JP6099701B2 - Decorative ceramic raw materials and decorative ceramics - Google Patents

Description

The present invention relates to decorative ceramics used as tangible cultural properties, murals, paintings, sculptures, restored or reproduced products of crafts, reproductions, three-dimensional molded articles for decoration, or building materials for decoration of interior and exterior And a decorative ceramic using the raw material.

Conventionally, as a material for expressing tangible cultural properties, murals, paintings, sculptures, etc., the original photographic data to be expressed is color-printed with an inkjet printer or the like on the surface of a support such as paper, cloth, etc. On the back side of the support, silk screen printing is performed with the first pigment using a screen made of a plate for reversing and printing the original, and further, the surface is subjected to the same or similar processing as the original, and the undercoat is applied. A material backed by a base material to which a metal is applied and a manufacturing method thereof are known (see Patent Document 1). In this example, the base material is a material base.
It can also be used as a base for materials for expressing tangible cultural properties, murals, paintings, sculptures, etc., from the group consisting of rhyolite, feldspar rock, tribute, slate, nacre, obsidian and expanded clay. There is known a porous ceramic formed by firing and foaming a mixture containing at least one selected 100 parts by weight as a main component (see Patent Document 2).

JP 2011-161863 A Japanese Patent Publication No. 4-15196

However, any of the above-mentioned conventional materials has a structure in which a soft molding layer having excellent moldability and expressibility is fixed on a high-strength substrate, and thus different material layers must be fixed and solidified. For this reason, when it is applied to a large-sized product or an elaborate three-dimensional molded product, the layers may be separated or cracks and cracks may occur due to the difference in heat shrinkage or moisture content of each material layer. In particular, when going through a firing step, the layers are easily separated or cracks and cracks are likely to occur. Further, even after molding, the layers may be separated due to deterioration over time or cracks may be generated on the surface, resulting in lack of storage stability.
Therefore, the present invention is intended for decorative ceramics having a molding layer on the substrate for expressing a representation object, for example, for obtaining a relatively large restored product, reproduced product, or duplicate product with high accuracy. It is a raw material, and the molding layer can express the object to be expressed with high accuracy in terms of shape, color, texture, etc., but has excellent heat resistance and fixability to the substrate, and molding the surface It is an object of the present invention to provide a raw material for decorative ceramics excellent in state retention and to provide a method for manufacturing a raw material for such decorative ceramics.
In addition, the present invention is a decorative ceramic using the raw material for the decorative ceramic according to the present invention, and the object to be expressed is expressed with high accuracy in shape, color, texture, etc., and has excellent heat resistance and fixing property to the substrate. It is an object of the present invention to provide a decorative ceramic that has excellent retention of the molded state of the surface.

In order to solve the above problems, the present invention provides the following raw materials for decorative ceramics and decorative ceramics using the raw materials.

1. Decorative ceramics raw material and decorative ceramics The decorative ceramic raw material of the present invention has the following basic structure:
A substrate having at least one layer-forming surface having fine irregularities;
A molded ceramic layer (excluding one made of a glassy coating) formed on the layer-forming surface of the substrate, and a raw material for decorative ceramics integrally formed,
Of the molding layer, at least the layer portion adjacent to the substrate is mainly composed of petalite, and is fixed along the fine irregularities of the substrate ,
At least the boundary surface adjacent to the substrate of the molding layer has a particle size distribution with a mode diameter of more than 10 μm and a D50 median diameter of more than 10 μm. The particle size distribution is a particle size logarithm with the horizontal axis as the particle diameter and the vertical axis as the frequency. In the frequency graph, it is shown as a dispersion curve having two or more peaks protruding in the vertical axis direction.
As described above, petalite having the characteristics described below is used as the main component of at least the layer portion adjacent to the base of the molding layer , and the molding layer is formed and fixed along the fine irregularities on the substrate. As a result, the molded layer has good fixability that is difficult to separate from the substrate.
The fine irregularities on the substrate layer forming surface are basically irregularities having an irregularity height of about 10 μm to 900 μm, which are formed on the substrate surface portion by firing a kneaded body of the substrate as a raw material of the substrate. That is.
The decorative ceramic according to the present invention is obtained by subjecting the raw material according to the present invention having the above basic configuration to a predetermined finishing treatment. Here, the finishing process, glazing treatment, coloring treatment, at least one processing of the transfer process of the pattern, or even means a process including a finishing firing.

2. A decorative ceramic raw material and a method of manufacturing the decorative ceramic using the raw material The decorative ceramic raw material of the present invention basically includes:
A substrate forming step of obtaining a molded body of a plate-like substrate by first firing a kneaded body of a substrate that is a raw material of the substrate;
A banking step of embedding a clay-like kneaded body obtained by kneading a powder mixture containing petalite and water, which is a raw material of the molding layer, on one side of the substrate;
A surface layer separation step of leaving the embankment of the kneaded body and separating the surface layer from the embankment,
including.
The fine irregularities on the substrate layer forming surface are basically irregularities having an irregularity height of about 10 μm to 900 μm, which are formed on the substrate surface portion by firing a kneaded body of the substrate as a raw material of the substrate. That is.
Moreover, the decorative ceramic according to the present invention includes a step of performing a predetermined finishing process on the raw material in addition to the step of obtaining the raw material of the decorative ceramic by the raw material manufacturing method according to the present invention having the above basic configuration. . Here, the finishing process means at least one of a glazing process, a coloring process, and a transfer process of a pattern to be expressed, or a process including finish firing.

The method for producing the decorative ceramic raw material will be further described. The embankment process results in an embankment state in which embankment is formed on the ground surface, and the embankment state in the embankment state is naturally formed in the surface layer part and the lower layer part by the surface layer separation process. A separated layer state is obtained.
In a typical example of the method for producing a raw material for decorative ceramics according to the present invention, the surface layer portion in a layer-separated state is removed by the surface layer removing step and only the lower layer portion (including the case where it is a part of the lower layer portion) is removed. Then, by the firing step, the lower layer portion in the state of removing the surface layer excluding the surface layer portion becomes a fired state in which the molded layer is fixed on the substrate. In this manufacturing method, a layer is not formed simply by embankment and firing, but a molded layer is formed through a surface separation state after the embankment step and a firing step after a surface layer removal state.
In the surface layer separation step, the lower layer portion that has been separated and settled out of the kneaded body is fixed on the layer forming surface of the substrate, and in the surface layer removal step, the lower layer portion is exposed on the upper surface of the kneaded body portion. Here, the lower layer portion of the kneaded body which has been separated and settled has a relatively rough uneven solidified layer surface as shown in, for example, the enlarged micrograph of FIG. 6 by subsequent firing, and the surface layer shown in the enlarged micrograph of FIG. Compared to the relatively flat solidified layer surface when fired without removing the part, the layer surface roughness is clearly different. Due to this relatively rough uneven layer surface, the upper part of the molding layer provides a further fixing layer that may be additionally formed on the molding layer, and good fixability such as a coloring agent or glaze. Further, the lower part of the molding layer exhibits good fixability with respect to the base layer forming surface.

(About Petalite)
In the above-mentioned raw materials for decorative ceramics and decorative ceramics according to the present invention, and methods for producing them,
Petalite is a monoclinic mineral of silicate, also called feldspar or petalite, and has a chemical composition of LiAlSi4O2. Petalite generally has a high thermal shock resistance and a low thermal expansion property.
(Meaning of the main agent)
Further, in the present invention, the “main agent” means a blending component having the highest blending weight ratio among all other blending components except water.

Hereinafter, the matter regarding the raw material of the decorative ceramic of the present invention, the decorative ceramic, and the manufacturing method thereof will be described by way of example.
First, in the raw material of decorative ceramics and decorative ceramics of the present invention and a method for producing the same,
The substrate is water-absorbing material that is preliminarily fired and molded by first firing before molding of the molding layer, for example. As a typical example, there can be mentioned one made of a fired plate material having water absorption.
In the molding layer, a kneaded body obtained by kneading a powder mixture containing petalite as a main ingredient and water is in a state where water is absorbed by the substrate on the layer forming surface of the substrate (water absorption state), and this state (water absorption state) Preferably, it is made of a fired material fired together with the substrate by second firing at a firing temperature lower than that of the first firing.
The kneaded body is obtained by kneading a powder mixture and water into a clay, and becomes a molded layer solidified by second firing. During the second firing or before the second firing, the kneaded body is embanked and allowed to stand so that the moisture of the kneaded body is absorbed by the water-absorbing substrate, and the fine uneven portions of the substrate are absorbed. It becomes a state when it is thrown (hereinafter simply expressed as “throwed / throwed”). In this way, the clay-like kneaded body is water-absorbed and fired together with the fired and molded substrate in the thrown state, thereby forming a molded layer in close contact with the substrate.

More specifically, the decorative ceramic raw material is, for example, a clay-like kneaded body obtained by kneading a powder mixture and water at a predetermined thickness on one side of a substrate formed into a plate shape by first firing. It is a raw material for decorative ceramics having a molded layer obtained by embankment and second firing the embankment at a temperature lower than the first firing temperature.
The substrate is, for example, in a state of a plate-shaped molded body before embankment of the kneaded body, and has a water absorption rate of 0.1% to 60%,
The molding layer formed on the substrate may be only one molding layer, but a plurality of molding layers (second molding layer, third molding layer,...) And the like described later are formed. Layers may be formed. In any case, among the layers other than the base material, at least the molding layer formed adjacent to the base material is at least 40 w (weight: refers to weight; hereinafter the same)% or more 75 w in the state of the dehydrated final molded body. % Or less is preferable.

One of the main features of the decorative ceramic raw material, the decorative ceramic, and the manufacturing method thereof of the present example is that the kneaded body containing petalite as a main ingredient is fixed as a molded layer by firing.
Here, “mainly containing petalite” means that the content of petalite in the kneaded body before firing is adjusted so that it contains 40 w% or more and 75 W% or less of petalite in the state of the final molded body that has been fired and dehydrated. Say. The kneaded body kneaded with petalite as the main component so as to contain 40 w% or more and 75 W% or less of petalite in the dehydrated final molded body is melted on the substrate by firing (second firing in the examples described later). It solidifies and becomes a molded layer having excellent heat resistance and fixability. The kneaded body is embanked on the substrate after the first firing molding in a clay state, and is fired together with the substrate (second firing) to melt and solidify into the substrate, thereby forming a fine uneven portion on the surface material of the substrate. The molded layer is integrated with the substrate in the thrown state. This molded layer has excellent fixability to the substrate, and the layer surface may be warped or separated from the substrate by drying and firing after the formation of the molded layer (after the second firing in the examples described later). Absent.
In addition to the above, the kneaded body preferably further has a moisture content of 15% or more (preferably 17% or more) and 50% or less. By firing the kneaded body adjusted for water content as described above together with the substrate (second firing in the examples) to form a molded layer, the overall linear expansion coefficient immediately after the first firing (second firing) of the kneaded body Is suppressed to 3.0 [× 10 ⁻⁶ / K] or less.

(Critical significance)
In the case where the kneaded body, which is the material of the molding layer on the substrate, is not mainly composed of petalite, or when the substrate does not have water absorption, drying and second firing, or subsequent, for example, third firing, 4th firing ... (3rd firing in the case of forming a molding layer, 4th firing ...) Shrinkage / deformation causes overall cracking or separation at the layer boundary of the molding layer There is a risk that. In particular, cracking is likely to occur when the blend ratio of petalite in the powder mixture of the kneaded body is less than 40 w%, or when the final blend ratio of the molded layer after molding is less than 40 w%. It becomes. Since the substrate is a pre-fired molded body that has been first fired in advance, most of the shrinkage has been completed in advance during the second firing. For this reason, it does not shrink | contract much more by the 2nd baking lower than a 1st baking temperature, and an excessive shrink deformation can be prevented by baking with the shaping | molding layer ... which uses a petalite as a main ingredient. Further, when the substrate does not maintain an appropriate water absorption rate, for example, when the water absorption rate of the substrate is less than 0.1%, the fixing property between the substrate and the kneaded body is poor, and cracks and cracks occur after firing. On the other hand, when the water absorption rate of the substrate exceeds 60%, for example, when it is too high, such as 65% or more, when the kneaded body that is the material of the molding layer is dried or during the second firing, or the subsequent third firing. If the water is excessively sucked from the kneaded body at times, the strength of the substrate is low and the durability is insufficient.

In the above-mentioned decorative ceramic raw material, decorative ceramic, and method for producing the same, the linear expansion coefficient of the whole integral member composed of the substrate and the molded layer after the second firing is 1.0 [× 10 ⁻⁶ / K] or more and 5.5 [× 10 ⁻⁶ / K] or less is preferable.
As described above, the molded layer is well fixed on the substrate, and the molded substrate and the molded layer are integrated with each other after molding (an additional layer should be formed on this member in the case of raw materials) In both cases, the linear expansion coefficient of the entire member is 1.0 [× 10 ⁻⁶ / K] or more and is suppressed to 5.5 [× 10 ⁻⁶ / K] or less. Further, peeling or separation due to expansion of each layer is difficult to occur. On the other hand, the linear expansion coefficient of the whole member after the second firing is too small than 1.0 [× 10 ⁻⁶ / K], or the linear expansion coefficient of the whole member after the second firing is 5.5 [× 10 ^−6]. If it is larger than / K], the layer surface may be warped and deformed during the subsequent finish firing, or the substrate and the molded layer may be separated.

  In addition to the above, or separately from the above, the kneaded body that is embanked adjacent to the substrate is, for example, in a clay-like state before the second firing, at least petalite, an inorganic peptizer, water, (That is, a “kneaded body obtained by kneading a powder mixture containing at least petalite and an inorganic peptizer” together with water). According to this example, the powder mixture containing petalite can be dispersed relatively uniformly in water by blending the inorganic peptizer. As a result, the kneaded body is melted and solidified in the base material in the second firing, and can be integrated in a state where it is cast on the fine irregularities of the surface material of the base material, and uniformly molded with a high blending ratio of 40 w% or more of petalite. The layer settles well on the substrate. However, the present invention is not intended to limit the present invention to those provided with these or any of these elements.

  Further, in any of the above-mentioned decorative ceramic raw materials and decorative ceramics and a method for producing the same, the kneaded body that is embanked adjacent to the base is, for example, at least petalite in a clay state before the second firing. A small amount of inorganic peptizer, and a clay material, and the kneaded body is separated into layers in a state of being embanked on the substrate before the second firing, so that the surface layer portion containing moisture is the lower layer It is preferable that the surface layer is separated at the upper part of the part.

The kneaded body is, for example, “peterite having a high blending ratio of 40 w% or more and a clay material (bath clay, rhostone, or ceramic stone) of 5 w% or more and 35 w% or less. The same)) and a small amount of a powder mixture containing at least a small amount of an inorganic peptizer "and a kneaded body kneaded with water. By leaving the kneaded body to stand still, a fine particle having a particle size of less than 100 µm contained in the clay material The particles are separated on the front side of the kneaded body as a surface layer portion having a high water content. When the surface layer part containing moisture is separated from the lower layer part to form the surface layer part, the fine particle content in the remaining lower layer part becomes extremely small. For this reason, the molded layer after drying and firing is less likely to be cracked or chipped. The surface layer portion is preferably composed of a particle size distribution in which the median diameter of D50 is 50% or less. Further, when the particle size is displayed as a frequency distribution, the surface layer portion is in the range of 1 μm to 100 μm, and more specifically, 1 μm to 20 μm. It is preferable to have a maximum peak value (ie, mode diameter) within the range .

Further, in any of the above-mentioned decorative ceramic raw materials and decorative ceramics and a method for producing the same, the molding layer is formed by removing only the lower layer portion remaining by removing the surface layer portion of the kneaded body embanked on the substrate. It is preferable that it consists of the 2nd baking body of the lower layer part which carried out 2nd baking.
According to the above, since the remaining removed surface is composed of the lower layer portion and the molding layer is composed of only the lower layer portion, it has excellent shape stability, or upper layer fixability when further upper layer is added Even better.

  For example, when the surface layer portion remains without being removed, the surface layer portion on the surface is warped and deformed, resulting in non-uniform surface properties. Further, in any of the above-mentioned decorative ceramic raw materials and decorative ceramics and a method for producing the same, an additional molding layer or a finishing layer may be formed on the molding layer. In some cases, microbubbles called pinholes may be generated due to poor fixability. On the other hand, if the molding layer is composed only of the lower layer portion by removing the upper layer portion of the molding layer, the surface properties are relatively uniform, so that an additional molding layer or finishing layer is formed on the molding layer. Fixation with the additional molding layer and finish layer when forming the surface does not deteriorate, and even when finishing treatment such as finishing glaze application is applied to the surface of the layer, minute bubbles called pinholes are generated. Is suppressed. However, the present invention is not intended to limit the present invention to those provided with these or any of these elements. In the examples described later, the surface layer portion is removed by removing the surface layer by the removing means in the surface layer removing step.

Moreover, in any of the above-mentioned decorative ceramic raw materials, decorative ceramics, and manufacturing methods thereof, the substrate is, for example, at least petalite as a main ingredient , or at least petalite as a main ingredient , and the petalite compounding ratio of the base There may be mentioned those in which (PR1) is less than or equal to the petalite blending ratio (PR2) of the molding layer. Further, for example, it is possible to include at least 40 w% or more of petalite, clay material and aggregate, and the petalite blending ratio (PR1) of the base is not more than the petalite blending ratio (PR2) of the molded layer.
According to the above configuration, in any of the above-mentioned decorative ceramic raw materials and decorative ceramics and a method for producing the same, the base material includes a clay material and mainly includes petalite, so that the kneaded body and many of the component compositions are common. Thus, the melt-fixing property by the second baking is excellent. In addition, since the petalite blending ratio (PR1) in the substrate is similar to or less than the petalite blending ratio (PR2) in the molded layer, the substrate can be fired at a higher temperature in the first firing. Further, since the substrate is pre-fired as the first firing before the second firing, it can be obtained as a primary molded article having a small shrinkage rate and excellent shape stability. However, the present invention is not intended to limit the present invention to those provided with these or any of these elements.

Further, in any of the above-mentioned decorative ceramic raw material, decorative ceramic, and method for producing the same, the kneaded body of the substrate before the first firing is further foamed in at least one of the plate forming and the first firing. It is preferable to include a blowing agent.
According to this aspect, since the base after molding includes a foamed portion, a high moisture content can be ensured regardless of the humidity condition of the dry atmosphere, and fine irregularities are formed on the surface and in the vicinity of the surface. When the kneaded body is melt cast, the fixability of the kneaded body becomes extremely good. However, the present invention is not intended to limit the present invention to those provided with these or any of these elements.

Moreover, in the representative example of the manufacturing method according to the present invention described in the above-mentioned “2. The raw material of decorative ceramics and the manufacturing method of decorative ceramics using the raw material”,
A surface layer removing step in which the surface layer part separated from the embankment of the kneaded body is removed to make only the lower layer part,
A firing step in which the lower layer portion of the kneaded body after the surface layer removing step is second-fired together with the substrate to form a molded layer.
Alternatively, in addition, in the decorative ceramic raw material and the decorative ceramic manufacturing method using the raw material, an additional molded layer (second molded layer, third molded layer,. (1) or 2 on the molding layer by embedding a clay-like additional kneaded material kneaded with the powder mixture and water, and performing additional firing (third firing, fourth firing ...). A layer addition step for forming the above additional molding layers (second molding layer, third molding layer,...) May be further included. This corresponds to the manufacturing method of Example 3 described later.
In addition to the above, the following method can also be mentioned as a method for producing the decorative ceramic raw material. That is, it becomes a raw material for the additional molding layer (second molding layer, third molding layer,...) On at least a part of the surface of the remaining kneaded body after the surface layer removing step. This is a method of forming a pre-firing molded layer having a laminated structure through a step of embedding a clay-like additional kneaded material obtained by kneading a powder mixture and water, and then firing them together with a substrate.
Alternatively, the average particle size of the additional kneaded body for forming the additional molded layer is smaller than the average particle size of the kneaded body in the embankment step, and the additional firing temperature (third firing temperature, fourth in the layer addition formation). It is preferable that the firing temperature... Does not exceed the firing temperature of any firing step (pre-baking step) performed before the additional firing step. Still more preferably, each firing temperature in the layer addition formation is lower than the firing temperature in any pre-baking step prior to the layer addition formation.
Alternatively, in the manufacturing method according to the present invention described in "2. Decorative ceramic raw material and decorative ceramic and manufacturing method thereof", at least 40 w% or more of petalite and 75 w% or less of the clay is used in the substrate forming step. It is good also as what carries out the 1st baking of the base material kneaded body which knead | mixed water and an aggregate with water. However, the present invention is not intended to limit the present invention to those provided with these or any of these elements.

  By the layer addition step, the second molding layer, which is an additional molding layer, the third molding layer,... Are formed on the first molding layer which is a molding layer. Here, by the surface layer removal step, the upper layer portion of the molding layer before the layer addition step is in a state in which the surface layer portion of the embankment is removed and the lower layer portion containing a relatively coarse particle size mixture is exposed on the upper surface. Then, by the above layer addition process, an additional kneaded body made of a powder mixture having a relatively small average particle size is embanked in the lower layer portion exposed on the upper surface, thereby making the unevenness of the upper surface of the relatively coarse layer in the lower layer portion finer. The powder mixture of the additional kneaded material enters and has particularly good fixability. In addition, since the third firing temperature is lower than the second firing temperature, the first firing layer, which is the substrate or the molding layer, is also less likely to be warped, cracked or cracked by the third firing, and the final state is excellent in durability. It becomes the raw material of.

  As described above, according to the present invention, for example, for the purpose of obtaining a relatively large restored product, reproduced product, or duplicate product with high accuracy, a molding layer for expressing an expression target is formed on the ground. It is a raw material for decorative ceramics, and the molding layer can express the object to be expressed with high accuracy in shape, color, texture, etc., and has excellent heat resistance and fixability to the substrate. Provided with a raw material for decorative ceramics that does not generate cracks or cracks even after molding or repeated firing after molding, is less prone to layer separation from the substrate, and has excellent surface molding state retention be able to. Further, according to the present invention, the decorative ceramic using the raw material for the decorative ceramic according to the present invention, the object to be expressed is expressed with high accuracy in shape, color, texture, etc., and has excellent heat resistance and desired state. It is possible to provide a decorative ceramic having excellent retention.

FIG. 3 is a flowchart showing a manufacturing method according to the first embodiment. FIG. 6 is a flowchart showing a manufacturing method of Example 2. FIG. 6 is a flowchart showing a manufacturing method of Example 3. Sectional drawing which shows each state in the manufacturing method of Example 1. FIG. Sectional drawing which shows each state in the manufacturing method of Example 2. FIG. Sectional drawing which shows each state in the manufacturing method of Example 3. FIG. The 30 times microscope enlarged photograph of the solidified layer surface after baking which baked without removing the surface layer part of a surface layer separation state. The 30 times microscope enlarged photograph of the solidified layer surface after baking of the lower layer part of a surface layer removal state. The 30-times microscope partial enlarged photograph which shows the base part (1) of the final state of Example 1, and the boundary part of a shaping | molding layer. The graph of the particle size distribution data of the surface layer part after the natural drying of Example 1. FIG. The graph of the particle size distribution data of the lower layer part after the natural drying of Example 1. FIG.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings showing examples of the present invention. In the following description, numerals and symbols in parentheses after each component and the like are reference symbols for the component and the like used for ease of understanding. It is not limited to the form or concept of the embodiments described with reference to FIG.

The embodiment of the present invention is a raw material of decorative ceramics or a finished product of decorative ceramics used for reproduction or restoration of tangible cultural properties, murals, paintings, sculptures, crafts, etc., and is an object to be expressed even though it is an inorganic material The shape, color, texture, etc. can be expressed.
As shown in (h) of FIG. 2 and FIG. 3 and (h3) of FIG. 4, in any of the examples, the base material of the decorative ceramics is formed into a plate shape by the first firing (1) And a molding layer (2) (first molding layer) formed on one side of the substrate (1), or an additional molding layer (second molding) further formed on the molding layer (2). The molding layer (3), the third molding layer (4), ...) are included.

Each embodiment has the following features.
The substrate (1) is a fired plate material having water absorption. Specifically, it was obtained by first firing a base material in a plate-shaped state before embedding the kneaded body (20) which is a forming material of the molding layer (2) at a predetermined first firing temperature. The fired plate-like material has a water absorption rate of 0.1% or more and 60% or less in a plate-like molded state before embankment of the kneaded body (20).
The molding layer (2) (first molding layer) or the additional molding layer (second molding layer (3), third molding layer (4),...) Has at least 40 w% or more of the petalite as the main agent. A clay-like kneaded body (20) formed by kneading a powder mixture containing water and water is embanked on the substrate (1) with a predetermined thickness, and the embanked kneaded body (20) is Obtained by second firing at a temperature lower than one firing temperature. However, the first molded layer is naturally dried after the substrate (1) has absorbed the moisture of the kneaded body (20) during the second firing for the formation or in the embankment state before the second firing. By being forcibly dried, the kneaded body (20) is in a water-absorbed state and dried state that is cast on the fine irregularities on the layer forming surface of the substrate (1). The kneaded body (20) in the water-absorbed state is second-fired together with the substrate (1) on the substrate (1), so that it is thrown along the fine irregularities of the substrate (1) as shown in FIG. And fixed as a molded layer (2) melted and solidified by

Hereinafter, each configuration and the like will be further described.
(Base (1))
The substrate (1) is a fired plate-like material mainly composed of either petalite or clay (including at least one of glazed clay, rholite, or ceramic stone). After the base kneaded body is formed into a plate shape and subjected to forced drying by heat drying, dehumidifying drying, hot air drying, infrared drying, far infrared drying, or a combination drying method of any two or more of these, 1200 ° C to Water absorption by first firing at a first firing temperature in the range of 1250 ° C. and a firing time in the range of about 3 hours to about 10 hours (preferably 5 hours to 10 hours, or 8 hours to 10 hours). It is obtained as a solidified fired plate-like material. On at least one side of the fired plate-like material of the substrate (1), a layer forming surface having fine uneven portions for embedding the kneaded body (20) is exposed. The substrate (1) is also repeatedly fired in the forming layer forming step together with the kneaded body (20) embanked on the layer forming surface as the second firing, or further as the third firing. In the plate-like molded state before embankment of the kneaded body (20), the substrate (1) has a water absorption rate of 0.1% or more and 60% or less, and 1.0 × 10 6 in advance before the second firing. ^{It has} a low expansion coefficient of ⁶ / K or more and 5.5 × 10 ⁶ / K or less.
For example, the forced drying can be performed by drying at a drying temperature in the range of 60 ° C. to 200 ° C. for 1 hour to 24 hours.

As an example of the substrate (1), a clay fired material mainly composed of either petalite or clay can be used as in the examples described later. For example, in Examples 2 and 3 to be described later, petalite is used as the main agent, and at least glazed clay, rhostone or porcelain stone, aggregate such as chamotte, and peptizer are added and mixed with water. The base kneaded body is baked. In Example 1 described later, clay is the main agent, and at least rhostone or porcelain stone, an aggregate such as chamotte, and a peptizer are added to the water. The kneaded body of the base material mixed with is fired. The base kneaded body is further kneaded with a foaming agent or a paste such as methylcellulose as necessary.

(Production method of kneaded body)
As a more specific method for producing a kneaded body, a mixture of at least one kind of glazed clay, rhostone or porcelain stone, and feldspar (petalite or Oohira feldspar) in a predetermined mixing ratio, and powder particles other than water Examples thereof include a method in which a powder mixture made of body materials is purified and a predetermined proportion of water is added little by little while kneading the powder mixture. By first refining the powder mixture other than water, the blending ratio / mixing amount of the main component can be easily adjusted, and by changing the blending ratio between the powder mixture other than water and water, Property and water absorption can be adjusted.

  Moreover, high fire resistance and non-shrinkability can be ensured while lowering the linear expansion coefficient by adding aggregate as one of the mixed materials of the powder mixture. In the present invention, since the base (1) after the first firing is repeatedly fired after the embankment of the kneaded body (20), it is important to ensure fire resistance and non-shrinkage. Alternatively, by adding a foaming agent as one of the mixed materials of the powder mixture, a large number of fine foamed portions can be formed by the first firing to ensure water absorption.

(Molded layer (2))
The raw material of the decorative ceramics has a molded layer (2) made of a solid fired material, which is layered with a predetermined thickness on the layer forming surface of the substrate (1). The molding layer (2) is formed by mixing a kneaded body (20) of a powder mixture (which is a mixture of a plurality of types of powders or granules) containing petalite with water and the first baking. The substrate (1) is embanked on one side and made into a water-absorbed state absorbed by the substrate (1), and then dried by natural drying and / or forced drying. It is a solid layer obtained by second baking at a temperature lower than the temperature of one baking.

  In addition, the said natural drying means standing still for any time of 6 hours-48 hours under normal temperature shade. The forced drying means drying by any one of heat drying, infrared drying, and far infrared drying. As forced drying, for example, heat drying in the range of 1 hour to 24 hours can be performed at a drying temperature in the range of 60 ° C. to 200 ° C.

Of molded layer (2), a layer portion adjacent to the at least base material (1) is intended to base compound petalite, and is fixed in the dehydrated state along the fine uneven part of the green body (1). In this molded layer (2), a kneaded body (20) obtained by kneading a powder mixture containing petalite as a main ingredient and water is formed in a predetermined thickness on the layer forming surface of the substrate (1), and then the kneaded body. (20) 1% or more and 50% or more of the moisture in the substrate is absorbed by the substrate (1), and the substrate (1) is subjected to the second firing at a firing temperature lower than that of the first firing in the absorbed state. It is formed by firing together, is closely formed in a throw-like manner on the fine irregularities on the plate-like substrate (1) without gaps, and has good fixability that is difficult to separate from the substrate (1).

(Petalite)
Petalite is also called feldspar and has a higher proportion of Li ₂ O than other stone materials such as rholite and mullite. Therefore, the water absorption rate is relatively high and the linear expansion coefficient tends to be relatively small (about 2.0 [× 10 ⁻⁶ / K]). By using petalite as the main component of the molding layer (2) and also as the main component of the additional formation layer, the molding layer can maintain a solid state that is well fixed to the substrate (1) after firing.

(Petalite compounding ratio)
When the powder mixture before blending water to form a green body or molding is blended with petalite as the main ingredient , `` with the main ingredient '' means all the ingredients except water Of these, it means that it is the blending component with the highest blending weight ratio. Specifically, the petalite content in the powder mixture is in the range of 40 w% to 75 w%, preferably 45 w% to 60 w%. The particle size of petalite is preferably about 100 μm or more and 300 μm or less. When the particle size of the petalite is too small, the water absorption is small and it is easy to crack, and when the particle size is too large, the surface becomes rough and the moldability deteriorates.

(Kneaded body (20))
The kneaded body (20) in a state before firing of the molding layer (2) is composed of a clay-like kneaded body (20) obtained by kneading a powder mixture containing at least 40 w% or more of petalite and water. The water content of the kneaded water in the kneaded body (20) is 15% or more.
A clay-like kneaded body (20) composed of the kneaded body (20) is embanked on the layer-forming surface of the surface of the base (1) after the first firing, and the second lower than the first firing together with the base (1). By performing the second baking at the baking temperature, the kneaded body (20) is absorbed into the substrate (1) from the layer forming surface, and the dehydrated molding layer (2) is formed into the substrate (1) by drying and baking. Fixed on top.

When the kneaded body (20) kneaded with 40% by weight or more of petalite is melted and solidified on the substrate by firing, a molded layer (2) having excellent heat resistance and fixability is obtained. Due to petalite having a high blending ratio of 40 w% or more, the linear expansion coefficient of the whole integral member of the molded layer (2) and the base (1) after the second firing is 3.0 [× 10 ⁻⁶ / K] or less. Can be suppressed. At the same time, the kneaded body (20) is integrated into the substrate (1) in a state where the kneaded body (20) is cast on the fine irregularities of the surface material of the substrate (1) by melting and solidifying. For this reason, the molding layer (2) having excellent fixability to the substrate (1) without warping and deforming the layer surface due to drying and firing, cracking of the layer itself, or layer separation from the substrate (1). ) Is obtained.

(Method for producing decorative ceramics)
And as a manufacturing method of the decorative ceramic of the Example of this invention, the basic process for obtaining the raw material of the following decorative ceramic at least is included. That is,
A substrate forming step of obtaining a molded body of a plate-like substrate (1) by first firing the substrate kneaded body (20) as a raw material of the substrate (1);
The embankment process (in each figure flow) which embanks the kneaded body (20) which knead | mixed the powder mixture and water used as the raw material of a shaping | molding layer (2) on one side of a base | substrate (1), and makes it into an embankment state (a). "Fill I" process)
Surface layer separation step (b) in which the surface layer portion (212) is naturally separated from the kneaded body (20) that has been left standing in the embankment state (a) and naturally dried for 24 hours or more and then embanked. In the “second drying A” step)
A surface layer removal step (c) in which the surface layer portion (212) separated from the kneaded body (20) that has been embanked is removed to form a surface layer removal state (c) of only the lower layer portion (211) (the “processing” step in each figure flow) When,
The lower layer part (211) of the kneaded body (20) after the surface layer removing step is second-fired together with the substrate (1), and the substrate (1) and the molded layer (2) are integrally formed (h And a firing step (step of “second firing” in each figure flow).

(Layer addition process)
In the manufacturing method of the raw material of the decorative ceramics, a layer addition step can be further provided after the above basic steps, if necessary. The layer addition step includes the steps of “fill II” and “fill III” in FIG. 3B, the step consisting of “fill II” and “third firing” in FIG. 3C, and “fill III” in FIG. 3C and As a process consisting of “fourth firing”, each is shown in a flow chart of a manufacturing method of each example. In the layer addition step, for example, at least a part of the removal surface after the surface layer removal step, a mixture of powder and water, which is a raw material for the additional molding layer (second molding layer (3), third molding layer (4)), The clay-like additional kneaded body (30, 40) kneaded with the clay is fired in the firing step (second firing step), and the additional molding layer (second molding layer (3), as well as necessary, together with the molding layer (2). In response to this, a third forming layer (4)) is further formed. Alternatively, in the layer addition step, for example, at least a part of the firing surface after the surface layer removal step and the firing step is used as a raw material for the additional molding layer (second molding layer (3), third molding layer (4)). The clay-like additional kneaded body (30, 40) obtained by kneading the mixture and water is embanked and third-fired, or further fourth-fired, and an additional molded layer (second molded layer) is formed on the molded layer (2). (3) A step of forming a third molding layer (4)). As a layer addition process, in Example 2 described later, the firing process is performed collectively after embankment for each molding layer / additional molding layer (see FIG. 1B). In Example 3 to be described later, the second and third firing steps for forming each embankment into a forming layer are performed every time embankment for each forming layer is performed (see FIG. 1C). In this way, when performing the banking multiple times by the layer addition process, the layer addition process includes a process in which the additional formation layer is formed by the firing process regardless of whether the firing after the banking is performed collectively or separately. Is completed.

(Finishing process)
In the method for producing decorative ceramics, a finishing step can be further provided after each of the basic steps or after the layer addition step, if necessary. In the finishing process, for example, glaze application and glaze firing of the decorative ceramics obtained as described above, or transfer of coloring and patterns, printing of patterns and the like, and finish firing for fixing them This is a step of forming the finishing layer (5 ′) by, for example. The finishing process may include one or more finishing processes such as surface cutting. Further, it may include a step of making the final state after finish firing and before mounting on the frame and the like. For example, in FIG. 1A (first embodiment), after the second firing, glazing, coloring finish, and finish firing are sequentially performed to obtain a final raw material. Moreover, in FIG. 1B and FIG. 1C (2nd Example, 3rd Example), after the 2nd baking, a glaze and a sinter, transfer and baking, and finish baking are performed in order, and the decorative ceramic of the final state is obtained.

(Ground formation flow, layer formation / coloring flow)
Of the above steps, the substrate forming step belongs to the substrate forming flow shown in the left diagrams of FIGS. 1A, 1B, and 1C. Of the above steps, each step from the embankment step to shipping / mounting belongs to the layer formation / coloring flow shown in the right diagrams of FIGS. 1A, 1B, and 1C.

(Variations such as layer formation and coloring flow)
Among the manufacturing methods described above, there are several variations in the layer formation / coloring flow and the like. Any one of these variations may be selected alone, or a plurality of variations may be selected in combination.

  First, as a first variation such as layer formation / coloring flow, a set of steps from the embankment step to the surface layer separation step may be repeated a plurality of times, and the firing step may be performed after the repetition. For example, in the layer formation / coloring flow shown in FIG. 1B (Example 2), the coarse texture I fill process set, the medium texture II fill process set having an average particle size smaller than the coarse texture, Further, the step of depositing finely ground soil III, which is an average particle smaller than the above, is performed in order, and then the second firing is performed. Specifically, in the flow shown in FIG. 2B, first, as a banking process set of coarse texture I, a surface layer removal process (processing) through a surface layer separation process (second drying A) from a plating process (laying I). Then, forced drying (second drying B) is performed. Next, as a banking process set for medium-sized preparation II, from the filling process (filling II) to the surface layer removal process (process B) of partial molding through a surface layer separation process (third drying) by natural or forced drying Then, a fine filling III filling step (filling III) is carried out, and the soils I, II, and III that have been filled in three layers by these are subjected to second firing.

  Next, as a second variation of the layer formation / coloring flow and the like, a set of a series of steps from the embankment step to the firing step through the surface layer removal step may be repeated several times in order. For example, in the layer formation / coloring flow of FIG. 1C (Example 3) as a layer formation / coloring flow in which a series of process sets is repeated twice, the embedding process using the kneaded body (20) is followed by a surface layer separation process and a surface layer removal process. After the molding layer (2) is solidified and molded by a set of steps up to the second firing step, on the solidified molding layer (2), from the embankment step by the second kneaded body (30) to the surface layer separation step, the surface layer removal step The second molding layer (3), which is an additional molding layer, is solidified by a set of steps up to the third firing step through which the third kneaded body (2, 3) is further solidified. 40) Solidify and mold the third molding layer (4), which is an additional molding layer, by a set of steps from the embankment step to the fourth firing step, and then surface treatment such as glazing and coloring and finish firing. As what to do in order There.

  Among these, FIGS. 2 to 4 show the states from the fill I to the finish firing in the right flow of FIGS. 1A, 1B, and 1C as conceptual diagrams. 2 shows each state of the first embodiment, FIG. 3 shows each state of the second embodiment, and FIG. 4 shows each state of the third embodiment. In any of the Examples, the embankment state (a) in which the kneaded body (20) is embanked on one side of the substrate (1) and the kneaded body (20) in the embankment state (a) are surface-layered (212) by natural drying. Through the layer separation state (b) separated into the lower layer part (211) and the surface layer removal state (c) in which the surface layer part (212) in the layer separation state (b) is removed by the removing means (C), In the embodiment of FIGS. 3 and 4, each layer is formed through a fired state (h, h3) in which a second molding layer (3) to a third molding layer (4) are formed on the removal surface. Will be in the final state.

(Surface layer separation of kneaded body (20))
Particularly in the examples of the present invention, as the surface layer separation step, the embankment kneaded body (20) is allowed to stand and dry before the second firing, whereby the surface layer portion (with a moisture content of 15% or more in the molding layer (2)) ( 212) is characterized in that the surface layer is separated (FIG. 2B). Specifically, the clay-like kneaded body (20) having a moisture content of 15% or more is naturally dried by standing for 24 hours or more after the embankment, so that a relatively high moisture content and a relatively fine particle layer can be obtained. The surface layer portion (212) is naturally separated into the upper layer of the lower layer portion (211) having a relatively low water content and a relatively coarse particle layer (FIG. 2 (b)). By forming the surface layer part (212) into a surface layer part and the lower layer part (211) sinking, the surface of the molding layer (2) is protected during drying, and the content of fine particles in the lower layer of the molding layer (2) is extremely small. Become. For this reason, generation | occurrence | production of a wrinkle is generated after drying and baking of a shaping | molding layer (2), and it will become difficult to produce a chip.

Here, the surface layer part (212) which appeared on the embankment surface by surface layer separation consists of a high water content layer with a water content of 15% or more, and after firing, the surface roughness as shown in the enlarged micrograph of FIG. contain relatively small has a flat layer surfaces, also for example as shown in the particle size distribution graphs in Figure 8, particulate mixture of the following particle size distribution less and D50 median diameter 10 [mu] m mode diameter 10 [mu] m.

The lower portion (211), the surface portion (212) smaller water content than, after firing, as shown in the enlarged photomicrograph of FIG. 6, for example, a layer surface of the relatively large unevenness of the surface roughness, Further, for example, as shown in the particle size distribution graph of FIG. 9, a powder mixture having a particle size distribution with a mode diameter exceeding 10 μm and a D50 median diameter exceeding 10 μm is contained.

(Surface layer removal process)
Next, as a surface layer removing step, the surface layer portion (212), which is a surface film separated from the surface layer, is completely removed from above the lower layer portion (211) by a removing means (C) such as a cutter, a laser knife, or a blast gun for performing a sandblast shot. It is removed (FIGS. 2B to 2C). By removing all the surface layer portion (212) by the surface layer removing step, the non-uniform fine particle layer is removed, and a relatively uniform rough surface of the lower layer portion (211) is exposed. By exposing the rough surface, the molded layer and the finish layer that are further superimposed on the removal surface have excellent fixability. The removal means includes both manual processing and mechanical processing by manual operation or automatic operation.

(First firing, second firing)
In the first firing, a base kneaded body formed into a plate shape and forcibly dried is subjected to a predetermined first firing temperature of 1200 ° C. or higher and about 3 hours to about 10 hours (preferably 5 hours to 10 hours, or The base body (1) of the molded body is obtained in advance before molding the molding layer (2) by firing alone for a predetermined firing time in the range of 8 hours to 10 hours. In the second firing, the kneaded body (20) embanked on the layer-forming surface of the base (1) after the first firing, together with the pre-fired base (1), does not exceed the first firing temperature. And by baking with the baking time which does not exceed said 1st baking temperature, the integral molded object of a base material (1) and a shaping | molding layer (2) is obtained. Here, the firing temperature of the second firing may be lower than the firing temperature of the first firing over the entire firing time, or the firing time of the second firing may be shorter than the first firing time. preferable. Thereby, the total amount of thermal energy applied by the second firing is smaller than the total amount of thermal energy applied by the first firing. Since the substrate (1) is a pre-fired molded body that has been first fired in advance, most of the thermal shrinkage has been completed in advance during the second firing. For this reason, it does not shrink further by the second baking after the first baking. Furthermore, by baking together with the molding layer (2) mainly composed of petalite having a relatively small linear expansion coefficient, both the substrate (1) and the molding layer (2) have relatively small heat shrinkability. For this reason, excessive shrinkage deformation due to heating can be prevented.

<Example 1>
The raw material of decorative ceramics and decorative ceramics of Example 1 and the manufacturing method thereof will be described with reference to FIGS. 1A and 2.
(A) Decorative ceramic raw material and decorative ceramic of Example 1 The decorative ceramic raw material of Example 1 shown in FIGS. 1A and 2 is a plate formed by first drying and subsequent first firing. The base material (1), which is a baked material, is stocked in advance (the left flow in FIG. 1A), and the powder mixture becomes the raw material of the forming layer (2) on the upper surface of the base material (1) cut into a predetermined size A kneaded body (20) formed by mixing and kneading with water (soil preparation I) is formed in one layer (banking I) with a predetermined thickness (right flow (a) and FIG. 2 (a) in FIG. 1A). Then, the surface layer portion (212) is separated from the layer of the kneaded body (20) in the embankment state by natural drying for 24 hours or more, which is the second drying thereafter, and the surface layer portion (212) from the lower layer portion (211) by shaving. (FIG. 1A right flow (c) and FIG. 2 (c)). Thereafter, the remaining lower layer portion (211 (211 ′)) is dried by forced drying (for example, drying within a range of 1 hour to 24 hours at a drying temperature of 60 ° C. to 200 ° C.). It is obtained as a molded layer (22 '(2)) by two firings (h) (FIG. 1A right flow (h) and FIG. 2 (h)).

The decorative ceramic of Example 1 can be obtained by finishing the raw material of the decorative ceramic thus obtained. In this example, as a finishing process, the raw material is glazed, hand-colored and colored by spray coating, and finally finished firing (z). In addition, you may perform the coloring by only one of the said hand coloring and spray application.
Here, the molding layer (2) has a petalite compounding ratio (PR2) of 40% by weight or more and 75% by weight or less in the final state of the molded body in a dehydrated state, and is mainly composed of petalite. However, in Example 1, the substrate (1) does not include petalite.

Specifically, the decorative ceramic raw material of Example 1 is as shown in FIG.
A substrate (1) that does not contain petalite, which is solidified in advance as a plate having water absorbency,
It includes a molding layer (2) containing petalite as a main ingredient, which is layered with a predetermined thickness on a layer forming surface which is the top surface of the substrate (1).
The decorative ceramic using this as a raw material is formed by integrally forming a finish layer (5 ') that is glazed with a predetermined thickness on the upper surface of the molding layer (2) (FIG. 2 (z)).

(Layer boundary part)
In FIG. 7, the elements on larger scale of the layer boundary part of the base body (1) of the final state of Example 1 and a shaping | molding layer (2) are shown. The left figure of FIG. 7 is a 30 times magnified photograph by an electron microscope, and the right figure of FIG. 7 shows a sketch of the layer boundary line of each layer. As shown in FIG. 7, the substrate (1) has fine uneven portions on the entire layer forming surface on which the molding layer (2) is formed. Then a layer portion adjacent to the at least base material (1) of the molded layer (2) is intended to base compound petalite, and along the said fine uneven portions of the matrix (1) (broken line in FIG. 7 right) And is anchored like throwing without gaps.

(Base (1))
The substrate (1) of Example 1 is mainly composed of clay that does not contain petalite , and is made of a calcined plate-like material that is calcined by adding rholite and feldspar. The raw material before firing molding of the base (1) of Example 1 is at least rhostone or porcelain, aggregate such as chamotte, and peptizer, and the foaming agent and paste. And kneaded body (20) obtained by mixing these with water. The substrate (1) of Example 1 is obtained by forming the kneaded body (20) of the substrate into a plate shape, and within a range of approximately 1 hour to 24 hours at a predetermined heating temperature of 60 ° C. or more and 200 ° C. or less as the first drying. After having been dried by heating, solidified having water absorption by passing through a first firing step of first firing at a first firing temperature set in a range of 1200 ° C. to 1250 ° C. and a firing time of about 10 hours. Obtained as a plate-like body (substrate forming step shown in the left flow of FIG. 1A).

(Molded layer (2))
The molding layer (2) of Example 1 was prepared by embedding a kneaded body (20) obtained by kneading water into the first powder mixture containing petalite as a main ingredient on one side of the substrate (1) ( a), the surface layer separation state (b) in which the surface layer portion (212) is separated into the surface layer by natural drying for 24 hours or more which is the second drying, and the surface layer removal state (c) in which the surface layer portion (212) is removed After forming the single layer only in the lower layer (211 (211 ')), the single layer (211 (211')) formed into a dry state with the substrate (1) by forced drying, It is formed by second firing at a second firing temperature in the range of 1150 ° C. to 1200 ° C., which is lower than the firing temperature, and for a firing time of about 10 hours which is substantially the same as the first firing time. The molding layer (2) of Example 1 is a solid layer that contains at least 40 wt% of # 52 petalite and is melted and solidified on the substrate (1) in a dehydrated state.

(Kneaded body (20))
The kneaded body (20), which is the raw material before solidification by the second firing of the molding layer (2), is a clay-like state before the second firing, a powder mixture containing petalite as a main ingredient, and water. It consists of a kneaded clay-like state. The kneaded body (20) is naturally dried for 24 hours or more while being embanked on the layer forming surface of the substrate (1) before the second firing, so that water in the embankment is allowed to flow from the substrate ( 1) It is absorbed in and becomes a water-absorbed state dehydrated to a semi-solidified state. The water content of the kneaded body (20) before embankment constituting the kneaded body (20) is 15% or more and 50% or less, preferably 17% or more and 50% or less. The kneaded body (20) is absorbed into the substrate (1) before the second baking and becomes semi-solidified and dried.

Specifically, the kneaded body (20) before firing and solidifying the molding layer (2) is # 52 petalite 40 w% or more and 75 w% or less, and a clay material (at least 2 out of Sasame clay, rhostone, pottery stone). Seed or higher) 4w% or more and 22w% or less, and 0.05w% or more and 0.4w% or less inorganic peptizer mixed with the powder mixture, so that the water content is 17% or more and 50% or less. It is made of a clay-like material kneaded with. By blending # 52 petalite with clay material consisting of at least two kinds of glazed clay, rhostone and porcelain, it contains coarse particles with a particle diameter range of 5 μm to 100 μm. . When the kneaded body (20) is second-fired to form a molded layer (2), the linear expansion coefficient of the molded layer (2) alone is 0.1 [× 10 ⁻⁶ / K] or more and 1.5 [× 10]. ⁻⁶ / K] or less, preferably 0.2 [× 10 ⁻⁶ / K] or more and 0.8 [× 10 ⁻⁶ / K] or less.

  The kneaded body (20) of Example 1 is obtained by kneading water into a powder mixture and preparing the soil. In the powder mixture before kneading water, which is a raw material of the kneaded body (20), the blending ratio of each mixed component is 55 w% or more and 65 w% or less for petalite, and 0.1 w% for the inorganic peptizer. It is preferable that it is 0.4 w% or less. If it is the said mixture rate, petalite will have sufficient dispersibility in a kneaded body (20), and will have sufficient water content for water absorption to a base material (1). Then, the petalite in the molded layer (2) after molding is melted and solidified with good fixability in a sufficiently dispersed state with a blending ratio of 55 w% to 65 w%.

  The embankment that has become water-absorbed by being absorbed by the substrate (1) is in an anchored state in which the clay-like powder mixture is anchored on the layer forming surface. The kneaded body (20) was second-fired together with the substrate (1) while being in the thrown and water-absorbed state, so that the kneaded body (20) was thrown onto the fine irregularities on the surface of the substrate (1) while melting with the substrate (1). The molded layer (2) is integrated with the substrate (1). The molded layer (2) after the integration is in close contact along the fine irregularities.

  According to the kneaded composition of the kneaded body (20), a fine particle dispersion layer in which the median diameter of D50 contained in the clay material is 10 μm or less or the mode diameter is 10 μm or less by natural drying for 24 hours or more after embankment I. However, it will be separated on the front side of the molding layer (2) as a surface layer portion having a high water content (FIG. 9). On the other hand, the lower layer portion (211) submerged below the surface layer portion (212) is a dispersed layer of coarse particles having a D50 median diameter of more than 10 μm or a mode diameter of more than 10 μm. By forming the surface layer part (212) into a surface layer part and the lower layer part (211) sinking, the surface of the molding layer (2) is protected during drying, and the content of fine particles in the lower layer of the molding layer (2) is extremely small. Become. For this reason, the molding layer (2) is less likely to be cracked, cracked or chipped after being dried and fired.

(B) The raw material of the decorative ceramic of Example 1 and the method of manufacturing the decorative ceramic The manufacturing method of the raw material of the decorative ceramic of Example 1 and the decorative ceramic using the raw material are shown in FIGS. 1A and 2. Thus, it comprises the following steps.
<Ground formation flow shown in the left figure of FIG. 1A>
The base material is prepared (prepared), mixed with water and finely ground to obtain a base kneaded body. After forming the kneaded body of this base into a plate shape and heat drying at 60 ° C. or more and 200 ° C. or less as the first drying, first firing at a first firing temperature within a range of 1200 ° C. to 1250 ° C. A substrate forming flow including a substrate forming step of making a plate-like substrate (1) in a baked state. The substrate (1) is stocked and cut into a predetermined planar shape before the next embankment process.
<Layer formation / coloring flow shown in the right figure of FIG. 1A>
The layer formation flow includes the following steps. That is,
A frame material (F) is attached to the periphery of the substrate (1) cut to a predetermined size, and the powder mixture of the particle raw material and water are kneaded on the layer forming surface which is the upper surface of the substrate (1) (Soil Preparation I ) A clay-like kneaded body (20) that is embanked at a predetermined thickness to form an embankment state (a);
A surface layer separation (second drying A) step in which the embankment with the kneaded body (20) in the embankment state is separated into a surface layer separated state (b) in a semi-solidified state by surface drying by natural drying by standing for 24 hours or more;
The surface layer part (212) separated by the surface layer separation step is removed by the removing means (C) (in this example, a cutting blade), and the upper part of the lower layer part (211) is cut from the surface side with a curved inclined cutting surface. And, as a semi-solidified lower layer portion (221 ') (precursor) that has been processed, a surface layer removal (processing) step that is a processing state and a surface layer removal state (c),
Both the embankment in the semi-solidified state of the surface layer removal state consisting only of the lower layer part (211 (211 ′)) and the base (1) solidified and molded in advance are 1150 ° C. to 1200 ° C. lower than the first firing temperature. A second firing step of obtaining the first molded layer as the molded layer (2) as a stacked solid layer in close contact with the substrate (1) by second firing at a second firing temperature within the range.
And the decorative ceramic of an Example is obtained by giving the following finishing processes to the raw material of the decorative ceramic obtained in this way, for example. That is,
A glazing step of glazing the entire surface of the second molding layer (3), which is an additional molding layer,
A coloring process for coloring the surface of the glaze by manual work or spray application,
A finish firing step in which the whole is collectively fired at a finish firing temperature lower than the second firing temperature to form a finish layer (5 ').

The steps in the manufacturing method of Example 1 will be further described.
(Base formation process)
First, as a substrate forming process that is a substrate forming flow, a clay-like raw material obtained by kneading a powder mixture and water is finely ground in a mill, kneaded, and molded into a plate shape, in a state of 60 to 200 ° C. The first baking is performed at a predetermined heating temperature of about 1 hour to 24 hours, and then first baking is performed at a first baking temperature within a range of 1200 ° C. to 1250 ° C. and a baking time of about 3 hours to about 10 hours. Pre-molded as a solidified material. The firing time for the first firing is preferably set in the range of 5 hours to 10 hours, and more preferably in the range of 8 hours to 10 hours. In this substrate forming step, the sintered material of the plate-like substrate (1) solidified and formed in advance is stocked in a dry state. This baked material serves as a base material, and is formed into a plate shape with a large number of micropores formed by foaming the foaming agent blended in the kneaded body (20) dispersed therein. The substrate (1) has water absorption due to the large number of fine holes. In addition, a fine uneven portion having a maximum height of unevenness of several μm (1 μm or more and 10 μm or less) is formed over the entire layer formation surface on the upper surface.

  The stocked substrate (1) is cut into a predetermined rectangular shape and used in the embankment process described below. Here, the cut dimensions of the substrate (1) are 900 mm × 3000 mm and thickness 20 mm in plan view. The thickness of the substrate (1) is preferably adjusted within a range of about 8 mm to 30 mm, but is not limited to the above range including the thickness and the cut dimensions. The dimensions of the substrate (1) are the same in Examples 2 and 3 described later.

(Filling process)
Next, as the embankment process, along the four sides around the cut substrate (1), stick the rod-shaped frame material (F) made of a non-water-absorbing material so that the upper half projects upward, and A clay-like kneaded body (20) obtained by kneading the powder mixture and water on a layer forming surface which is an upper surface of the substrate (1) in a frame formed by the frame material (F) has a predetermined thickness. Fill with a substantially uniform thickness. After this step, the clay-like kneaded body (20) surrounded by the frame material (F) is filled on the layer forming surface of the solid substrate (1) (FIG. 2 (a)). ). The kneaded body (20) is made of # 52 petalite having a high blending ratio of 40 w% or more and 75 w% or less, and a clay material of 4 w% or more and 22 w% or less (at least two kinds of glazed clay, rhostone, and ceramic stone) ) And an inorganic peptizer of 0.05 w% to 0.4 w%, and both relatively coarse and fine particles due to the blend of clay material and a high water content of 17% or more. The kneaded body (20) containing

  The embankment thickness of the kneaded body (20) is about 10 mm in this case with respect to the substrate (1) of the above-described cut dimension example. The layer thickness of the molding layer (2) by embankment is preferably adjusted within a range of 3 mm to 20 mm smaller than the base (1) thickness, but is not limited to the plate. The same applies to the embankment thickness of the kneaded body (20) in Examples 2 and 3 described later.

(Surface layer separation process)
Next, as the surface layer separation step, the embankment 20 and the base material (1) in the embankment state are left to stand and dry at room temperature, so that the embedding body (20) that has been embanked is a thin layer with a moisture content of 15% or more (15 to 80%). Are separated into a surface layer portion (212) and a lower layer portion (211) having a water content of less than 15% (0.1% to 14.0%). This layer separation occurs when a clay material having a relatively small particle diameter becomes charged with a large amount of water particles and floats in a thin film shape on the surface layer portion of the embankment layer. On the other hand, the remaining relatively large particle size clay material and petalite material settled to the lower part of the kneaded body (20) by natural drying (drying process A) by standing for 24 hours or more, and contacted the lower part of the embankment layer. By absorbing water from the layer forming surface to the substrate (1), it becomes a lower layer part (211) having a large thickness of a semi-solidified state (FIG. 2 (b)).

(Surface part (212))
The surface layer part (212) was raised on the surface of the embankment by naturally drying the kneaded body (20) having a water content of 15% or more on the water-absorbing substrate (1) over a long period of 24 hours or more. A thin layer with a high water content containing a large amount of fine particles. Specifically, only fine particles having a high water content of 15% or more in the embankment 20 layers, the median diameter of D50 contained in the clay material being 10 μm or less, or the mode diameter being 10 μm or less. It is a dispersed thin layer of fine grains. This surface layer portion (212) is preferable as a dispersed thin layer of fine particles if it satisfies at least one of the conditions of D50 median diameter of 10 μm or less, or mode diameter of 10 μm or less. It is more preferable for the dispersion thin layer of fine particles for constituting a flat surface to have a D50 median diameter of 10 μm or less and a mode diameter of 10 μm or less.

  The representative particle size distribution of the surface layer portion (212) of Example 1 shows a dispersion curve having one prominent peak as shown in the particle size logarithmic frequency graph of FIG. 8, and both the D50 median diameter and the mode diameter are 5 μm or more. 8 μm or less (in FIG. 8, the median diameter is 7.25 μm and the mode diameter is 7.18 μm). In Example 1, the surface layer portion (212) is completely removed by the subsequent surface layer removing step and then fired. However, if the surface layer portion (212) is directly fired without removing the surface layer, The solidified layer surface is a flat surface in which no granular material of 100 μm appears in a scanning electron microscope observation of less than 100 times as shown in FIG. 5 (acceleration voltage 20.00 kV, magnification 30 times in FIG. 5).

(Lower layer part (211))
The lower layer portion (211) is composed of a semi-solidified clay layer mainly composed of petalite having a representative diameter of 10 μm or more and a clay material, which has settled and separated from water within the 20 embankments. In the embodiment, the embankment 20 is dehydrated by being absorbed by the water-absorbing substrate (1) and evaporating from the surface, and becomes a clay layer having self-molding properties even when the frame material is removed. Specifically, the lower layer portion (211) has a low water content of less than 15% (0.1% to 14.0%) in the 20 layers of the embankment, the median diameter of D50 is more than 10 μm, and This is a coarse-grained dispersion layer containing only coarse particles with a mode diameter of 10 μm or less. The typical particle size distribution of the lower layer portion (211) of Example 1 shows a dispersion curve having two or more prominent peaks as shown in the particle size logarithmic frequency graph of FIG. 9, and both the D50 median diameter and the mode diameter are 10 μm. Is in the range of 50 μm or more and 150 μm or less (median diameter 59.17 μm, mode diameter 82.96 μm in FIG. 9). However, strictly speaking, in the lower layer portion (211), the lower portion closer to the substrate, the larger the average particle diameter of the dispersed particles contained in the layer, and conversely, the upper portion closer to the lower surface. The average particle size of the dispersed particles contained in the layer is reduced. In the semi-solidified water-absorbed state, even if the frame material (F) is removed, the embankment is in a semi-solidified state until it has a self-holding property.

(Surface layer removal process)
Next, as the surface layer removing step of Example 1, the frame material (F) is removed, and the surface layer portion (212) that has been separated and floated on the upper part of the embankment is completely removed by the removing means (C) (in this example, a cutting blade). At the same time, the upper part of the lower layer part (211) is cut with a cutting surface that is curved and inclined from the surface side, and consists only of the lower layer part (221 ') (precursor) in a semi-solidified state, a processed state, and a surface layer removed state. It shall be (FIG. 1A, FIG.2 (b)-FIG.2 (c)). The removal means (C) (removal blade in this example) removes the upper layer portion of the lower layer portion or the upper thin portion of the lower layer portion at a time, and the entire removal of the surface layer portion (212). The molding step for adjusting the thickness of the subsequent lower layer portion (211) to a predetermined shape is performed simultaneously.

  As an example different from the present embodiment, removal of the surface layer portion and cutting of the lower layer portion may be performed as separate steps. In this case, for example, the surface layer portion (212) is entirely removed by the cutting blade that is the removal means (C) first to make only the lower surface portion (211) of the flat surface, and the lower layer portion (211) is subsequently different from the removal device ( (Or the same) The surface is formed by removing means. An example of the removing means is a blast shotgun that performs sandblasting. By performing a sandblasting process at an appropriate position as necessary, local uneven molding and partial removal molding of the lower layer can be performed.

By firing only the lower layer portion (211 (211 ')) that has undergone the surface layer removal step, the solidified layer surface becomes a rough surface in which a large number of stone-like portions are scattered when viewed at a magnification of 30 times. That is, the solidified layer surface of the lower layer portion (211 (211 ')) after the surface layer removing step and the subsequent firing step was observed with a scanning electron microscope less than 100 times shown in FIG. 6 (acceleration voltage 20.00 kV, magnification 30 in FIG. 6). 2), stone-like portions having a representative diameter of about 50 μm to 200 μm are interspersed, and a large and small granular portion having a porous representative diameter of 50 μm or less gathers and becomes an uneven surface. This solidified layer surface (FIG. 6) does not have a flat surface with an area of 1000 μm ² or more as compared with the solidified layer surface (FIG. 5) when the baking step is performed without the surface layer removal step from the surface layer separation state. There are significant differences in that a large number of stone-like parts and granular parts having different sizes are accumulated and that there are no cracks of 500 μm or more in length.

  (Second drying step (B)) Next, as the second drying step (B), the remaining lower layer portion (211 (211 ')) from which the surface layer portion (212) has been removed is dried by heating together with the substrate (1), and the moisture content The dehydrated state is 5% or less. The said heat drying is performed within the heating time of the range of 1 hour-24 hours at the drying temperature of the range of 60 degreeC-200 degreeC, for example.

(Baking process)
Next, as a firing step (second firing step), the clay-like kneaded body (20) providing the lower layer portion (211 (211 ')) is first heated at a second firing temperature lower than the first firing temperature. The second firing is performed for the same firing time as the firing temperature. Specifically, the second firing temperature of Example 1 is set within a range of 1150 ° C. to 1200 ° C., and the first until the kneaded body (20) becomes a molded layer (22 ′ (2)) in a molded state. Firing and heating are performed at a firing time in the range of about 3 hours to about 10 hours that is the same as the firing step. The firing time of the second firing is preferably set within the range of 5 hours to 10 hours, as with the first firing time, and more specifically, within the range of 8 hours to 10 hours as with the first firing time. Is preferred. In this way, by setting only the firing temperature in order for each firing step while maintaining the same firing time, the total amount of heat energy for firing (heat energy in the reaction temperature region of the kneaded body of each forming layer) It is made smaller than the 1st baking process which is a baking process. Prior to or during the second firing, the kneaded body (20) is absorbed into the substrate (1) from the layer-forming surface of the substrate (1) and thrown onto the fine irregularities of the substrate (1). It becomes a water-absorbed state. This water-absorbed kneaded body (20) is second-fired together with the substrate (1), whereby the molded layer (2) is formed in close contact with the substrate (1) ((h) in FIG. 1, FIG. (H1) in 2.). The raw material of Example 1 in the fired state (FIG. 2 (h)) is in the form of a plate having a corrugated processed surface with a side-view wave shape on the top surface.

  Each firing temperature in the first firing in the substrate forming step or each firing temperature in the second firing as the firing step means a set value of the maximum firing temperature in each firing. Actually, in the firing process of each step, the heating of the kneaded body (20) or the additional kneaded body is started from a temperature lower than the reaction temperature range. Then, after the temperature of the kneaded body (20) is raised to the set firing temperature, the temperature of the kneaded body (20) is gradually lowered to set the temperature again lower than the reaction temperature range, and the firing step is finished. In the series of steps of the firing step, the longer the time in the reaction temperature range, the greater the total amount of heat energy for firing.

As described above, the decorative ceramic raw material of Example 1 is obtained. Here, for example, the following finishing process is performed to obtain the decorative ceramic. That is,
The surface of the molding layer (22 ′ (2)) is subjected to glazing and finish coloring, and a finish layer (5 ′) is formed through finish firing ((z) in FIG. 1, (z) in FIG. 2)). . The decorative ceramics thus finished are shipped as they are or after being attached to a predetermined mounting portion.

<Example 2>
The raw material of decorative ceramics and decorative ceramics of Example 2 and a method for producing them will be described with reference to FIGS. 1B and 3.
(A) Decorative ceramic raw material and decorative ceramic of Example 2 The decorative ceramic raw material of Example 2 shown in FIG. 1B and FIG. 3 is a base (1) preformed as having water absorption, and a base The molding layer (2) (lower layer part (221 ′)) formed on the upper surface of (1) and the second molding layer (3) (solidified layer) which is an additional molding layer superimposed on the molding layer (2) (32 ')) and a third molding layer (4) (solidified layer (40')) which is an additional molding layer superimposed on the molding layer (2) and the second molding layer (3). It is a raw material with a four-layer structure.
The decorative ceramic of Example 2 is composed of a final state of a total of five layers of solid molding material in which a finishing layer (5 ′) is further formed by glazing, smoldering, or the like on the entire surface of the raw material (FIG. 3 (z)). . Other configurations and manufacturing methods not specifically mentioned are the same as those in the first embodiment.

Here, the base material (1) of Example 2 has a petalite compounding ratio (PR) of 40% to 75% by weight in the entire molded product in a final state which is a dehydrated state, together with each molded layer (2, 3, 4). Petalite is the main ingredient . The kneaded body for obtaining the substrate (1) includes a clay material and an aggregate in addition to petalite, and further includes a foaming agent that foams by drying during molding. However, the petalite blending ratio (PR1) of the substrate (1) is smaller than the petalite blending ratio (PR2) of the molding layer (2).
The base material (1) contains a clay material and contains petalite as a main component, so that many of the component compositions are common to the kneaded body (20) similar to the case of Example 1 for forming the molding layer (2). Thus, the melt-fixing property to the substrate (1) of the molding layer (2) by the second baking is excellent. Moreover, since the petalite compounding ratio (PR1) in the substrate is smaller than the petalite compounding ratio (PR2) in the molded layer, the substrate (1) can be fired at a higher temperature in the first firing. Further, since the substrate is pre-fired once, the shrinkage rate due to the subsequent firing (second firing, third firing, etc.) is small, and the shape stability of the whole raw material is excellent.

Specifically, the base (1), the molding layer (2), the second molding layer (3) as the additional molding layer, and the third molding layer (4) as the additional molding layer are all 40 w% of petalite. It mix | blends as what is used as a main ingredient in the predetermined ratio in the range below 75 w%. However, the petalite blending ratio of each layer in the final state after dehydration by finish firing is higher in the petalite blending ratio (PR2) in the molding layer than the petalite blending ratio (PR1) in the substrate, and the petalite blending ratio (PR2) in the molding layer. The petalite blending ratio (PR3) in the second molding layer as the additional molding layer is larger than that in the third molding layer as the additional molding layer again than the petalite blending ratio (PR3) in the second molding layer as the additional molding layer. The petalite compounding ratio (PR4) is larger. Moreover, the average particle size of the powder mixture obtained by removing water from the kneaded body (20) that is the raw material before firing of each layer is the largest in the powder mixture of the substrate (1), and then the powder mixture of the molding layer (2) is Next, the granule mixture of the second molding layer (3), which is the additional molding layer, is next, and the granule mixture of the third molding layer (4), which is the additional molding layer, is the smallest.

(B) The raw material of decorative ceramics of Example 2 and the manufacturing method of decorative ceramics The raw material of decorative ceramics and decorative ceramics of Example 2 are obtained by the manufacturing method shown below. First, as a substrate forming step, a material to be a substrate raw material is prepared (prepared), mixed with water, and finely polished to obtain a base kneaded body. After forming the kneaded body of this base into a plate shape and heat drying at 60 ° C. or more and 200 ° C. or less as the first drying, first firing at a first firing temperature within a range of 1200 ° C. to 1250 ° C. A plate-like substrate (1) in a baked state is formed as a stock (left flow in FIG. 1B).

  Next, as the embankment process, a frame material (F) is attached around the substrate (1) cut to a predetermined size, and on the layer forming surface which is the upper surface of the substrate (1), The clay-like kneaded body (20) obtained by kneading (soil preparation I) is embanked at a predetermined thickness to obtain an embankment state (FIG. 3 (a)).

  Next, the embedding kneaded body (20) is separated into a surface layer by natural drying for 24 hours or more, which is the second drying, and a semi-solidified surface layer separated state composed of a surface layer portion (212) and a lower layer portion (211) is obtained ( FIG. 3 (b)). Then, after removing the frame material (F), a single layer of the lower layer portion (211) is formed by a surface layer removing step (FIG. 3 (b) to FIG. 3 (c2)) that removes all the surface layer portion (212). The single layer is further subjected to forced drying (here, drying at a drying temperature in the range of 60 ° C. to 200 ° C. for 1 hour to 24 hours) to form a semi-solid and dry surface layer removed (FIG. 3). (C2)). Thus, the precursor (lower layer part (221)) of the molding layer (2) is obtained.

  Thereafter, as a layer addition step, a second kneaded body (30) (obtained by the soil preparation II), which is a raw material before firing of the additional molded layer of the second forming layer (3), is used as a precursor of the molded layer (2). On the (lower layer part (221)), the earth is filled with a thickness less than half the layer thickness of the precursor (lower layer part (221)) (Fig. 3 (d) "banking II"), natural and forced third dry By drying, a dehydrated semi-solidified second kneaded body (30) is obtained. Subsequently, as a processing step, a predetermined portion of each of the second kneaded body (30) and the precursor (lower layer portion (221)) is cut with a cutting surface that is curved and inclined so that each layer is exposed from the surface side, and the processed state (FIG. 3 (f)). Furthermore, the third kneaded body (40) (obtained by the soil preparation III), which is a raw material before firing of the additional molding layer (third formation layer (4)), is uniformly applied to the entire exposed layer surface in this processed state. Embanking to a thin film thickness (“Embedding III”), a cut four-layer structure is obtained. Then, as the second firing step, the cut four-layer structure is subjected to second firing at a second firing temperature lower than the first firing temperature within a range of 1150 ° C. to 1200 ° C., and FIG. The processed fired material having the four-layer structure shown, that is, the decorative ceramic raw material of Example 2 is obtained.

  In FIG. 3 (h), what is indicated by reference numeral (221 ') is a forming layer (2) as a first forming layer obtained from the precursor (lower layer part (221)), and what is indicated by reference numeral (32') The solidified layer of the second molded layer (3) obtained from the precursor and indicated by the reference numeral (40 ') is the solidified layer of the third molded layer (4) obtained from the third kneaded body (40). is there.

As described above, the decorative ceramic raw material of Example 2 is obtained. Here, for example, the following finishing treatment is performed to obtain the decorative ceramic. That is,
As a glazing process, the glaze is uniformly applied to the surface exposed surface of the processed fired material (decorative ceramic raw material) after the second calcination, followed by calcination, and then, as a transfer process, the desired material is reproduced on the surface. The color pattern is transferred and transferred and fired, and finally finish firing (FIG. 3 (z)) is performed as a finish firing step.

  However, in each of the first firing, the second firing, the sinter firing, the transfer firing, and the finish firing, at least one of the firing temperature (maximum firing temperature) or the firing time is set lower in order so as to be a later step. The firing temperature and pre-baking time are not exceeded. This prevents deformation, layer separation, cracks and cracks due to repeated firing. In this embodiment, the finish firing temperature is set lower than any firing temperature of the first firing, second firing, smoldering, and transfer firing, and the transfer firing temperature is any of the first firing, second firing, or smoldering. It is set lower than the firing temperature, the calcination temperature is set to 1150 ° C. or lower, which is lower than both firing temperatures of the first firing and the second firing, and the second firing temperature is from 1150 ° C. lower than the first firing temperature. It is set within the range of 1200 ° C.

  Further, in this embodiment, the first baking and the second baking are set to the same baking time, and only the baking temperature is set to be smaller in order than the pre-baking temperature. This is the heat energy for firing (that is, the heat energy in the reaction temperature range of the kneaded body (20) to the additional kneaded body (second kneaded body 30, third kneaded body 40,...) Of each forming layer). It means that the total amount of becomes smaller as it becomes a subsequent firing step.

<Example 3>
The raw material of decorative ceramics and decorative ceramics of Example 3 and the manufacturing method thereof will be described with reference to FIGS. 1C and 4.
(A) The decorative ceramic raw material and decorative ceramic of Example 3 The decorative ceramic raw material of Example 3 shown in FIGS.
A substrate (1) preformed as having water absorption in the same manner as in Example 2,
A kneaded body (20) similar to that in Example 2 (obtained by soil preparation II) was embanked (filled I) on the upper surface of the substrate (1) (FIG. 4 (a)), and the second dried A · The surface layer part (222) and the lower layer part (221) are separated into the surface layer (222) and the lower layer part (221) by natural drying and forced drying as B (FIG. 4 (b)), and cut into a predetermined uneven shape along with the removal of the surface layer part (222) ( FIG. 4 (c2)), a lower layer portion (221) (FIG. 4 (c2)) which is a precursor of the molding layer (2) is obtained, and this is subjected to second firing to form a molding layer (2 (221 ′)). (FIG. 4 (h1))
A second kneaded body (30) similar to that in Example 2 (obtained by soil preparation II (a coarse-grained coarse particle mixture smaller than soil preparation I and larger than soil preparation III)), On the surface of the molding layer (2 (221 ′)) after the second firing, the bank is filled with a thickness thinner than that of the molding layer (2 (221 ′)) (FIG. 4 (d2) “banking I”), and the third drying The surface layer is separated into the surface layer portion (312) and the lower layer portion (311) by both natural drying and forced drying (FIG. 4 (e2)).

In this way, a lower layer portion (311) which is a precursor of the second molding layer (3) having a processed shape obtained by cutting the surface layer portion (312) together with the removal of the surface layer portion (312) is obtained. A second molded layer (3) (FIG. 4 (h2)), which is an additional molded layer formed by third firing, is obtained. By forming this additional molding layer, a three-layer structure is obtained.
Further, using the same kneaded body (obtained by the soil preparation III) as that of the kneaded body in Example 2 (obtained by the soil preparation III in FIG. 1B), spraying was performed so as to cover the entire surface of the three-layer structure. Filling (banking III) is performed by a coating process, and this is subjected to fourth firing to obtain a third forming layer (4) which is an additional molding layer. A four-layer structure is obtained by forming the third forming layer (4) as the additional molding layer (FIG. 4 (h3)).

  The decorative ceramic of Example 3 is finally subjected to calcination after uniformly glazing on the surface of this raw material, and further transfer calcination after transferring a desired (for example, reproduction target) colored pattern to the glazed surface. It consists of a final state of a total of 5 solid molding materials in which a finish layer (not shown) is formed by finish firing. In the final state, the molding (1), the molding layer (2) composed of the lower layer part (221 '), the second molding layer (3) composed of the solidified layer (311'), and the third molding composed of the solidified layer (40 '). In each layer (4), the petalite compounding ratio (PR1) is 40 w% or more and 75 w% or less. Other configurations and manufacturing methods not specifically mentioned are the same as those in the second embodiment.

  Examples of the characteristic configuration of the decorative ceramic raw material and the decorative ceramic of Example 3 include the following. That is, the first molding layer as the molding layer (2), the second molding layer (3) as the additional molding layer, and the third molding layer (4) are preceded by the kneaded bodies (20, 30, 40) as the raw materials. After embankment on the solidified surface after firing, the layers are solidified and fired one by one in each firing step (second firing, third firing, fourth firing). Further, the molding layer (2) and the second molding layer (3) are subjected to a drying step (second drying, third drying) to be in a surface layer separation state, and the remaining surface layer portions (222, 312) are removed and the remaining layers are removed. The lower layer portions (221, 311) are cut into a predetermined shape and fired.

  The first molding layer as the molding layer (2), the second molding layer (3) as the additional molding layer, and the third molding layer (4) all have a petalite compounding ratio (PR1) of 40 w% or more and 75 w% or less. is there. However, the petalite compounding ratio of each layer in the final state after forming the raw material and after finish firing is higher than the petalite compounding ratio (PR3) in the second molding layer as the additional molding layer, rather than the petalite compounding ratio (PR2) in the molding layer. Is larger by 1 to 10 w%, and the petalite blending ratio (PR4) in the third molding layer as the additional molding layer is larger by 1 to 10 w% than the petalite blending ratio (PR3) in the second molding layer. The petalite blending ratio (PR3) in the second molding layer and the petalite blending ratio (PR4) in the third molding layer are both different only in petalite blending ratio and clay stone blending ratio. The amount of preparation is the same. Moreover, the average particle size of the powder mixture obtained by removing water from the kneaded body (20) that is the raw material before firing of each layer is the largest in the powder mixture of the substrate (1), and then the powder mixture of the molding layer (2) is Large, then the second mixture layer (3) has the largest powder mixture, and the third molding layer (4) has the smallest powder mixture.

Each forming layer will be further described.
(Molded layer (2))
The molded layer (2) of Example 3 is embanked on the substrate (1) in the state of a clay-like kneaded body (20) having a moisture content of about 45% to 55%, and is a natural material as the second drying step A / B. -After fixing to the substrate (1) by forced drying, the surface portion including the surface layer portion is cut by the surface cutting as the processing steps A and B. After that, the surface portion including the surface layer portion is cut, and then lower than the first firing temperature, 1150 ° C to 1200 ° C It is formed by solidification by the second firing at the firing temperature in the temperature range. This is the same as the surface layer separation step, the surface layer removal step, and the subsequent second firing in Example 1. That is, the kneaded body is made into a semi-solid state in which the surface layer is separated and dehydrated by natural drying for 24 hours or more after embankment and subsequent forced drying, and the surface portion including the surface layer portion is removed and cut into a predetermined shape. Thus, only the semi-solidified kneaded body (20) portion made of relatively coarse particles is left in a dehydrated state, and the second firing is performed after the molding by such a cutting process, thereby promoting the molding retainability of the molding layer. The final molded layer (2) after firing is mainly composed of petalite, and specifically has a petalite blending ratio (peterite blending ratio (PR2) in the molding layer) of 45 to 40% by weight as a whole.

(Additional molding layer (second molding layer (3), third molding layer (4)))
In the second molding layer (3) as the additional molding layer of Example 3, the second kneaded body (30) is surface-separated by natural drying / forced drying (FIG. 4 (e2)), and the surface layer portion (312). It consists of a solidified layer (311 ') obtained by baking and solidifying only the lower layer part (311) which is a precursor of the second molding layer (3) after removing (Fig. 4). That is, as a layer addition process, the second kneaded body (30), which is a raw material before firing, is embanked on the lower layer portion (221 ') after cutting and after the second firing, and then by natural / forced drying which is third dried. The surface layer portion (312) and the lower layer portion (311) are separated into surface layers (FIG. 4 (e2)), and the surface layer portion (312) is removed and the remaining lower layer portion (311) is cut into a predetermined processing shape. Then, the second molding layer (3) is solidified and molded by third firing.

  During the layer addition process, the lower layer part of relatively coarse particles is in contact with the fine irregularities of the solidified layer of the previously formed layer between adjacent layers by a natural / forced drying process, so The improvement of the fixing property between the layers is promoted (FIG. 4 (h2)). In addition, after the surface layer is separated by the drying steps A and B before solidification by baking, the surface layer is removed by cutting the surface with a high water content, and the lower layer portion is molded into a molded shape and then fired (see FIG. 4 (c2) (h2)). By firing and solidifying the second molding layer (3) after the surface layer separation and molding process, relatively coarse particles are evenly dispersed in the layer, and the fixing property with the adjacent preceding layer is improved and molding is performed. The shape stability of the layer surface is improved.

  Moreover, in Example 3, after solidifying and molding the second molding layer (3) as an additional molding layer in the layer addition process, a third kneaded body (40) is formed on the surface of the second molding layer (3) as a second layer addition process. And the third molding layer (4), which is an additional molding layer, is solidified and molded. The powder mixture of the third kneaded body (40) is composed of the same mixed components as the powder mixture of the second kneaded body (30). By forming the kneaded body (20) having the same mixed components as a layer addition process again, the difference in the thermal expansion coefficient of each layer is reduced, and the fixing property between the layers can be improved.

(B) The decorative ceramic raw material and the decorative ceramic manufacturing method of Example 3 The decorative ceramic raw material and the decorative ceramic of Example 3 are manufactured by the manufacturing method shown in FIGS. 1C and 4.
First, as a substrate forming step, a material to be a substrate raw material is prepared (prepared), mixed with water and finely polished to obtain a base kneaded body which is a first kneaded body using petalite as a main agent.
The kneaded body of this base is formed into a plate shape, heat-dried at 60 ° C. or higher and 200 ° C. or lower as the first drying, and then subjected to a first baking within a range of 1200 ° C. to 1250 ° C. The substrate (1) is stock-formed (FIG. 1C left flow).

  Next, as a banking process, after attaching a frame material (F) around the substrate (1) cut into a predetermined size, a kneaded body (20) containing petalite as a main ingredient (obtained by the preparation I) A thing) is further filled with a predetermined thickness ("filling I") to obtain a filling state (FIG. 1C and FIG. 4 (a)).

  Next, the embankment layer of the kneaded body (20) is separated into a dried surface layer part (222) and a lower layer part (221) by natural / forced drying, which is the second drying A / B process, and also serves as a surface layer removing process. Surface removal / working state in which the single layer of the lower layer part (221) that has been shaped is formed on the substrate (1) by cutting and shaping the surface by the machining A and B processes (FIG. 1C and FIG. 4 (c2)) )). Thus, the precursor of the molding layer (2) which consists of a lower layer part (221) is obtained.

  Next, the substrate (1) and the precursor of the molded layer (formed of the lower layer portion (221)) which has been molded at the second firing temperature in the temperature range of 1150 ° C. to 1200 ° C., which is lower than the first firing temperature. Second firing is performed to obtain a processed two-layer solidified molded body composed of the substrate (1) and the molded layer (2) composed of the lower layer portion (221 ′) (FIG. 1C and FIG. 4 (h1)).

  Further, as a layer addition step, the second kneaded body (30) containing petalite as a main agent is partially embanked so as to have a uniform thickness along the processed shape of a part of the surface of the processed molded layer (2). (FIG. 1C and FIG. 4 (d2)). In this partial embankment state, natural drying and forced drying are performed as a third drying step, and the embankment layer of the second kneaded body (30) is separated into a surface layer part (312) and a lower layer part (311) (surface layer separated state ( 1C and FIG. 4 (e2)). Subsequently, as a processing A / B step, a part of the surface exposed portion including all of the surface layer portion (312) and a part of the lower layer portion (311) of the second kneaded body (30) subjected to additional embankment is removed by a removing means. The second surface layer is removed and processed ((f) in FIG. 1C).

  Next, the molding layer (2) composed of the substrate (1), the lower layer portion (221 ′), and the second kneaded body (30) at a third firing temperature in a temperature range of 1100 ° C. to 1150 ° C. lower than the second firing temperature. ) Is subjected to third firing to obtain a processed three-layer solidified molded body comprising the substrate (1), the molding layer (2) and the second molding layer (3) (FIG. 1C and FIG. 4 (h2)).

  Furthermore, as a layer addition process again, the third kneaded body (40) mainly composed of petalite is embanked by spray coating over the entire surface of the three-layered state ("bank III"), and as the fourth firing process By forming a third molding layer (4) composed of a solidified layer (40 ′) by fourth firing at a fourth firing temperature within a temperature range of 1150 ° C. to 1200 ° C., which is lower than the third firing temperature. The base material of the decorative ceramic of Example 3 which is a processed fired material having a four-layer structure shown in 1C and (h3) in FIG. 4 is obtained.

  As the glaze process, the decorative ceramic of Example 3 was applied to the surface exposed surface of the raw material of the decorative ceramic of Example 3 thus manufactured. It is obtained by transferring a desired color pattern (for example, a reproduction target) onto the surface, transferring and firing, and finally performing finish firing as a finish firing step.

  Here, the kneaded body (20) as the first kneaded body is a clay-like kneaded body (20) obtained by kneading water with a first powder mixture having a first average particle size within a predetermined range. 30) is obtained by kneading water into a second powder mixture having a second average particle size smaller than the first average particle size, and the third kneaded body (40) has a particle size smaller than the second average particle size. Water is kneaded with a third powder mixture having a third average particle size. However, the amount of kneading water is larger in each kneaded body of the first kneaded body (kneaded body (20)), second kneaded body (30), and third kneaded body (40) than in the substrate (1), and before firing. In the kneaded state, each of the kneaded bodies ((kneaded body (20)), second kneaded body (30), and third kneaded body (40)) that is embanked than the substrate (1) has a higher water content. Yes.

  Further, the calcination temperature in the glazing step is lower than the second baking temperature, the transfer baking temperature after the transfer of the colored pattern is the same as or lower than the calcination temperature, the finish baking temperature is It is set to be approximately equal to or lower than the transfer baking temperature. This means that the total amount of thermal energy in each firing of the second firing, sinter firing, transfer firing, and finish firing decreases with each firing repetition.

The substrate is preliminarily fired and molded by first firing before molding of the molding layer,
In the molded layer, a kneaded body obtained by kneading a powder mixture containing petalite as a main ingredient and water is in a state where water is absorbed by the substrate on the layer forming surface of the substrate, and in this state, the firing temperature is lower than that of the first firing. It is preferable that the second baking is performed together with the substrate.

In the clay state before the second firing, the additional molding layer is allowed to stand in an embankment state in which a kneaded body including at least petalite, an inorganic peptizer, and a clay material is embanked on the substrate, It is preferable that the surface layer portion containing moisture from within the embankment layer is fired after a layer separation step in which the surface layer is separated on the lower layer portion.
Furthermore, the layer-added molding layer is formed by removing only the lower layer portion remaining after the surface layer removing step after the surface layer removing step of removing the surface layer portion of the kneaded body embanked on the substrate after the layer separating step. It consists of a fired body obtained by two firings. Moreover, it is preferable that the kneaded body before the first firing of the substrate further includes a foaming agent that foams in at least one of the plate-shaped molding and the first firing.

  The above is the configuration of the present invention and the embodiment of the present invention. However, the present invention is not limited to the configuration or manufacturing method of the above-described embodiment, and layer formation can be performed without departing from the technical idea of the characteristic portion. It is possible to change the aspect, change various ratios, exchange manufacturing processes, combine manufacturing processes between the embodiments, and perform partial extraction.

  The present invention relates to decorative ceramics used as tangible cultural properties, murals, sculptures, paintings, restorations and reproductions of crafts, reproductions, three-dimensional molded articles for decoration, or building materials for decoration of interior and exterior It can be used for providing decorative raw materials and decorative ceramics using the raw materials.

(1) Base (2) Molded layer (first molded layer)
(20) Kneaded body (22 ') (32') (211 ') (221') (311 ') (40') Solidified layer (212) (222) (312) Surface layer part (211) (221) (311) ) Lower layer part (3) Second molded layer (30) Second kneaded body (4) Third molded layer (40) Third kneaded body (5 ') Finished layer (a) Embankment state (b) Surface layer separation state (c ) Surface layer removed state (d2) Partial embankment state (e2) Surface layer separated state (f) Surface layer removed / processed state (C) Removal means (F) Frame material (PR) Petalite compounding ratio in the entire molded body (PR1) Blending ratio (PR2) Petalite blending ratio in the molding layer (first molding layer) (PR3) Petalite blending ratio in the second molding layer (PR4) Petalite blending ratio in the third molding layer

Claims (7)

A substrate having at least one layer-forming surface having fine irregularities, and a molding layer (excluding one made of a glazed layer ) formed on the layer-forming surface of the substrate, and integrally formed The raw material of decorated ceramics,
Of the molded layer, the layer portion adjacent to the base is mainly composed of petalite , and is fixed along the fine irregularities of the base .
At least the boundary surface adjacent to the substrate of the molding layer has a particle size distribution with a mode diameter of more than 10 μm and a D50 median diameter of more than 10 μm. The particle size distribution is a particle size logarithm with the horizontal axis as the particle diameter and the vertical axis as the frequency. A raw material for decorative ceramics, which is shown as a dispersion curve having two or more peaks protruding in the vertical axis direction in a frequency graph . The base is made of a fired plate-like material having water absorption, and the molding layer is mainly made of petalite, and is made of a fired material having a layer thickness of 3 mm to 10 mm smaller than the layer thickness of the base. Item 1. A decorative ceramic raw material according to Item 1. 3. The decorative ceramic raw material according to claim 1, wherein at least a boundary surface adjacent to the substrate of the formed layer has a particle size distribution in which a median diameter and a mode diameter of D50 are both in a range of 50 μm to 150 μm . The decorative ceramic raw material according to any one of claims 1 to 3, wherein at least one additional molding layer (excluding one made of a glazed layer) is formed on the molding layer . The raw material for decorative ceramics according to any one of claims 1 to 4, wherein the base material comprises at least petalite as a main agent, and a petalite compounding ratio of the base material is equal to or less than a petalite compounding ratio of the molding layer . A decorative ceramic obtained by subjecting the decorative ceramic raw material according to any one of claims 1 to 5 to a finishing treatment . The decorative ceramic according to claim 6, wherein at least one of a glazing process, a coloring process, and a pattern transfer process on the raw material of the decorative ceramic and a finish firing process are performed as the finishing process .