μm to 15.0 μm, and the product of the open porosity P u of the surface heterogeneous layer and the average thickness T u [mm] of the surface heterogeneous layer is 0.01 mm to 0.30 mm, and the pore median diameter D u of the surface heterogeneous layer is smaller than the pore median diameter D m of the shaped body main body, being a manufacturing method of a shaped body. <14> Forming a surface heterogeneous layer on at least a part of the surface of a shaped body main body including an aggregate and a binder that binds the aggregate, wherein the parameter A m represented by the following formula (1) for the surface heterogeneous layer is smaller than the parameter A u represented by the following formula (2) for the shaped body main body, being a manufacturing method of a shaped body. A m = 0.5[SiO 2 m - 0.2[ZrO 2 m - 5[TiO 2 m + 5[R 2 O] m + 2[RO]​​​m -0.2[Al 2 O 3 m ···Formula (1) A u =0.5[SiO 2 u -0.2[ZrO 2 u -5[TiO 2 u +5[R 2 O] u +2[RO] u -0.2[Al 2 O 3 u ···Formula (2) Here, [SiO 2 , [ZrO 2 , [TiO 2 , and [Al 2 O 3 are the numbers representing the amounts of SiO 2 , ZrO 2 , TiO 2 , and Al 2 O 3 respectively in terms of mass percentage based on the oxide. [R 2 O] is the number representing the total amount of Li 2 O, Na 2 O, and K 2 O in terms of mass percentage based on the oxide. [ReO] is the number representing the total amount of MgO, CaO, SrO, and BaO in terms of mass percentage based on the oxide. Each subscript m represents the amount contained in the main body of the formed body, and each subscript u represents the amount contained in the surface heterogeneous layer.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a formed body capable of suppressing the occurrence of defects in the glaze layer when forming the glaze layer on a formed body with excellent dimensional accuracy, a formed body with a glaze layer using this formed body, and a method for manufacturing this formed body.

Brief Description of the Drawings

[0008]

Figure 1

Embodiments for Carrying Out the Invention

[0009] Hereinafter, embodiments according to the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, which do not limit the present disclosure.

[0010] In the present disclosure, in the numerical range indicated by "~", the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerically described range. Also, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. In the present disclosure, each component may contain a plurality of corresponding substances. When there are a plurality of substances corresponding to each component in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may contain a plurality of types of particles. When there are a plurality of types of particles corresponding to each component in the composition, the particle diameter of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified. In the present disclosure, the term "layer" or "film" includes not only the case where it is formed over the entire region where the layer or film exists, but also the case where it is formed only in a part of the region when observing the region where the layer or film exists. In the present disclosure, the term "lamination" indicates stacking layers, and two or more layers may be bonded, or two or more layers may be detachable. In the present disclosure, the term "process" includes not only a process independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved.

[0011] In the present disclosure, the thickness of a layer is measured by observing a cross-section of the measurement object using a scanning electron microscope (SEM) or an electron probe microanalyzer (EPMA).

[0012] In the shaped body of the present disclosure, an intermediate layer may exist as a region where the constituent components of the surface heterogeneous layer and the constituent components of the shaped body main body coexist. In this case, the surface heterogeneous layer refers to a region including the intermediate layer.

[0013] <Shaped body> The first shaped body of the present disclosure has a shaped body main body including an aggregate and a binder that binds the aggregate, and a surface heterogeneous layer provided on at least a part of the surface of the shaped body main body. And the surface heterogeneous layer has a pore median diameter D u of 0.1 μm to 15.0 μm, and the product of the open porosity P u of the surface heterogeneous layer and the average thickness T u [mm] of the surface heterogeneous layer is 0.01 mm to 0.30 mm, and the pore median diameter D u of the surface heterogeneous layer is smaller than the pore median diameter D m of the shaped body main body. The unit of P u is dimensionless.

[0014] By configuring the first shaped body, it becomes possible to suppress the occurrence of defects in the glaze layer when forming the glaze layer on a shaped body having excellent dimensional accuracy. Specifically, even in a shaped body having excellent dimensional accuracy, the color development property and glossiness of the glaze layer are excellent. Although the reason for this is not clear, it is considered as follows.

[0015] A surface heterogeneous layer is provided on at least a part of the surface of the shaped body main body, and the pore median diameter D u of this surface heterogeneous layer is smaller than the pore median diameter D m of the shaped body main body, and the pore median diameter D u of the surface heterogeneous layer and the open porosity Pu and the average thickness T u By setting the product with to within a specific range, the solid components in the glaze are likely to appropriately stay on the surface heterogeneous layer, and the excess moisture in the glaze layer is likely to be absorbed by the shaped body main body, suppressing color unevenness of the glaze when glazing, and forming a smooth glassy surface with the glaze.

[0016] The second shaped body of the present disclosure has a shaped body main body including an aggregate and a binder that binds the aggregate, and a surface heterogeneous layer provided on at least a part of the surface of the shaped body main body, and a parameter A represented by the following formula (1) for the shaped body main body m is smaller than the parameter A represented by the following formula (2) for the surface heterogeneous layer u . Parameter A m and A u are dimensionless.

[0017] A m = 0.5[SiO 2 m - 0.2[ZrO 2 m - 5[TiO 2 m + 5[R 2 O] m + 2[RO] m - 0.2[Al 2 O 3 m ··· Formula (1) A u = 0.5[SiO 2 u - 0.2[ZrO 2 u - 5[TiO 2 u + 5[R 2 O] u + 2[ReO] u - 0.2[Al 2 O 3 u ··· Formula (2)

[0018] Here, [SiO 2 , [ZrO 2 , [TiO 2 ​​​​​​​​and [Al 2 O 3 are numbers representing the amounts of SiO 2 ZrO 2 TiO 2 and Al 2 O 3 respectively in mass percentage based on oxides, and [R 2 O] is a number representing the total amount of Li 2 O, Na 2 O and K 2 O in mass percentage based on oxides, [ReO] is a number representing the total amount of MgO, CaO, SrO and BaO in mass percentage based on oxides, each with a subscript m represents the amount contained in the shaped body main body, and each with a subscript u represents the amount contained in the surface heterogeneous layer.

[0019] By configuring the second shaped body, it becomes possible to suppress the occurrence of defects in the glaze layer when forming the glaze layer on the shaped body with excellent dimensional accuracy. Specifically, the adhesion between the shaped body and the glaze layer is improved. Although the reason for this is not clear, it is considered as follows.

[0020] The shaped body main body with excellent dimensional accuracy has a small thermal shrinkage rate. On the other hand, a general glaze applied to the surface of the shaped body shrinks thermally. If the difference in thermal shrinkage rate between the shaped body and the glaze layer is large, the adhesion of the glaze layer to the shaped body decreases due to sintering. Since the glaze is a material directly related to the design, it is desirable to use a general glaze as it is. Therefore, a surface heterogeneous layer is provided on at least a part of the surface of the shaped body main body with excellent dimensional accuracy to suppress the difference in thermal shrinkage rate between the glaze layer and the shaped body during sintering. As a method for suppressing the difference in thermal shrinkage rate, the inventors have experimentally found a second shaped body in which the composition of the shaped body main body and the composition of the surface heterogeneous layer are adjusted to a specific range. When a glaze layer is provided on the second shaped body, since a specific surface heterogeneous layer is interposed between the glaze layer and the shaped body main body, it is considered that this surface heterogeneous layer functions to alleviate the difference in thermal shrinkage rate between the glaze layer and the shaped body main body.

[0021] Note that the method of the second shaped body, that is, the parameter A represented by formula (1)m and parameter A represented by formula (2) u Satisfying the relationship with may also be applied to the first shaped body. Combining the method of the first shaped body and the method of the second shaped body can obtain a shaped body with improved adhesion of the glaze layer and excellent color development and glossiness.

[0022] A method for discriminating between the shaped body main body and the surface heterogeneous layer in the shaped body of the present disclosure will be described. Since the first shaped body of the present disclosure has different pore median diameters in the shaped body main body and the surface heterogeneous layer, the shaped body cross-section obtained by cutting the shaped body with a water-cooled rotary blade cutter is observed by SEM or EPMA to obtain a backscattered electron image. Thus, the shaped body main body and the surface heterogeneous layer can be discriminated. It can be discriminated that the portion with a sparse structure is the shaped body main body, and the portion with a dense structure is the surface heterogeneous layer. Specifically, the backscattered electron image is observed by SEM or EPMA in a state where the magnification is adjusted so that the surface of the shaped body and the interface between the surface heterogeneous layer and the shaped body main body are within the same visual field, and a region having a structure as dense as the cross-sectional structure up to a depth of 0.1 μm from the surface of the shaped body is defined as the surface heterogeneous layer. As a specific example of the shaped body, FIG. 1 shows a backscattered electron image when the cross-section of the shaped body of Example 18 in the examples was observed by SEM. It can be seen that the surface heterogeneous layer formed on the surface side (the upper side in the photograph) has a dense structure, and the shaped body main body on the inner side (the lower side in the photograph) has a sparse structure. The upper region up to the upper dotted line in FIG. 1 is the surface heterogeneous layer. Further, in FIG. 1, a region where the constituent components of the surface heterogeneous layer partially penetrate into the shaped body main body is confirmed, and this region is defined as the intermediate layer. The intermediate layer is the region between the upper dotted line and the lower dotted line in FIG. 1.

[0023] In the second shaped body of the present disclosure, since the compositions of the shaped body main body and the surface heterogeneous layer are different, the shaped body main body and the surface heterogeneous layer can be discriminated by composition analysis. The composition analysis can be carried out by, for example, scanning electron microscope - energy dispersive X - ray spectroscopy (SEM - EDX), electron probe micro analyzer, etc. Specifically, the shaped body including the surface heterogeneous layer and the shaped body main body is embedded in resin. This resin is polished and finally mirror - polished to expose the interface between the shaped body main body and the surface heterogeneous layer. Composition analysis of the shaped body main body and the surface heterogeneous layer is performed from near this interface.

[0024] (Shaped body main body) The shaped body main body includes an aggregate and a binder that binds the aggregate. The aggregate is preferably a material having heat resistance and a small thermal shrinkage rate during sintering. From the viewpoint of suppressing dimensional variation of the shaped body, inorganic particles are preferred. Examples of the inorganic particles include silica particles, magnesia particles, and foundry sand. The foundry sand may be new sand or recycled sand. The aggregate may be used alone or in combination of two or more. The shape of the aggregate is not particularly limited, and from the viewpoint of fluidity during shaping, it is preferably spherical. Examples of the spherical aggregate include spherical silica and silica sand processed into a spherical shape.

[0025] As commercially available products, the aggregate includes, for example, FINE - Bz (manufactured by AGC Ceramics Co., Ltd.), Lunamos (registered trademark) (manufactured by Kao Quaker Co., Ltd.), AR SAND (manufactured by Gun Ei Chemical Industry Co., Ltd.), NIGAI CERABEADS (manufactured by Itochu Ceratec Co., Ltd.), zircon sand, chromite sand, Esperal (manufactured by Yamakawa Sangyo Co., Ltd.), etc.

[0026] The average particle diameter of the aggregate is preferably 5 μm to 200 μm from the viewpoints of the surface properties of the formed body, fluidity during forming, etc. In view of the fluidity in manufacturing by a 3D printer, the average particle diameter of the aggregate is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more. Further, from the viewpoint of reducing the surface roughness of the formed body, the average particle diameter of the aggregate is preferably 200 μm or less, and more preferably 100 μm or less.

[0027] The average particle diameter of the aggregate is determined by observing a cross-section of the formed body by SEM by the above method, measuring the diameters of any 100 particles in the visual field for the formed body main body, and taking the average value.

[0028] The binder may be any material that can bind the aggregate. From the viewpoints of improving the dimensional accuracy of the formed body and heat resistance, an inorganic binder is preferable. Examples of the binder include various cement materials such as alumina cement, Portland cement, rapid-hardening cement, and phosphate cement; metal alkoxide materials used in the production methods of phosphoric acid compounds, water glass, ceramics by the sol-gel method, etc.; sulfates such as aluminum sulfate and magnesium sulfate; chlorides containing polyaluminum chloride; and the like. These may be used alone or in combination of two or more. When using two or more binders in combination, it is preferable to use alumina cement in combination with other binders.

[0029] In the first formed body, the pore median diameter D of the formed body main body m is larger than the pore median diameter D of the surface heterogeneous layer described later. u Also in the second formed body, it is preferable that D m is larger than D u . By D m being larger than D u , excess moisture in the glaze layer is easily absorbed by the formed body main body, unevenness in the color of the glaze during glazing is suppressed, and a smooth glassy surface by the glaze is formed. Further, by D m being larger than D u , the workability during glazing also tends to be improved.

[0030] Median pore diameter D of the shaped body body m is preferably 1 μm to 50 μm from the viewpoint of suppressing deformation before and after sintering and improving dimensional accuracy. D m is preferably 1 μm or more, more preferably 3 μm or more, still more preferably 6 μm or more, particularly preferably 9 μm or more, extremely preferably 12 μm or more, and most preferably 15 μm or more from the viewpoint of absorbing excess moisture in the glaze layer. Also, D m is preferably 50 μm or less, more preferably 45 μm or less, still more preferably 40 μm or less, particularly preferably 35 μm or less, extremely preferably 30 μm or less, and most preferably 25 μm or less from the viewpoint of mechanical strength.

[0031] D m The measurement method of D is as follows. After distinguishing the shaped body body and the surface heterogeneous layer by the above method, a sample obtained by cutting out the region corresponding to the shaped body body is prepared, and the pore size distribution of the shaped body body is measured by the mercury intrusion method. The pore diameter with the highest frequency in the obtained pore size distribution is defined as D m As an apparatus used for the measurement by the mercury intrusion method, for example, PoreMaster-60-GT (manufactured by Quantachrome) can be mentioned. The mercury parameters are set to a mercury contact angle of 130.0° and a mercury surface tension of 485.0 mN / m (485.0 dynes / cm). A sample (about 0.3 g) is placed in a standard cell and measured under the condition of an initial pressure of 9 kPa (about 1.3 psia, corresponding to a pore diameter of about 139 μm).

[0032] Open porosity P of the shaped body body m is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.12 or more, particularly preferably 0.16 or more, and extremely preferably 0.20 or more from the viewpoint of maintaining the absorption rate of excess moisture in the glaze layer and the homogeneity of the surface of the glaze layer after glazing. P m The unit of P is dimensionless. Also, from the viewpoint of facilitating the control of the thickness of the glaze layer and enabling the expression of a fine surface shape, P mis preferably 0.85 or less, more preferably 0.80 or less, still more preferably 0.75 or less, particularly preferably 0.70 or less, and extremely preferably 0.65 or less.

[0033] P m After distinguishing the formed body main body and the surface heterogeneous layer by the above method, a sample obtained by cutting out the region corresponding to the formed body main body is prepared and measured according to the method described in JIS R1634:1998. Three samples are prepared, and the average value of the three points is defined as P m .

[0034] The parameter A represented by the following formula (1) for the formed body main body m is preferably -35 or more, more preferably -30 or more, still more preferably -25 or more, and particularly preferably -20 or more from the viewpoint of maintaining the adhesion to the surface heterogeneous layer. Also, from the viewpoint of maintaining dimensional accuracy, A m is preferably 50 or less, more preferably 45 or less, still more preferably 40 or less, particularly preferably 35 or less, and extremely preferably 30 or less.

[0035] A m = 0.5[SiO 2 m - 0.2[ZrO 2 m - 5[TiO 2 m + 5[R 2 O] m + 2[RO] m - 0.2[Al 2 O 3 m ··· Formula (1)

[0036] Here, [SiO 2 m , [ZrO 2 m , [TiO 2 m and [Al 2 O 3 m are the contents of SiO 2 , ZrO 2 , TiO​​​​​​​​2 and Al 2 O 3 are numbers representing the respective amounts in terms of mass percentage based on the oxide, and [R 2 O] m is a number representing the total amount in terms of mass percentage based on the oxide of [Li 2 O], [Na 2 O] and [K 2 O] contained in the shaped body main body, and [ReO] m is a number representing the total amount in terms of mass percentage based on the oxide of MgO, CaO, SrO and BaO contained in the shaped body main body.

[0037] A m is obtained as follows. After distinguishing the shaped body main body and the surface heterogeneous layer by the above method, the contents of SiO 2 , ZrO 2 TiO 2 Al 2 O 3 R 2 O and ReO in the shaped body main body are determined by fluorescent X-ray analysis. Using the determined contents of the respective components as numbers representing the amounts in terms of mass percentage based on the oxide, the calculation is performed based on the above formula (1).

[0038] The shaped body main body preferably contains, based on the oxide, 1 to 30% by mass of SiO 2 40 to 95% by mass of Al 2 O 3 and 0 to 30% by mass of ZrO 2 . In the shaped body main body, ZrO 2 is more preferably 1% by mass or more based on the oxide.

[0039] The shape of the shaped body main body may be any, and may be plate-shaped, curved surface-shaped, bent-shaped, or a combination thereof. The shape of the shaped body main body is determined in view of the shape of the shaped body with glaze which is the final product.

[0040] (Surface heterogeneous layer) The surface heterogeneous layer is provided on at least a part of the surface of the shaped body main body. In the first shaped body, the pore median diameter D of the surface heterogeneous layeru is from 0.1 μm to 15.0 μm, and the pore median diameter D of the surface heterogeneous layer u is smaller than the pore median diameter D of the shaped body main body m . In the second shaped body, D u is not particularly limited, but is preferably from 0.1 μm to 15.0 μm, and it is preferable that it is smaller than D m .

[0041] D u is preferably 0.2 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, particularly preferably 0.7 μm or more, and extremely preferably 1.0 μm or more from the viewpoint of water absorption. Also, D u is preferably 12.0 μm or less, more preferably 10 μm or less, still more preferably 8.0 μm or less, particularly preferably 6.0 μm or less, and extremely preferably 4.0 μm or less from the viewpoint of appropriately retaining the solid components in the glaze on the surface of the shaped body.

[0042] D u The measurement method of D is the same as the measurement method of D except that a sample obtained by cutting out a region corresponding to the surface heterogeneous layer is used. m

[0043] D u and D m The difference of D is not particularly limited, but D m - D u is preferably 5.0 μm or more, more preferably 6.0 μm or more, still more preferably 8.0 μm or more, particularly preferably 10.0 μm or more, extremely preferably 12.0 μm or more, and most preferably 14.0 μm or more. Also, D m - D u The upper limit value of D is not particularly limited, but from the viewpoints of mechanical strength and ease of forming the surface heterogeneous layer, it is preferably 49.0 μm or less, more preferably 45.0 μm or less, still more preferably 40.0 μm or less, particularly preferably 35.0 μm or less, and extremely preferably 30.0 μm or less.

[0044] In the first shaped body, the open porosity P of the surface heterogeneous layer u ​and the average thickness T of the surface heterogeneous layer u [mm] and the product: P u ×T u [mm] is 0.01 mm to 0.30 mm. In the second shaped body, P u ×T u is not particularly limited, but 0.01 mm to 0.30 mm is preferable. The inventors have experimentally found that when P u ×T u is 0.01 mm to 0.30 mm, excess moisture in the glaze layer is absorbed by the surface heterogeneous layer, and further that moisture is sufficiently absorbed by the shaped body main body.

[0045] P u ×T u is preferably 0.02 mm or more, more preferably 0.03 mm or more, still more preferably 0.04 mm or more, particularly preferably 0.05 mm or more, and extremely preferably 0.06 mm or more from the viewpoint of improving the homogeneity of the surface of the glaze layer while maintaining the absorption rate of excess moisture in the glaze layer. Also, from the viewpoints of ease of controlling the thickness of the glaze layer and being able to express a fine surface shape, P u ×T u is preferably 0.25 mm or less, more preferably 0.20 mm or less, still more preferably 0.17 or less, particularly preferably 0.13 mm or less, and extremely preferably 0.11 mm or less.

[0046] T u If it has a thickness of 0.01 mm or more, there is a tendency to relieve the unevenness on the surface of the shaped body regardless of the average particle diameter of the aggregate. Tu is preferably 0.03 mm or more, more preferably 0.05 mm or more, still more preferably 0.07 mm or more, and particularly preferably 0.09 mm or more. From the viewpoint of suppressing defects in the surface heterogeneous layer, it is preferable to suppress the thickness of the intermediate layer, and from this viewpoint, T u is preferably 0.55 mm or less, more preferably 0.45 mm or less, still more preferably 0.40 mm or less, particularly preferably 0.35 mm or less, and extremely preferably 0.30 mm or less.

[0047] Tu is measured by the following method. The regions of the shaped body main body and the surface heterogeneous layer are confirmed by the above method, and the thickness of the surface heterogeneous layer is measured by the reflected electron image of SEM or EPMA. T u is the average value of the thicknesses at three locations within the same field of view of the reflected electron image.

[0048] P u From the viewpoint of further improving the homogeneity of the glaze layer surface after glazing while maintaining the absorption rate of excess moisture in the glaze layer, 0.20 or more is preferable, 0.25 or more is more preferable, 0.30 or more is further preferable, 0.33 or more is particularly preferable, and 0.35 or more is extremely preferable. Also, from the viewpoints of ease of controlling the thickness of the glaze layer and being able to express a fine surface shape, P u is preferably 0.60 or less, more preferably 0.55 or less, further preferably 0.50 or less, particularly preferably 0.45 or less, and extremely preferably 0.40 or less. P u The measurement method of P is the same as the measurement method of P except that a sample obtained by cutting out the region corresponding to the surface heterogeneous layer is used. m is the same as the measurement method of P.

[0049] Parameter A represented by the following formula (2) for the surface heterogeneous layer u From the viewpoint of maintaining strength, 30.0 or more is preferable, 35.0 or more is more preferable, 40.0 or more is further preferable, and 45.0 or more is particularly preferable. Also, from the viewpoint of maintaining adhesion to the shaped body main body, A u is preferably 75.0 or less, more preferably 70.0 or less, further preferably 65.0 or less, and particularly preferably 60.0 or less.

[0050] A u =0.5[SiO 2 u -0.2[ZrO 2 u -5[TiO 2 u +5[R 2 O] u +2[ReO] u -0.2[Al​​​2 O 3 u ··· Formula (2)

[0051] Here, [SiO 2 u , [ZrO 2 u , [TiO 2 u and [Al 2 O 3 u are the numbers representing the respective amounts in terms of mass percentage based on oxides of SiO 2 , ZrO 2 , TiO 2 , and Al 2 O 3 contained in the surface heterogeneous layer. [R 2 O] u is the number representing the total amount in terms of mass percentage based on oxides of Li 2 O, Na 2 O, and K 2 O contained in the surface heterogeneous layer. [ReO] u is the number representing the total amount in terms of mass percentage based on oxides of MgO, CaO, SrO, and BaO contained in the surface heterogeneous layer. A u is obtained in the same way as A m except that the region corresponding to the surface heterogeneous layer is taken as the measurement target.

[0052] The content of SiO 2 in the surface heterogeneous layer is preferably 65 - 85% by mass, more preferably 66 - 80% by mass, still more preferably 67 - 75% by mass, and particularly preferably 68 - 72% by mass in terms of mass percentage based on oxides. The content of ZrO 2 in the surface heterogeneous layer is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less in terms of mass percentage based on oxides. The Al 2 O 3 ​​​​​The content of is preferably 15 to 35% by mass, more preferably 18 to 33% by mass, still more preferably 20 to 30% by mass, and particularly preferably 22 to 28% by mass, expressed as a mass percentage based on oxides. TiO in the surface heterogeneous layer 2 The content of is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, expressed as a mass percentage based on oxides. R in the surface heterogeneous layer 2 The content of O is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, still more preferably 2.5 to 10% by mass, and particularly preferably 3 to 7% by mass, expressed as a mass percentage based on oxides. The content of ReO in the surface heterogeneous layer is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, still more preferably 0.1 to 1% by mass, and particularly preferably 0.12 to 0.8% by mass, expressed as a mass percentage based on oxides. The surface heterogeneous layer preferably contains 65 to 85% by mass of SiO 2 15 to 35% by mass of Al 2 O 3 1 to 20% by mass of R 2 O, and 0.1 to 5% by mass of ReO, expressed as a mass percentage based on oxides.

[0053] In the second shaped body, the parameter A of the shaped body main body m is smaller than the parameter A of the surface heterogeneous layer u In the first shaped body as well, it is preferable that the parameter A of the shaped body main body m is smaller than the parameter A of the surface heterogeneous layer u A u and A m The difference between: A u -A m is not particularly limited, but A u -A m is preferably 5.0 or more, more preferably 10.0 or more, still more preferably 15.0 or more, particularly preferably 20.0 or more, and extremely preferably 25.0 or more. Also, A u -A m ​The upper limit is not particularly limited, but from the perspective of suppressing the occurrence of defects such as cracks, it is preferably 100.0 or less, more preferably 95.0 or less, still more preferably 90.0 or less, particularly preferably 85.0 or less, and extremely preferably 80.0 or less.

[0054] From the perspective of applying glaze and coloring on it, the surface heterogeneous layer is preferably white. In terms of making the surface heterogeneous layer white, the total content of transition metal elements and rare earth elements in the surface heterogeneous layer is preferably 1.5% by mass or less, more preferably 1.2% by mass or less, still more preferably 0.9% by mass or less, particularly preferably 0.7% by mass or less in terms of oxide conversion.

[0055] The measurement of the total content of transition metal elements and rare earth elements in the surface heterogeneous layer is obtained by the following method for the surface heterogeneous layer after distinguishing the shaped body main body and the surface heterogeneous layer by the above method. The composition analysis can be carried out by scanning electron microscope - energy dispersive X-ray spectroscopy (SEM-EDX), electron probe micro analyzer, etc. Specifically, the shaped body including the surface heterogeneous layer and the shaped body main body is embedded in resin. This resin is polished and finally mirror-polished to expose the interface between the shaped body main body and the surface heterogeneous layer. The composition analysis of the shaped body main body and the surface heterogeneous layer is carried out from near this interface.

[0056] The surface heterogeneous layer only needs to be provided on at least a part of the surface of the shaped body main body, can be formed in the area where glazing is planned, and can also be formed in other areas where glazing is not performed. In view of the fact that glazing is for the purpose of improving the design, the surface heterogeneous layer is preferably provided on the visible surface of the shaped body main body, and specifically, it is preferably provided in any area other than the bottom. The surface heterogeneous layer is preferably provided on at least a part of the surface with the largest area, and may also be provided in the entire area of the surface with the largest area.

[0057] Examples of the shaped body with a glaze layer as the final product include plate-shaped articles, dish-shaped (shallow dish-shaped) articles, bowl-shaped (deep dish-shaped) articles, articles with lids, plate-shaped articles, pots, statues, frame structures, etc. In the case where the shaped body with a glaze layer is a plate-shaped article or a dish-shaped (shallow dish-shaped) article, the one surface with the largest area is often the upper surface. It is preferable to provide a surface heterogeneous layer on at least a part of the upper surface of the shaped body main body, and it may be provided over the entire area of the upper surface of the shaped body main body. Also, in the case where the shaped body with a glaze layer is a plate-shaped article, it may be provided on a surface other than the surface with the largest area, for example, at least a part of the side surface of the shaped body main body. A surface heterogeneous layer may or may not be provided on the lower surface as another surface with the largest area. In the case where the shaped body with a glaze layer is a dish-shaped (shallow dish-shaped) article, a surface heterogeneous layer may or may not be provided on the raised platform disposed on the lower surface. Also, a surface heterogeneous layer may be provided on a part of the raised platform.

[0058] In the case where the shaped body with a glaze layer is a bowl-shaped (deep dish-shaped) article or a pot, the one surface with the largest area is often the outer surface. It is preferable to provide a surface heterogeneous layer on at least a part of the outer surface of the shaped body main body, and it may be provided over the entire area of the outer surface of the shaped body main body. Also, a surface heterogeneous layer may or may not be provided on the inner surface as another surface with the largest area. The one surface with the largest area may be the inner surface. When providing a surface heterogeneous layer on the inner surface, it may be provided on a part of the inner surface or over the entire inner surface. In the case where the shaped body with a glaze layer is a bowl-shaped (deep dish-shaped) article or a pot, a surface heterogeneous layer may or may not be provided on the bottom. When a raised platform is disposed on the bottom, a surface heterogeneous layer may or may not be provided on the raised platform. Also, a surface heterogeneous layer may be provided on a part of the raised platform.

[0059] The article with a lid includes a container part and a lid. When the container part is a dish-shaped (shallow dish-shaped) article, a bowl-shaped (deep dish-shaped) article, or a pot, it is preferable to provide a surface heterogeneous layer in the above-described regions respectively. Regarding the lid, it is preferable to provide a surface heterogeneous layer on at least a part of the outer surface, and it may be provided over the entire area of the outer surface. Also, a surface heterogeneous layer may or may not be provided on the inner surface of the lid. When providing a surface heterogeneous layer on the inner surface, it may be provided on a part of the inner surface or over the entire inner surface.

[0060] In addition, when the shaped body with a glaze layer is a tableware, it is preferable to provide a surface heterogeneous layer at the edge from the viewpoints of improving the mouthfeel and enhancing the strength.

[0061] In the case of a statue, it is preferable to provide a surface heterogeneous layer on at least a part of the outer surface of the shaped body main body, and it may be provided over the entire region of the outer surface of the shaped body main body. When the shaped body with a glaze layer is a statue, a surface heterogeneous layer may be provided at the bottom, but it is not necessary.

[0062] In the case of a frame structure, the surface heterogeneous layer may be provided on a part of the shaped body main body or over the entire surface.

[0063] The surface heterogeneous layer may be a single layer or a multi-layer of two or more layers. In the case where the surface heterogeneous layer is a multi-layer, the numerical values related to the surface heterogeneous layer are the values for the entire multi-layer.

[0064] For the shaped body of the present disclosure, it is preferable that the parameter T represented by the following formula (3) is 0 to 50.0.

[0065] T=(1 - P m )×A m +P m ×A u Formula (3)

[0066] It has been experimentally found that when T is within the range of 0 to 50, the adhesion between the shaped body main body and the surface heterogeneous layer tends to be improved. At the boundary between the shaped body main body and the surface heterogeneous layer, the above-mentioned intermediate layer may exist. The formation state of this intermediate layer is expressed by the parameter T.

[0067] In addition to improving the adhesion between the shaped body main body and the surface heterogeneous layer, from the viewpoint of stress relaxation between the glaze layer and the shaped body, T is more preferably 2.0 or more, further preferably 5.0 or more, particularly preferably 7.0 or more, and extremely preferably 10.0 or more. Also, from the viewpoint of the adhesion between the shaped body main body and the surface heterogeneous layer, T is more preferably 45.0 or less, further preferably 40.0 or less, particularly preferably 37.0 or less, and extremely preferably 35.0 or less.

[0068] Volume V of the shaped body main body 2 Volume V of the surface heterogeneous layer with respect to 1 Volume ratio: V 1 / V 2 is preferably 1×10 -9 ~1. V 1 / V 2 When it is in the range of 1×10 -9 ~1, the color development property and glossiness after glazing tend to improve. From these viewpoints, V 1 / V 2 is more preferably 1×10 -6 or more, even more preferably 1×10 -5 or more, particularly preferably 5×10 -4 or more. Also, V 1 / V 2 The upper limit value of is not particularly limited, but from these viewpoints, 1×10 -1 or less is more preferable, 5×10 -2 or less is even more preferable, and 2×10 -2 or less is particularly preferable.

[0069] Volume V 1 and V 2 The measurement methods of are as follows. Place the shaped body in a container with a volume V 0 that can completely submerge it, weigh the total mass, then fill the container with water until it is full and weigh it, and obtain the volume V of the water poured into the container from the difference in mass w . Here, V 1 =V 0 -V w is. Next, measure the surface area of the surface where the surface heterogeneous layer exists in the shaped body main body with a 3D scanner or the like. The 3D scanner to be used is not particularly limited, and examples include the handy 3D scanner OPT MX manufactured by Opt Co., Ltd. Multiply the obtained surface area by T u measured separately to obtain V 2 .

[0070] <Shaped body with glaze layer> The shaped body with a glaze layer of the present disclosure has the shaped body of the present disclosure and a glaze layer provided on at least a part of the surface heterogeneous layer in the shaped body. The shaped body of the present disclosure is excellent in dimensional accuracy, and the occurrence of defects in the glaze layer generated when forming the glaze layer on the shaped body is suppressed. Therefore, the occurrence of defects in the glaze layer when it is a shaped body with a glaze layer is suppressed. Specifically, the shaped body with a glaze layer of the present disclosure is excellent in dimensional accuracy, excellent in the color development property and glossiness (lustre) of the glaze layer, excellent in the adhesion between the shaped body and the glaze layer, or exhibits both of these effects.

[0071] Since the occurrence of defects in the glaze layer of the shaped body with a glaze layer of the present disclosure is suppressed, it is excellent in design. Therefore, the shaped body with a glaze layer of the present disclosure is suitably used for tableware, artworks, etc. Examples of tableware include shallow dishes, deep dishes, bowls, covered bowls, ceramic plates, etc. Examples of artworks include pots, statues, frame structures, etc.

[0072] <Manufacturing method of the shaped body> The manufacturing method of the first shaped body of the present disclosure includes forming a surface heterogeneous layer on at least a part of the surface of the shaped body main body including an aggregate and a binder that binds the aggregate, and the surface heterogeneous layer has a pore median diameter D u of 0.1 μm to 15.0 μm, and the product of the open porosity P u of the surface heterogeneous layer and the average thickness T u [mm] of the surface heterogeneous layer is 0.01 mm to 0.30 mm, and the pore median diameter D u of the surface heterogeneous layer is smaller than the pore median diameter D m of the shaped body main body. The manufacturing method of the second shaped body of the present disclosure includes forming a surface heterogeneous layer on at least a part of the surface of the shaped body main body including an aggregate and a binder that binds the aggregate, and the parameter A m represented by the above formula (1) for the surface heterogeneous layer is smaller than the parameter A u represented by the above formula (2) for the shaped body main body. Each parameter in the manufacturing method of the shaped body of the present disclosure has the same meaning as each parameter described for the above-shaped body.

[0073] The manufacturing method of the shaped body main body is not particularly limited, and known methods can be appropriately applied. For example, there is a method of preparing a composition in which a powdery precursor containing a binder as a curing component and an aggregate are mixed, and manufacturing the shaped body main body with a 3D printer using this composition. The powdery precursor may further contain a curing acceleration component. As the curing acceleration component, a lithium salt or quicklime is preferable. Examples of the lithium salt include lithium carbonate, lithium hydrogen carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium oxalate, etc. The curing acceleration component may be used alone or in combination of two or more. Illustrating the mixing ratio of the aggregate and the powdery precursor, the ratio of aggregate:powdery precursor is preferably approximately 65 - 95 mass%:5 - 35 mass%. For example, when using Lunamos (registered trademark) manufactured by Kao Quaker Co., Ltd. as the aggregate and alumina cement (curing component) and lithium carbonate (curing acceleration component) as the powdery precursor, the ratio of aggregate (Lunamos (registered trademark)):powdery precursor (alumina cement + lithium carbonate) may be mixed at a ratio of approximately 65% - 75 mass%:25 - 35 mass%. When using FINE-Bz (trade name) manufactured by AGC Ceramics Co., Ltd. as the aggregate and alumina cement (curing component) and lithium carbonate (curing acceleration component) as the powdery precursor, the ratio of aggregate (FINE-Bz):powdery precursor (alumina cement + lithium carbonate) may be mixed at a ratio of approximately 80 - 95 mass%:5 - 20 mass%.

[0074] The surface heterogeneous layer may be formed by coating or the like as a separate process after forming the shaped body main body, or may be formed in a series of processes from the formation of the shaped body main body. As a method of forming in a series of processes, there is a method of forming the shaped body main body using a powder lamination type 3D printer, and then continuously laminating and forming the surface heterogeneous layer.

Example

[0075] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Here, Examples 1 to 19 are examples, and Examples 20 to 24 are comparative examples. "%" in Tables 1 to 3 represents "mass %". "Specific metal oxide" in Tables 1 to 3 refers to "oxides of transition metal elements and rare earth elements".

[0076] (Examples 1 to 5) Approximately 70.0 mass % of Kao Corporation's Lunamos (registered trademark), which had been pre-classified with a 300 - 635 mesh sieve, was used as an aggregate (spherical particles), about 28.0 mass % of Asahi alumina cement No. 1 manufactured by AGC Ceramics Co., Ltd., and about 1.0 mass % of lithium carbonate (special grade) manufactured by Kishida Chemical Co., Ltd. were mixed to prepare a composition. Using this composition, a 50 mm × 50 mm × 20 mm molded body was produced by Projet660 manufactured by 3D Systems. The molded body was cured for 24 hours or more in an environment of 22°C and 40% relative humidity, then immersed in a colloidal silica dispersion to impregnate the molded body with colloidal silica, and then dried for 2 hours or more. The obtained dried body was heat-treated at 1290°C for 3 hours using a high-temperature-rising electric furnace NH-2045D (hereinafter abbreviated as the electric furnace) manufactured by Motoyama Co., Ltd. to obtain a shaped body main body.

[0077] Clay (1) was pulverized in water so that the average particle size was about 8 μm, and a clay slurry with a solid content concentration of 50 mass % was prepared as a surface heterogeneous layer forming material. Clay (1) is a mixture of minerals such as quartz, sericite, and kaolin. The entire shaped body main body was immersed in this clay slurry and then pulled out. The immersion time of the shaped body main body in the clay slurry was 10 seconds in Examples 1 to 3, 5 seconds in Example 4, and 30 seconds in Example 5. Thereafter, it was dried at 25°C for 2 days and at 80°C for 10 hours, and finally lightly sintered in an electric furnace at the temperature shown in Table 1 for 30 minutes to obtain a shaped body.

[0078] The entire obtained shaped body was immersed in glaze for glazing, then dried at 25°C for 1 day and at 80°C for 5 hours, and finally heat-treated in an electric furnace at 1300°C to obtain a shaped body with a glaze layer.

[0079] The appearance of the shaped body with the obtained glaze layer was visually observed. The various evaluation criteria are as follows. -Dimensional variation- A: The dimensions of the shaped body with the glaze layer are almost the same as those of the shaped body. F: The dimensions of the shaped body with the glaze layer are significantly reduced compared to those of the shaped body, or the shape of the shaped body with the glaze layer is distorted. -Glassy luster- A: It has a glassy luster and is shiny. F: It has no glassy luster and is not shiny. -Glaze homogeneity- A: The glaze is baked evenly. F: There are irregularities in the thickness of the glaze layer, or the thickness of the glaze layer is overall thin.

[0080] Table 1 shows the composition of the surface heterogeneous layer and the shaped body main body of the shaped body, various measurement results, and the appearance evaluation results of the shaped body with the glaze layer. In Examples 1 to 5, the dimensions of the shaped body with the glaze layer were almost the same as those of the shaped body, the surface of the glaze layer of the shaped body with the glaze layer had a glassy luster, and the glaze was baked evenly.

[0081]

Table 1

[0082] (Examples 6 to 12) A shaped body main body was produced in the same manner as in Example 1, except that about 83.0% by mass of FINE-Bz manufactured by AGC Ceramics Co., Ltd. was used as an aggregate (spherical particles), and about 28.0% by mass of Asahi alumina cement No. 1 manufactured by AGC Ceramics Co., Ltd. and about 0.5% by mass of high-purity lithium carbonate (UF-300: purity 99.60%) manufactured by Honjo Chemical Co., Ltd. were mixed.

[0083] The formation of the surface heterogeneous layer on the surface of the shaped body main body was carried out in the same manner as in Example 1 in Examples 6 to 8, in the same manner as in Example 4 in Example 9, and in the same manner as in Example 5 in Example 10. In Examples 11 and 12, kaolin (2) with a higher kaolin content than kaolin (1) was used. It was pulverized in water to have an average particle size of about 8 μm, and a kaolin slurry with a solid content concentration of 50% by mass was used to form a surface heterogeneous layer. The immersion time of the shaped body body in the kaolin slurry was 15 seconds in Example 11 and 30 seconds in Example 12. Thereafter, it was dried at 25°C for 2 days and at 80°C for 10 hours, and finally lightly sintered in an electric furnace at the temperature shown in Table 2 for 30 minutes to obtain a shaped body. Using this shaped body, glazing, drying, and light sintering were performed in the same manner as in Example 1 to obtain a shaped body.

[0084] Table 2 shows the composition of the surface heterogeneous layer and the shaped body body of the shaped body, various measurement results, and the appearance evaluation results of the shaped body with a glaze layer. In Examples 6 to 12, the dimensions of the shaped body with a glaze layer were almost the same as those of the shaped body, and the surface of the glaze layer of the shaped body with a glaze layer had a glassy luster, and the glaze was baked evenly.

[0085]

Table 2

[0086] (Examples 13 to 19) Taking about 93.9% by mass of FINE - Bz manufactured by AGC Ceramics Co., Ltd. as the aggregate (spherical particles), about 5.0% by mass of high - alumina cement (Al 2 O 3 about 70% by mass, CaO about 28% by mass) and about 0.1% by mass of lithium carbonate (special grade) manufactured by Kishida Chemical Co., Ltd., a shaped body body was produced in the same manner as in Example 1 except for this.

[0087] The formation of the surface heterogeneous layer on the surface of the shaped body body was carried out in the same manner as in Example 1 in Examples 13 to 15, in the same manner as in Example 4 in Example 16, and in the same manner as in Example 5 in Example 17. Example 18 was carried out in the same manner as Example 11, except that the immersion time was changed to 3 seconds to form a surface heterogeneous layer on the surface of the shaped body. Example 19 was carried out in the same manner as Example 12 to form a surface heterogeneous layer on the surface of the shaped body. FIG. 1 shows a backscattered electron image obtained by observing the cross section of the shaped body of Example 18 with a scanning electron microscope (SEM).

[0088] Thereafter, it was dried at 25°C for 2 days and at 80°C for 10 hours, and finally lightly sintered in an electric furnace at the temperature shown in Table 3 for 30 minutes to obtain a shaped body. Using this shaped body, glazing, drying, and light sintering were carried out in the same manner as in Example 1 to obtain a shaped body.

[0089] Table 3 shows the composition of the surface heterogeneous layer and the shaped body main body of the shaped body, various measurement results, and the appearance evaluation results of the shaped body with a glaze layer. In Examples 13 to 19, the dimensions of the shaped body with a glaze layer were almost the same as those of the shaped body, and the surface of the glaze layer of the shaped body with a glaze layer had a glassy luster, and the glaze was baked evenly.

[0090]

Table 3

[0091] (Examples 20 to 23) A shaped body main body was produced in the same manner as in Example 13. In Examples 20 and 21, a surface heterogeneous layer was formed on the surface of the shaped body main body in the same manner as in Example 1. In Example 22, a surface heterogeneous layer was formed on the surface of the shaped body main body in the same manner as in Example 1, except that the immersion time was changed to 1 second. In Example 23, a surface heterogeneous layer was formed on the surface of the shaped body main body in the same manner as in Example 1, except that the immersion time was changed to 60 seconds. Thereafter, it was dried at 25°C for 2 days and at 80°C for 10 hours, and finally lightly sintered in an electric furnace at the temperature shown in Table 4 for 30 minutes to obtain a shaped body. Using this shaped body, glazing, drying, and light sintering were carried out in the same manner as in Example 1 to obtain a shaped body.

[0092] Table 4 shows the composition of the surface heterogeneous layer and the shaped body main body of the shaped body, various measurement results, and the appearance evaluation results of the shaped body with a glaze layer. The surface of Example 20 had a generally glassy luster, but there was unevenness in the thickness of the glaze layer, and the desired appearance could not be obtained. The surface of Example 21 had no glassy luster and the thickness of the glaze layer was also generally thin, and the desired appearance could not be obtained. The surfaces of Examples 22 and 23 had a generally glassy luster, but there was unevenness in the thickness of the glaze layer, and the desired appearance could not be obtained.

[0093]

Table 4

Claims

1. A shaped body main body including an aggregate and a binder for binding the aggregate, and a surface heterogeneous layer provided on at least a part of the surface of the shaped body main body. The pore median diameter D of the surface heterogeneous layer ｕ is 0.1 μm to 15.0 μm, The open porosity P of the surface heterogeneous layer ｕ and the average thickness T of the surface heterogeneous layer ｕ [mm] satisfy a product of 0.01 mm to 0.30 mm, The pore median diameter D of the surface heterogeneous layer ｕ is a shaped body in which the pore median diameter D ｍ is smaller than that of the shaped body main body.

2. The average thickness T ｕ The shaped body according to claim 1, wherein the average thickness T is from 0.01 mm to 0.55 mm.

3. Said D ｍ and said D ｕ The difference between: D ｍ -D ｕ is 5.0 μm to 49.0 μm. The shaped body according to claim 1 or 2

4. Parameter A represented by the following formula (1) for the shaped body main body ｍ is smaller than Parameter A represented by the following formula (2) for the surface heterogeneous layer ｕ The shaped body according to any one of claims 1 to 3 A ｍ = 0.5[SiO ２ ｍ - 0.2[ZrO ２ ｍ - 5[TiO ２ ｍ + 5[R ２ O] ｍ + 2[ReO] ｍ - 0.2[Al ２ O ３ ｍ ... Equation (1)​​​​ A ｕ = 0.5[SiO ２ ｕ - 0.2[ZrO ２ ｕ - 5[TiO ２ ｕ + 5[R ２ O] ｕ + 2[ReO] ｕ - 0.2[Al ２ O ３ ｕ ... Equation (2)​​​​ Here, [SiO ２ , [ZrO ２ , [TiO ２ , and [Al ２ O ３ are numbers representing the amounts of SiO ２ , ZrO ２ , TiO ２ , and Al ２ O ３ respectively in terms of mass percentage based on oxides. [R ２ O] is a number representing the total amount of Li ２ O, Na ２ O, and K ２ O in terms of mass percentage based on oxides. [ReO] is a number representing the total amount of MgO, CaO, SrO, and BaO in terms of mass percentage based on oxides. Each with a subscript m represents the amount contained in the shaped body main body, and each with a subscript u represents the amount contained in the surface heterogeneous layer.

5. A shaped body main body including an aggregate and a binder for binding the aggregate, and a surface heterogeneous layer provided on at least a part of the surface of the shaped body main body. Parameter A represented by the following formula (1) for the shaped body main body ｍ is a shaped body that is smaller than Parameter A represented by the following formula (2) for the surface heterogeneous layer ｕ ​ A ｍ = 0.5[SiO ２ ｍ - 0.2[ZrO ２ ｍ - 5[TiO ２ ｍ + 5[R ２ O] ｍ + 2[RO] ｍ - 0.2[Al ２ O ３ ｍ ... Equation (1)​​​​ A ｕ = 0.5[SiO ２ ｕ - 0.2[ZrO ２ ｕ - 5[TiO ２ ｕ + 5[R ２ O] ｕ + 2[ReO] ｕ - 0.2[Al ２ O ３ ｕ ... Equation (2)​​​​ Here, [SiO ２ , [ZrO ２ , [TiO ２ , and [Al ２ O ３ are numbers representing the amounts of SiO ２ , ZrO ２ , TiO ２ , and Al ２ O ３ respectively in terms of mass percentage based on oxides. [R ２ O] is a number representing the total amount of Li ２ O, Na ２ O, and K ２ O in terms of mass percentage based on oxides. [ReO] is a number representing the total amount of MgO, CaO, SrO, and BaO in terms of mass percentage based on oxides. Each with subscript m represents the amount contained in the shaped body main body, and each with subscript u represents the amount contained in the surface heterogeneous layer.

6. Said A ｍ and said A ｕ and the open porosity P of said shaped body body ｍ are used, and the parameter T represented by the following formula (3) is 0.0 to 50.

0. The shaped body according to claim 4 or 5. T = (1 - P ｍ ) × A ｍ + P ｍ × A ｕ ... Equation (3)

7. The surface heterogeneous layer contains, based on oxide, 65 to 85% by mass of SiO ２ , 15 to 35% by mass of Al ２ O ３ , 1 to 20% by mass in total of Li ２ O, Na ２ O and K ２ O, and 0.1 to 5% by mass in total of MgO, CaO, SrO and BaO, The shaped body main body contains, on an oxide basis, 1 to 30% by mass of SiO ２ , 40 to 95% by mass of Al ２ O ３ , and 0 to 30% by mass of ZrO ２ The shaped body according to any one of claims 1 to 6.

8. The volume V of the shaped body main body ２ The volume V of the surface heterogeneous layer with respect to １ Volume ratio: V １ / V ２ is 10 －９ The shaped body according to any one of claims 1 to 7, which is from 1 to 1.

9. The shaped body according to any one of claims 1 to 8, wherein the binder includes an inorganic binder.

10. A shaped body with a glaze layer, comprising the shaped body according to any one of claims 1 to 9, and a glaze layer provided on at least a part of the surface heterogeneous layer of the shaped body.

11. The shaped body with a glaze layer according to claim 10, which is used as tableware.

12. The shaped body with a glaze layer according to claim 10, which is used as a work of art.

13. Forming a surface heterogeneous layer on at least a part of the surface of a shaped body main body including an aggregate and a binder for binding the aggregate. The surface heterogeneous layer has a pore median diameter D ｕ of 0.1 μm to 15.0 μm, The open porosity P of the surface heterogeneous layer ｕ and the average thickness T ｕ [mm] of the surface heterogeneous layer satisfy 0.01 mm to 0.30 mm, The pore median diameter D of the surface heterogeneous layer ｕ is smaller than the pore median diameter D ｍ of the shaped body main body, and a method for manufacturing the shaped body

14. Forming a surface heterogeneous layer on at least a part of the surface of a shaped body main body including an aggregate and a binder for binding the aggregate. Parameter A represented by the following formula (1) for the surface heterogeneous layer ｍ is a method for manufacturing a shaped body that is smaller than parameter A represented by the following formula (2) for the shaped body main body. ｕ ​ A ｍ = 0.5[SiO ２ ｍ - 0.2[ZrO ２ ｍ - 5[TiO ２ ｍ + 5[R ２ O] ｍ + 2[RO] ｍ - 0.2[Al ２ O ３ ｍ ... Equation (1)​​​​ A ｕ = 0.5[SiO ２ ｕ - 0.2[ZrO ２ ｕ - 5[TiO ２ ｕ + 5[R ２ O] ｕ + 2[RO] ｕ - 0.2[Al ２ O ３ ｕ ... Formula (2)​​​​ Here, [SiO ２ , [ZrO ２ , [TiO ２ , and [Al ２ O ３ are numbers representing the amounts of SiO ２ , ZrO ２ , TiO ２ , and Al ２ O ３ respectively in terms of mass percentage based on oxides. [R ２ O] is a number representing the total amount of Li ２ O, Na ２ O, and K ２ O in terms of mass percentage based on oxides. [ReO] is a number representing the total amount of MgO, CaO, SrO, and BaO in terms of mass percentage based on oxides. Each subscript with m represents the amount contained in the shaped body main body, and each subscript with u represents the amount contained in the surface heterogeneous layer.

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