JP2015178429A - Method for producing ceramic product, and ceramic product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of producing, at low cost, ceramic products having a crystalline pattern precipitated on a glaze layer, and enabling stably obtaining products having a similar total view with good reproducibility.SOLUTION: There are included: a first step S11 of forming a nucleus formation body containing metal of the same kind as metal contained in crystal to be precipitated; a second step S12 of mixing a green body and the nucleus formation body and molding so as to form a basis material part derived from a green body, and a backing material formation body where the plurality of nucleus formation bodies are scattered in the basis material part, and part of the nucleus formation body appears on a glazed surface; a third step S13 of applying crystalline glaze containing metal to be precipitated to the backing material formation body; and a fourth step S14 of burning a glazed product. Crystal generated from components contained in the crystalline glaze precipitates due to a nucleus body derived from the nucleus formation body so as to express a pattern. Two or more kinds of materials to be mixed are mixed and molded so as to mechanize operation, reduce production cost, and stably obtain ceramic products of a similar total view in good reproducibility.

Description

  The present invention relates to a method for manufacturing a ceramic product and a ceramic product, and more particularly to a method for manufacturing a ceramic product having a pattern formed by crystals deposited on a glaze layer and the ceramic product.

  Conventionally, there are many types of ceramic products such as tiles, restaurants, vases, etc. that have a glassy glaze layer on the surface, and the glaze layer allows the product strength, product surface hardness, wear resistance, Product properties such as chemicals are improved, and ceramic products are decorated to give a beautiful appearance.

  In addition, as one of the decoration techniques using the glaze layer, decoration using crystal glazing is known. This technique involves applying a crystal habit to the base of the ceramic product, attaching a nucleation body that becomes a nuclei by firing on the glazed surface of the obtained glazed product, and firing the glazed product with the nucleation body attached thereto. In particular, by controlling the cooling process, a specific component melted in the melt phase of the glaze is precipitated due to the nucleation body-derived nuclei, and the precipitated crystals can be observed with the naked eye. By growing to a size, a crystal pattern is developed.

Such crystal habits include zinc crystal habits containing zinc white (ZnO), diopside crystal habits containing dolomite (CaCO ₃ .MgCO ₃ ), and titanium crystal habits containing titania (TiO ₂ ). Bone ash / iron oxide crystal candy containing bone ash (3CaO · P ₂ O ₃ ) is known.

  In addition, as a similar technique, in Patent Document 1 below, a titanium dioxide aqueous solution as a decorating agent is attached to the surface of a glaze of ceramics, and the day-changing nucleating agent portion is used as a nucleus, and the day-of-day change including the luster in the peripheral part. A day-changing pattern ceramic characterized by generating a pattern is disclosed.

  As described above, in any of these techniques, a nucleus (the first trigger for generating a microcrystal when a crystal is precipitated from the melt) is indispensable for pattern formation. In other words, the above technique causes the glaze layer to change by making the glaze composition low in stability to firing. Therefore, the presence or absence of change (crystal generation) is unstable and reliable. In order to generate crystals and to form a pattern, the resulting nucleus is required.

JP 2009-196875 A

  However, in order to attach the nucleation body to the glaze surface, for example, a powder or granule of the nucleation body is suspended in water (for example, a binder such as Na-CMC (carboxymethylcellulose sodium salt) is added. Suspended in water), this suspension may be contained in a water absorbent body such as a brush or sponge and attached to the glazed surface, but it seems that it is essential to attach the nucleation body to the glaze surface In the forming method, it is difficult to mechanize the attaching operation of the nucleation body, and it mainly depends on the manual operation.

  The overall view of the pattern depends greatly on the crystal precipitation state such as the number of crystals, the size of the crystals, and the density of the crystals (the number of crystals per unit area). In the method, it is difficult to level the crystal precipitation state and stably obtain a product having the same overall view with good reproducibility.

  Accordingly, the present invention provides a ceramic product that can produce a ceramic product having a pattern formed by crystals precipitated in the glaze layer at low cost, and can stably obtain a product having the same overall view with good reproducibility. It aims at providing the manufacturing method of.

  The present invention was created to solve the above problems, and firstly, a ceramic substrate, a vitreous glaze layer stacked on at least a part of the substrate surface, A method for producing a ceramic product having a crystal formed in a glaze layer and forming a pattern, the nucleator forming a nuclei by firing, and a metal contained in the crystal to be precipitated A first step of forming a nucleation body containing the same type of metal, and a second formation of a substrate forming body in which a crystal habit is applied to a surface to be coated, by a substrate forming body that becomes a substrate by firing. In the process, by mixing and molding the clay and the nucleation body formed in the first process, a base part derived from the clay, and a plurality of nucleation bodies scattered in the base part A part of the nucleation body is exposed on the surface to be coated. A second step of forming a material forming body, a third step of applying a crystal habit containing a metal contained in a crystal to be deposited on a surface to be coated of the base material forming body, in a crystal habit that becomes a glaze layer by firing, In the fourth step of firing the glazed product obtained in the third step, the substrate forming body is sintered, and the temperature is raised to a temperature equal to or higher than the temperature at which the crystal habit is melted, and the first temperature is maintained. The components contained in the crystal habitat are caused by the nucleus from the nucleator by lowering the temperature from the maximum temperature in the step and the first step to the temperature range in which the crystals are precipitated and maintaining the crystal precipitation temperature range. And a fourth step including a second step of precipitating a crystal generated from the above and aging the crystal to develop a pattern.

  In the manufacturing method of the ceramic product of the first configuration, the present invention can be carried out by a simple method that has been conventionally performed by blending and molding two or more compounds to be blended. The mechanization is easy, and the manufacturing cost can be reduced by the mechanization of the work. In addition, the mechanization of the work leveles the dispersion of the nucleation bodies between multiple base material formation bodies, so that the overall view does not differ greatly between products, and a ceramic product with the same overall view is reproduced. It can be obtained with good stability. Moreover, the manufactured ceramic product can provide a new texture and taste different from the conventional product by having a pattern of a plurality of crystals uniformly distributed in the glaze layer.

  Second, in the first configuration, the nucleation body is a granule granulated from the glaze raw material powder, the clay is a clay powder, and the base material formation body is the powder body. And the kneaded clay powder.

  In the manufacturing method of the ceramic product of the second configuration, since the compound to be blended is powdery, the nucleation body and the clay powder can be homogeneously mixed and dry-pressed. Since the nucleation body is more uniformly distributed over the entire surface to be coated of the base material formation body, a ceramic product in which the crystal pattern is more uniformly distributed over the entire glaze layer can be obtained.

  In addition, since firing is performed in a state where the unfired nucleation body and the unfired crystal habit are in contact with each other, they are influenced by each other during firing, so that crystals are more likely to precipitate, and the growth of crystals is promoted. .

  As the 2-1 configuration, in the second configuration, the glaze raw material powder is contained in the glaze raw material powder containing the same type of metal as the metal contained in the crystal to be precipitated and the crystal to be precipitated. It is good also as a mixed powder which mix | blended the glaze raw material powder | flour which does not contain the same kind of metal as the metal which is. In this method of manufacturing a ceramic product, the behavior during the firing of the nucleation body (starting of melting, melting than in the case of a single body made of a glaze raw material powder containing the same type of metal as the metal contained in the crystals to be precipitated. Therefore, the precipitation of crystals can be easily controlled by setting the crystal precipitation temperature and the holding time in the firing process, which further stabilizes the product quality.

  In the method for manufacturing a ceramic product having the first, second, or 2-1 configuration, the metal contained in the crystal to be precipitated may be zinc. Therefore, zinc white can be used as a supply source of zinc. Since zinc white is a glaze raw material with stable quality, the crystal precipitation state is further stabilized.

  Thirdly, in the first or second configuration, in the third step, the crystal glaze is formed into a sheet shape to produce a glaze sheet, and the glaze sheet is applied to the surface of the substrate forming body. It is characterized in that the crystal habit is applied to the surface to be applied of the substrate forming body by being attached to the substrate.

  In the third method for manufacturing a ceramic product, it is easy to handle irregular glazing. For example, when it is desired to partially form the glaze layer by dispersing it at a plurality of locations on the surface of the substrate, the shape of each of the above locations (surfaces to be treated) where the glaze layer is to be formed by cutting the glaze layer is substantially the same. By simply forming a glaze sheet section in the shape and sticking this glaze sheet section to each of the above-mentioned glazed surfaces, it is possible to reliably and easily cope with complicated glazing, and thereby, the glaze layer portion and the non-glaze layer It is possible to create a unique texture in which the portion is mixed and the glaze layer portion has a pattern of precipitated crystals.

  Fourth, a ceramic substrate, a glassy glaze layer formed on at least a part of the substrate surface, and a crystal that forms a pattern with crystals deposited on the glaze layer; In the manufacturing process, a nucleation body that forms nuclei by firing, and a nucleation body that contains the same type of metal as the metal contained in the crystal to be precipitated is formed and fired. The base material forming body to be the base material, and the base material forming body in which the crystallized surface is subjected to crystal habit, and by mixing and molding the clay and the nucleation body, A base material forming body comprising: a base portion derived from the base material; and a plurality of nucleation bodies scattered in the base portion, wherein a part of the nucleation body is exposed on the surface to be coated It is a crystal habit that forms a glaze layer by firing and is contained in crystals to be precipitated Applying a crystal glaze containing a genus to the surface to be coated of the base material forming body, heating the glazed product, heating the base material forming body, and raising the temperature to a temperature equal to or higher than the temperature at which the crystal glaze melts, After maintaining the maximum temperature, the temperature is lowered to a temperature range in which the crystals are precipitated, and by maintaining the crystal precipitation temperature range, the crystals generated from the components contained in the crystal habitat due to the nuclei derived from the nucleators And the crystal is aged to develop a pattern.

  In the ceramic product having the fourth structure, the manufacturing process can reduce the manufacturing cost as well as the ceramic product having the same general view as in the method of manufacturing the ceramic product having the first structure. It can be obtained stably with good reproducibility, and by having a pattern of a plurality of crystals uniformly distributed in the glaze layer, it is possible to provide a new texture and taste different from conventional products.

  As the 4-1 configuration, in the above fourth configuration, the base material has agglomerates derived from the nucleator and formed by firing, and the aggregates in the base material and the glaze layer It is good also as having a pattern which expands radially centering on a contact or its vicinity. In ceramic products with this structure, a radial pattern is formed on the deepest part side (base material side) of the glaze layer, so that the glaze layer has a three-dimensional effect and deepness and provides a texture with excellent visual appeal. can do.

  Moreover, in the ceramic product having the above-described configuration of 4-1 above, the agglomerates may be glassy. In a ceramic product with this structure, even if a part of the agglomerate protrudes into the glaze layer and remains in the center of the pattern, the agglomerate is visually vitreous that is the same quality as the glaze layer. The remaining part is assimilated to the surroundings and cannot be visually recognized. This makes it possible to make the pattern look more beautiful.

  In addition, the fifth aspect includes a ceramic substrate, a glassy glaze layer formed on at least a part of the substrate surface, and a crystal that is deposited on the glaze layer to form a pattern. It is a ceramic product, and a plurality of agglomerates containing the same type of metal as the metal contained in the precipitated crystal are scattered in the base material, and the pattern touches the glaze layer in the agglomerates in the base material It is characterized by spreading radially around the contact point between the agglomerate and the glaze layer or in the vicinity thereof.

  Since the ceramic product having the fifth configuration is obtained by the method for manufacturing the ceramic product having the first configuration, the manufacturing cost can be reduced and a ceramic product having the same general view can be reproduced with high reproducibility. Product quality can be further stabilized by using zinc white which can be obtained stably and the quality is stable as a main raw material for forming a pattern.

Sixth, in the fifth configuration, the metal contained in the precipitated crystal is zinc, and a main component of the crystal is willemite (2ZnO · SiO ₂ ).

  In addition, in each said structure, as a ceramic product, ceramic tiles, ceramic eating and drinking devices, ceramic vases, and the like can be given.

  Moreover, it is good also as the following structures as another structure. That is, “a ceramic tile base material, a glassy glaze layer formed on the surface side of the tile base material, a zinc crystal deposited on the glaze layer, and a zinc crystal forming a pattern, In the manufacturing process, zinc powder and other glaze raw material powders are blended and granulated to form a nucleation body, and the nucleation body and clay powder And forming a molded body having a base part derived from clay powder and a plurality of nucleating bodies scattered in the base part, and the front side of the molded body The surface portion of the product is coated with zinc crystal soot prepared by containing zinc white, the glazed product is heated, the molded body is sintered, and the temperature is raised to a temperature equal to or higher than the melting temperature of the zinc crystal soot. After maintaining the maximum temperature, the temperature is lowered to the temperature range where zinc crystals precipitate, By maintaining the crystal precipitation temperature range, the zinc crystals generated from the components contained in the zinc crystal soot are precipitated due to the nuclei derived from the nucleation bodies, and the zinc crystals are aged to develop a pattern. It may be a ceramic style characterized by that. "

  In the ceramic style of the above other configurations, a new tile different from the conventional tiled surface (tiled wall surface, tiled floor surface, etc.) due to the tile having a pattern of crystals distributed uniformly in the glaze layer. A tiled surface with a texture and taste can be constructed.

  According to the method for producing a ceramic product and the ceramic product according to the present invention, the present invention can be carried out by a simple method which has been conventionally performed by blending and molding two or more kinds of compounds. Such a method is easy to mechanize and can reduce the manufacturing cost by mechanizing the work. In addition, the mechanization of the work leveles out the dispersion of nucleation bodies between multiple substrates, so the overall view does not differ greatly between products, and ceramic products with the same overall view are stable with good reproducibility. Can be obtained.

  Moreover, according to the ceramic product based on this invention, it can provide the new texture and taste different from a conventional product by having the pattern by the some crystal | crystallization distributed uniformly in the glaze layer.

It is a photograph which shows the principal part of the ceramic product (Example 1) based on this invention, and is a photograph which shows an example of the pattern expressed in the glaze layer. It is a photograph which shows the principal part of the ceramic product (Example 2) based on this invention, and is a photograph which shows an example of the pattern comprised by the glaze layer part and the non-glaze layer part. It is a flowchart which shows the manufacturing process of the ceramic product based on this invention. It is a top view of a base-material formation body. It is an AA cross-section principal part enlarged view of FIG.

  In the present invention, a ceramic product having a pattern formed by crystals deposited on the glaze layer can be produced at low cost, and a product having the same overall view can be stably obtained with good reproducibility. The purpose of providing the manufacturing method was realized as follows.

  The ceramic product according to the present invention includes a ceramic substrate, a glassy glaze layer formed on at least a part of the substrate surface, and crystals C deposited on the glaze layer (see FIGS. 1 and 2). ) And crystals C forming a pattern. Specifically, the crystal C is precipitated in the glaze layer. In FIGS. 1 and 2, the crystals indicated by the lead lines are only some of the many crystals shown in the drawings.

  Here, the ceramic product is mainly a tile made of ceramics, and may be a ceramic eating and drinking device, a ceramic vase, etc. For example, in the case of a ceramic tile, the surface portion on the front side of the substrate A glaze layer is formed on the surface portion opposite to the surface portion to be bonded to the work surface such as a wall substrate or floor substrate.

  A method of manufacturing the ceramic product of this example will be described with reference to FIG. First, a nucleation body is formed (first step S11 which is a nucleation body formation step). That is, glaze raw material powder containing the same type of metal as the metal contained in the crystal to be precipitated, and other glaze raw material powder (glaze raw material powder not containing the same type of metal as the metal contained in the crystal to be precipitated) And the resulting mixed powder (glaze raw material powder) is granulated to obtain a nucleation body formed into a granular form. Here, the term “powder body” refers to an aggregate in which a plurality of primary particles of powder (one solid particle to which no other particles adhere) are aggregated.

  As the granulation method, the above mixed powder is put into a ball mill, water is added thereto, mixed and stirred, the obtained slurry is dried, the dried product is roughly pulverized, and the same as the target maximum particle size The extruded coarsely pulverized product is classified by a sieve having the same opening as the target minimum particle size, and the sieve top (which does not pass through the sieve) is recovered as a nucleator.

  As for the granulation method, instead of the above method, a nucleation body may be prepared using a spray dryer (spray dryer) or a stirring blade type powder mixing stirrer.

  A spray dryer is a dryer that sprays a material to be dried, such as a slurry, into hot air, and instantaneously deprives moisture from the fine droplets of the material to be dried to obtain a granular dried product, With this spray dryer, the slurry of the glaze raw material powder is sprayed into hot air, the obtained dried product is classified with a sieve, and the granular material having a target particle diameter is recovered to form a nucleator. .

  The stirring blade type powder mixing stirrer is a container body, a stirring portion provided inside the container body, a rotatable shaft portion, and a plurality of stirring blades radially connected from the shaft portion; And a driving unit for supporting and rotating the shaft portion of the stirring unit. The dried glaze raw material powder is put into the container body of the powder mixing stirrer and mixed and stirred. At the same time, by adding a small amount of water to the stirring glaze raw material powder, a powder granule of the glaze raw material powder is formed, and the obtained granule is classified by a sieve to obtain a granule having a target particle size. The body may be recovered and used as a nucleator.

  In addition, the granular material granulated as described above is not used as a nucleation body as it is, and the granular material is temporarily set at a suitable temperature (a temperature at which the granular material is not densely sintered or vitrified). It is good also as baking and making it semi-sinter and making the said semi-sintered body into a nucleation body.

  Note that the glaze raw material powder may be a single powder of the glaze raw material powder containing the same type of metal as the metal contained in the crystals to be precipitated, not the mixed powder as described above. In this case, granulation may be performed as in the case of the mixed powder.

  Here, the glaze raw material powder contains the same type of metal as the metal contained in the crystal to be precipitated. The metal element which is a component element of the compound (crystal) that the glaze raw material powder is to be precipitated from the crystal habit. It contains or contains a compound containing the same metal element as the main component.

That is, if the crystal to be precipitated is a crystal containing zinc (Zn), it is a glaze raw material powder containing zinc (Zn), such as zinc white (ZnO) powder, and the crystal to be precipitated is calcium (Ca). In the case of containing crystals, glaze raw material powder containing calcium (Ca), for example, lime (CaCO ₃ ) powder, wollastonite (CaSiO ₃ ) powder, dolomite (CaCO ₃ · MgCO) powder, etc. Is a glaze raw material powder containing magnesium (Mg), such as dolomite (CaCO ₃ · MgCO) powder, talc (3MgO · 4SiO ₂ · H ₂ 0) powder, etc. If the crystal to be precipitated is a crystal containing titanium (Ti), it is titania (TiO ₂ ) powder or the like.

Further, the other glaze raw material powder is a glaze raw material powder that does not contain the metal contained in the crystal to be precipitated. If the metal contained in the crystal to be precipitated is zinc, for example, lime, wollastonite, feldspar (Na, K) , Ca, Ba) (Si, Al) ₄ O ₈ ), alumina (Al ₂ O ₃ ), silica (SiO ₂ ), etc., and if the metal contained in the precipitated crystals is calcium, for example, feldspar, alumina, silica If the metal contained in the precipitated crystal is magnesium, for example, lime, wollastonite, feldspar, alumina, silica, etc. If the metal contained in the precipitated crystal is titania, for example, lime, wollastonite, feldspar, etc. , Alumina, silica and the like.

  Thus, by blending the glaze raw material powder containing the same type of metal with the metal contained in the crystal to be precipitated and the other ceramic raw material powder, the same type of metal as contained in the crystal to be precipitated Compared to the case of a single powder of glaze containing metal, the behavior of the nucleation body during firing (start of melting, speed of melting, influence on crystal habit, etc.) is more stable and it is easier to control crystal precipitation. Become.

  Next, a base material forming body is formed (second step S12 which is a base material forming body forming step). That is, the kneaded clay powder and the plurality of nucleating bodies formed in the previous step (S11) are blended and molded to produce a molded body (base material forming body).

  The clay is the same as that of general ceramic products, for example, ceramic tiles, ceramic eating and drinking devices, ceramic vases, and the like. In other words, one or two or more ceramic raw materials such as porcelain stone, wax stone, feldspar, lime, wollastonite, clay, kaolin, silica stone, and alumina are selected and blended, and the blend is pulverized and mixed with a ball mill or the like. Prepared.

  The mixing ratio of the ceramic raw material in the clay is appropriately determined in consideration of various conditions such as the firing temperature in the subsequent process, the thermal expansion coefficient of the formed body (base material forming body), and the thermal expansion coefficient of the crystal habit to be combined. That's fine.

  In this way, by blending and molding the clay and the nucleation body, as shown in FIGS. 4 and 5, in the clay (base part) 20 molded into the base shape of the product. A plurality of nucleation bodies 30 are scattered, and a part of the scattered nucleation bodies 30 is exposed on the surface to be treated of the molded body.

  In addition, the granular nucleation body and the clay powder are easy to mix homogeneously, whereby the nucleation body is uniformly dispersed in the molded body, and on the surface to be coated, The exposed nucleation bodies will be distributed uniformly.

  Further, since the nucleation body becomes a nucleation body by firing and induces the precipitation of crystals, the number of nucleation bodies exposed on the surface to be coated of the base material formation body is the number of crystals to be precipitated. Affects the overall view of the pattern formed by the crystals. Therefore, the blending ratio of the clay and the nucleation body may be appropriately determined in consideration of the overall view of the target pattern.

  The base material may have a multi-layer structure. For example, in the case of a two-layer tile base material, the front side (upper side) is not blended with the nucleation body in the clay forming the back side (lower side) layer. By blending the nucleation body only in the layer, an equivalent crystal pattern can be formed with a smaller number of nucleation bodies than in the case of a single-layer substrate.

  In addition, the molded body molded as described above is not used as a base material formed body as it is, but the molded body is appropriately baked at a temperature (a temperature at which the molded body is not densely sintered or vitrified). The obtained baking base may be used as a base material forming body.

Next, crystal habit is applied to the surface to be applied of the substrate forming body formed in the previous step (S12) (third step S13, which is an application step). As the crystal habit, zinc crystal habit containing zinc white (ZnO), diopside crystal habit containing dolomite (CaCO ₃ .MgCO ₃ ), titanium crystal habit containing titania (TiO ₂ ), bone ash ( Examples include bone ash and iron oxide crystallized soot containing 3CaO · P ₂ O ₃ ). That is, the crystal habit contains the metal contained in the crystal to be precipitated. For example, if the crystal to be precipitated contains zinc (Zn), it contains zinc white (ZnO). If the crystal to be precipitated is a crystal containing calcium (Ca), a zinc ash containing dolomite (CaCO ₃ · MgCO ₃ ) or bone ash containing bone ash (3CaO · P ₂ O ₃ ) If it is an iron oxide crystal habit and the crystal to be precipitated is a crystal containing magnesium (Mg), it is a diopside crystal habit containing dolomite (CaCO ₃ · MgCO ₃ ), and the crystal to be precipitated is a crystal containing titanium (Ti) if, the titanium crystal glaze containing titania (TiO _2).

  As the blending raw material of each of these cocoons, feldspar, lime, zinc white, silica and the like are mentioned for zinc crystal cocoons, feldspar, dolomite, silica and the like are mentioned for diopside crystal cocoons, Examples of feldspar, lime, zinc white, kaolin, silica stone, and titania. Examples of bone ash and iron oxide crystal habit include feldspar, talc, barium carbonate, kaolin, silica, bone ash, and the like.

  The raw material blending ratio in each crystal kneaded may be appropriately determined in consideration of the firing conditions, the thermal characteristics of the base material forming body to be combined, etc., as in the case of the kneaded clay.

  As the glazing method, for example, a conventional glazing method such as a spray method or a waterfall method can be applied, but a glaze sheet may be used instead.

  A glaze sheet is a slurry in which crystal habit is suspended in water, a water-soluble binder is added, and this is mixed and stirred to prepare a sheet-forming slurry. The sheet-forming slurry is formed into a sheet by a doctor blade method. After being molded, it is dried to remove moisture. That is, the glaze sheet is obtained by forming crystal habit into a sheet shape, and primary powders constituting the crystal habit are bound together by a binder.

  At the time of glazing, the glaze sheet may be attached to the surface of the substrate forming body, and the binder contained in the glaze sheet can be crimped by simply pressing the glaze sheet against the substrate forming body. What is necessary is just to make it like that, and you may make it affix through suitable glue, such as Na-CMC aqueous solution.

  Further, the glazing with this glaze sheet is easy to deal with irregular glazing. For example, in the case of a tile having a glaze layer, the glaze layer is generally provided in the entire area of the front surface portion of the base material (the surface portion on the opposite side of the surface portion bonded to the work surface such as a wall base or floor base). Although it is formed, for example, when it is desired to form the glaze layer only on a part of the base surface side surface portion, in the conventional glazing method, the portion (surface to be glazed) where the glaze layer of the base material surface side surface portion is to be formed is excluded. It is necessary to apply a masking treatment to the exposed portion with a release paper or the like, and then apply glazing, and then remove the release paper and fire. That is, in the conventional method, not only is it time-consuming, but when removing the release paper, a part of the glazed glaze may be peeled off to cause a defect. Therefore, in the present invention, by using the glaze sheet, the above-described trouble is not required and the occurrence of the above-mentioned defects can be prevented.

  In other words, by cutting the glaze sheet or the like, paste the glaze sheet section (this is referred to as the “glaze sheet section”) prepared in approximately the same shape as the surface to be coated, and paste the glaze sheet section. A tile in which a glaze layer is formed only on a part of the surface portion on the front side of the substrate can be obtained simply by firing the already formed substrate forming body.

  Further, for example, a plurality of types of glaze sheet sections having different firing colors (that is, sections of a plurality of glaze sheets containing pigments, and a plurality of types of glaze sheets having different blending of pigments contained in each glaze sheet) Slices) and pasting each glaze sheet slice to the desired location on the base material, glaze layers with different colors are arranged in the desired form, and in each glaze layer, crystals are deposited and patterns appear In other words, according to this glazing method, it is possible to easily manufacture a ceramic product having a unique texture not found in conventional products.

  Next, the firing step (fourth step S14) for firing the glazed product obtained in the previous step (S13) will be described. First, the substrate forming body is sintered, and the temperature is raised to a temperature equal to or higher than the temperature at which the crystal habit melts, and the maximum temperature is maintained (first step). Next, the temperature is lowered from the maximum temperature to a temperature range in which crystals precipitate, and the crystal precipitation temperature range is maintained (second step). Finally, the temperature is lowered to room temperature (third step).

  Here, the precipitation of crystals will be described by taking the case of zinc crystal soot as an example. By calcination as described above, the zinc white that is excessively contained in the zinc crystal cake is melted in the melt in the first step and is scattered on the surface to be coated of the base material forming body. Similarly, the nucleated body melts.

  The above-mentioned “excessive zinc white” means zinc white necessary to supply the amount of zinc component necessary for melting the zinc crystal soot at the temperature at which the zinc crystal soot is fired. The amount of zinc component required for the zinc crystal soot to be melted is more than the amount of zinc in the zinc crystal soot, for example, the potassium component in the zinc crystal soot. It is a necessary amount of a zinc component which can be calculated from a flux component other than a zinc component such as a sodium component and a calcium component, an alumina component, a silica component and the like using the Zegel formula.

  Then, by lowering the temperature in the second step, the zinc in the glaze melt phase becomes supersaturated, and particularly in the site where the nucleation body is scattered, the molten zinc derived from the nucleation body causes another site. Compared with the above, the zinc concentration is locally high, and the portion (nuclear body) where the zinc concentration is locally high is likely to precipitate crystals than the other portions.

Therefore, first, an extremely fine crystal (willemite: 2ZnO · SiO ₂ ) is precipitated at the core part, and this is used as a core, and subsequently, zinc derived from the crystal habit is deposited on the surface of the crystal (core) on which the crystal is deposited first. This is continuous, and the crystal grows radially around the nucleus. In addition, although a crystal | crystallization precipitates in a glaze layer, specifically, it precipitates in the inside of a glaze layer.

  That is, by maintaining the crystal precipitation temperature range in the second step, the crystals precipitated due to the nuclei are aged and develop a pattern with a size that can be observed with the naked eye.

  In addition, the part exposed to the to-be-glazed surface of the base-material formation body in a nucleation body and the part embedded in the base-material formation body in a nucleation body are the behavior in a baking process (4th process S14). Depending on whether the melting point of the nucleation body is below the maximum temperature in the first step of the firing process (low melting point) or exceeds the maximum temperature in the first step (high melting point). The effects on body behavior and crystal precipitation are different.

  First, the case of a low melting point nucleation body will be described. In the low melting point nucleation body, the entire nucleation body is melted in the first step of the firing step, and in the second step, the substrate formation body is covered. As described above, the portion exposed on the glazed surface forms a nucleus and precipitates crystals from the crystal habit, and also precipitates crystals from the nucleus itself.

  In other words, a compound containing zinc derived from the crystal habit as a component is generated and crystallized, and a compound containing zinc derived from the nucleus as a component is generated and crystallized into a crystal and nucleus derived from the crystal habit. It grows together with the crystal of origin.

  In addition, the component contained in the nucleator and not involved in the generation of the compound to be crystallized is solidified, vitrified and integrated with the glaze layer in the third step. Components contained in the portion exposed on the glazed surface that are not involved in the formation of the crystallizing compound are not visible, and the pattern can be made more beautiful.

  Further, the portion of the low melting point nucleation body that has been buried in the base material formation body is melted as described above in the first step, and the temperature is lowered in the second step and the third step, thereby solidifying. Thus, a vitreous agglomerate is formed. In addition, regarding the part not participating in the formation of crystals in the nucleation body partly exposed from the surface of the base material, the exposed part is vitrified to form a part of the glaze layer (in addition, one part from the surface of the base material). The portion involved in the formation of crystals in the nucleation body where the portion is exposed is crystallized). Therefore, it can be said that the vitrified agglomerates inside the exposed portion (that is, in the base material) are in contact with the glaze layer.

  That is, when manufactured with a low melting point nucleation body, a plurality of agglomerates of vitrified nucleation body are scattered in the base material after firing (that is, contained in the crystal precipitated in the base material). There are a plurality of agglomerates containing the same type of metal as the metal). Among them, some of the agglomerates that are directly under the glaze layer are in contact with the glaze layer. The crystal grows and develops a pattern so as to spread radially around the contact point or its vicinity, and the radial pattern is the deepest part in the glaze layer by having the pattern formed in this way. It is formed on the side (base material side), and a three-dimensional feeling and a deep taste are increased in the glaze layer, and a texture excellent in visual appeal effect is created.

  Next, the case of a high melting point nucleator will be described. In the first step and the second step of the firing process, sintering of the entire nucleation body proceeds, but the portion that has been exposed on the surface of the substrate forming body is contained in the nucleation body. Zinc (or zinc contained in the nucleator and some of the components other than the surrounding zinc) is melted by contact with the molten crystal habit, and the molten zinc becomes nucleated As a result, a site (nuclear body) having a locally high zinc concentration is formed in the molten crystal habit.

  In this way, there is a region where the zinc concentration is locally high in the molten crystal habit, and a fine solid that is not melted in the molten crystal habit (mainly components other than zinc in the nucleation body). Sintered as a component), it becomes easy for crystals to precipitate at the interface between the portion with a high zinc concentration and the fine solid, as in the case of the low melting point nucleator. A compound containing zinc derived from the crystal habit is generated and crystallized, and a compound containing zinc derived from the nucleus is generated and crystallized, and the crystal derived from the crystal habit and derived from the nucleus It grows as a single crystal.

  In addition, the component contained in the nucleator and not involved in the generation of the compound to be crystallized remains in the center of the pattern as a fine sintered body (the fine solid).

  Further, the portion buried in the base material forming body in the nucleation body is sintered in the first step and the second step to form a non-glassy (considered ceramic) agglomerate. In addition, about the part which does not participate in the production | generation of the crystal | crystallization in the nucleation body which one part exposed from the surface of the base material, an exposed part forms a part of glaze layer as non-glassy (in addition, from the surface of a base material) The part involved in the formation of crystals in the partially exposed nucleation body is crystallized). Therefore, it can be said that the non-glassy agglomerates inside the exposed portion (that is, in the base material) are in contact with the glaze layer.

  In other words, when manufactured with a high melting point nucleation body, a plurality of nucleation bodies are scattered as non-glassy agglomerates in the base material after firing (that is, contained in the crystal precipitated in the base material). There are a number of agglomerates containing the same type of metal as the metal that is present). Among them, some of the agglomerates that are directly under the glaze layer are in contact with the glaze layer. The crystal grows and develops a pattern so as to spread radially around the contact point or the vicinity thereof, and by having the pattern formed in this way, the radial pattern is the deepest in the glaze layer. Formed on the part side (base material side), the three-dimensional effect and deepness of the glaze layer are increased, and a texture excellent in visual appeal effect is created.

  Note that crystals do not precipitate at all if nuclei are not present, and even when nuclei are not present in the glaze melt phase, for example, if the composition of crystal habits and firing conditions are optimally adjusted, crystals will precipitate. However, if the aging time is long, the crystal grows to a size that can be observed with the naked eye. However, in this case, the probability of crystal precipitation is significantly reduced due to slight deviations in the firing conditions, and it takes a long time to grow the crystal. Therefore, in the present invention, the nuclei derived from the nucleation body reliably precipitate the crystal and increase the growth rate of the crystal. By reliably depositing the crystal, the product yield is improved, and the crystal By growing in a short time, the firing time can be shortened, the fuel cost can be reduced, and the manufacturing cost can be reduced.

  Next, the present invention will be described in more detail with reference to examples.

  First, zinc white powder, feldspar powder, and water were put into a ball mill, mixed and stirred, and finely polished to a suitable particle size to produce a slurry of glaze raw material powder. The blending ratio of zinc white powder and feldspar powder was 66.7% by weight of zinc white powder and 33. 3% by weight.

  Next, the glaze raw material powder slurry is dried, and the resulting dried product is coarsely pulverized and then extruded from a sieve having an aperture of 0.5 mm. All were recovered as nucleators.

  Next, the clay powder for porcelain tiles granulated by a spray dryer and the nucleation body are blended, and the blend is mixed by a rotary drum mixer, and then a mold for tile molding is prepared. The resulting molded body (tile fabric) was used as a substrate forming body. Regarding the blending ratio of the kneaded clay powder and the nucleating body, the nucleating body was 0.3% by weight with respect to 100% by weight of the whole kneaded clay powder.

  Then, by a spray method, crystal glazing was applied to the surface of the tile fabric to be applied, and the glazed product was baked to obtain a tile having a pattern of precipitated crystals. Regarding the blending of crystal habit, the weight ratio of zinc white is 23.8 wt%, feldspar is 47.6 wt%, lime is 9.5 wt%, and quartzite is 14.3 wt% with respect to the entire crystal habit. %, And barium carbonate was 4.8% by weight.

  As for the firing conditions, the substrate forming body is sintered and porcelain from room temperature, and the temperature is raised to 1240 ° C., which is a temperature equal to or higher than the melting temperature of the crystal habit, and the maximum temperature is increased to 1.5 hours. After holding, the temperature was lowered to 1120 ° C., which is a temperature range in which crystals precipitate, and the temperature was held for 3 hours, and then lowered to room temperature.

  In the tile obtained in this example, as shown in FIG. 1, the glaze layer was formed in the entire region of the surface of the base material, and the precipitated crystals were dispersed almost uniformly throughout the glaze layer. The pattern formed by the crystals was expressed throughout the glaze layer.

  First, zinc white powder, feldspar powder, and water were put into a ball mill, mixed and stirred, and finely polished to a suitable particle size to produce a slurry of glaze raw material powder. The blending ratio of zinc white powder and feldspar powder was 66.7% by weight of zinc white powder and 33. 3% by weight.

  Next, the glaze raw material powder slurry is dried, and the resulting dried product is coarsely pulverized and then extruded from a sieve having an aperture of 0.5 mm. All were recovered as nucleators.

  Next, the clay powder for porcelain tiles granulated by a spray dryer and the nucleation body are blended, and the blend is mixed by a rotary drum mixer, and then a mold for tile molding is prepared. The molded body (tile fabric) was baked and dry-molded, and the obtained tile substrate was used as a substrate forming body. Here, the tile substrate is obtained by firing only the tile fabric (molded body) at a temperature lower than the maximum temperature in the subsequent firing step (baking step for precipitating crystals in the crystal cake). That is, the base material forming body which is a tile base is in a completely sintered state as a porcelain, and has some porosity and water absorption. In addition, about the mixture ratio of a kneaded clay powder and a nucleation body, a nucleation body was 0.3 weight% with respect to the whole 100 weight% of a kneaded clay powder by weight ratio.

  Next, a water-soluble binder is added to the slurry in which the crystal habit is suspended in water, mixed and stirred to prepare a sheet-forming slurry, and this sheet-forming slurry is formed into a sheet by the doctor blade method The glaze sheet was prepared by drying. Regarding the blending ratio of the crystal habit and the binder, the crystal habit was 98% by weight and the binder was 2% by weight with respect to the entire crystal habit and binder. As for the blending of crystal habit, the ratio of zinc white is 23.8 wt%, feldspar is 47.6 wt%, lime is 9.5 wt%, and quartzite is 14.4 wt% with respect to the entire crystal habit. 3 wt% and barium carbonate were 4.8 wt%.

  Next, the above glaze sheet is cut to produce three substantially triangular glaze sheet sections having different sizes, and each glaze sheet section is individually attached to the front side surface portion of the same tile substrate. The crystallized glazing was applied to the base material forming body, and the glazed product was fired. As firing conditions, the substrate forming body is sintered and porcelain from room temperature, and the temperature is raised to 1240 ° C., which is higher than the melting temperature of the crystal habit, and the maximum temperature is maintained for 1.5 hours. After that, the temperature was lowered to 1120 ° C., which is a temperature range in which crystals precipitate, and the temperature was maintained for 3 hours, and then lowered to room temperature.

  In the tile obtained by this example, as shown in FIG. 2, the glaze layer is partially formed at three locations on the surface of the base material, and the precipitated crystals are substantially homogeneous over the entire area of each glaze layer. The pattern which was disperse | distributed and was formed of the crystal | crystallization was expressed in the whole area of each glaze layer. In other words, the pattern formed by the crystals is limitedly expressed within a certain range at a plurality of locations on the front side of the porcelain tile, and a tile having a new texture not found in the conventional product can be obtained. In FIG. 2, the region where the pattern does not appear does not appear because the crystal habit is not applied.

  As described above, according to the method for producing a ceramic product according to the present invention, it is easy to mechanize the production of a ceramic product having a pattern formed by crystals deposited on the glaze layer, and the production by the mechanization of the work. Cost can be reduced.

  That is, the method of blending and molding two or more compounds to be blended is easy to mechanize, and such a method is a conventional method for attaching a nucleation body, that is, nucleation. Compared to the method of suspending the body in water and including this suspension in a water absorbent body such as a brush or sponge and attaching it to the glazed surface by hand, it is less expensive and less expensive to manufacture. Is possible.

  In addition, due to the mechanization of work, there is less variation in the degree of dispersion of nucleation bodies between the plurality of base material formation bodies compared to the above-mentioned manual work, and the degree of dispersion is leveled. A ceramic product having the same overall view can be stably obtained with good reproducibility without greatly differing.

  Moreover, since the kneaded material powder and the powdery powder material (nucleating body) are blended to form a molded body (base material forming body), both the compounds to be blended are powdery. Therefore, the nucleation body and the clay powder can be mixed homogeneously and dry-type pressure molding can be performed, whereby the nucleation body is more spread over the entire surface to be coated of the base material formation body. Since it is uniformly distributed, it is possible to obtain a ceramic product in which the crystal pattern is more evenly distributed throughout the glaze layer.

  In addition, since the green body is fired in a state where the unfired nucleation body and the unfired crystal habit are in contact with each other, the crystals are more precipitated by being affected by each other during firing. Easy to promote crystal growth.

  In addition, since the glaze raw material powder is a mixed powder containing a glaze raw material powder containing the same type of metal as the metal contained in the crystal to be precipitated, and other glaze raw material powders, it is precipitated. Compared to the case of a single powder made of a glaze raw material containing the same type of metal as the metal contained in the crystal, the behavior of the nucleation body during firing (onset of melting, speed of melting, effect on crystal habit, etc.) In order to stabilize, it becomes easy to control the precipitation of crystals by setting the crystal precipitation temperature, holding time, etc. in the firing process, and this further stabilizes the product quality.

  In addition, since the metal contained in the crystal to be precipitated is zinc, zinc white can be used as a zinc supply source. Since zinc white is a glaze raw material with stable quality, the crystal precipitation state is It becomes more stable.

  Also, in the firing process, the glaze was formed into a sheet shape to produce a glaze sheet, and the glaze sheet was affixed to the surface of the substrate forming body, so that it was easy to handle irregular glazing. It is. For example, when it is desired to partially form the glaze layer by dispersing it at a plurality of locations on the surface of the substrate, the shape of each of the above locations (surfaces to be treated) where the glaze layer is to be formed by cutting the glaze layer is substantially the same. By simply forming a glaze sheet section in the shape and sticking this glaze sheet section to each of the above-mentioned glazed surfaces, it is possible to reliably and easily cope with complicated glazing, and thereby, the glaze layer portion and the non-glaze layer It is possible to create a unique texture in which the portion is mixed and the glaze layer portion has a pattern of precipitated crystals.

  Further, the ceramic product manufactured by the manufacturing method of the present invention has a texture and a taste different from those of conventional products by having a pattern of a plurality of crystals that are homogeneously distributed in the glaze layer.

Step of forming C crystal S11 nucleator (first step)
S12 Substrate forming body forming step (second step)
S13 Glazing process (third process)
S14 Firing step (fourth step)
20 Base 30 Nucleus

Claims (6)

Manufacture of a ceramic product comprising a ceramic substrate, a glassy glaze layer formed on at least a part of the substrate surface, and crystals formed on the glaze layer to form a pattern A method,
A first step of forming a nucleator containing a metal of the same type as a metal contained in a crystal to be precipitated, which is a nucleator that forms a nuclei by firing;
In a second step of forming a base material forming body in which a crystal habit is applied to the surface to be coated, in a base material forming body that becomes a base material by firing, clay and a nucleation body formed in the first step; Is formed into a base material body having a base part derived from the clay and a plurality of nucleation bodies scattered in the base part, and a part of the nucleation body is covered. A second step of forming a substrate forming body exposed on the glazed surface;
A third step of applying a crystal glaze containing a metal contained in a crystal to be deposited to a glaze surface of the base material forming body in a crystal glaze that becomes a glaze layer by firing;
In the fourth step of firing the glazed product obtained in the third step, the substrate forming body is sintered, and the temperature is raised to a temperature equal to or higher than the temperature at which the crystal habit is melted, and the first temperature is maintained. The components contained in the crystal habitat are caused by the nucleus from the nucleator by lowering the temperature from the maximum temperature in the step and the first step to the temperature range in which the crystals are precipitated and maintaining the crystal precipitation temperature range. A method for producing a ceramic product, comprising: a fourth step comprising: a second step of precipitating a crystal generated from the above and aging the crystal to develop a pattern. The core forming body is a granule granulated from the glaze raw material powder, the kneaded material is a kneaded clay powder, and the base material forming body is formed by blending the granule and the kneaded powder. The method for producing a ceramic product according to claim 1, wherein the method is a molded body. In the third step, the crystal glaze is formed into a sheet shape to produce a glaze sheet, and the glaze sheet is affixed to the surface to be coated of the base material forming body, whereby the crystal glaze is applied to the surface of the base material forming body. The method for producing a ceramic product according to claim 1, wherein the method is applied to the ceramic product. A ceramic product comprising a ceramic substrate, a vitreous glaze layer formed on at least a part of the substrate surface, and crystals that form a pattern with crystals deposited on the glaze layer. And
In the manufacturing process,
A nucleation body that forms nuclei by firing, a nucleation body that contains the same type of metal as the metal contained in the crystals to be deposited, and a base material formation body that becomes a base material by firing. A base material forming body on which crystal habit is applied, and by mixing and forming kneaded clay and the nucleating body, a base portion derived from the kneaded clay, and a plurality of the base portion In a base material forming body having interspersed nucleation bodies, forming a base material formation body in which a part of the nucleation body is exposed on the surface to be coated, and crystal glaze that becomes a glaze layer by firing, Applying crystal habit containing metal contained in the crystals to be deposited on the surface of the base material forming body, heating the glazed product, sintering the base material forming body, and at least the temperature at which the crystal habit melts After maintaining the maximum temperature, the temperature is decreased to a temperature range where crystals are precipitated, By maintaining the precipitation temperature range, the crystal formed from the component contained in the crystal habit is precipitated due to the nucleate derived from the nucleator, and the pattern is matured to express the pattern. Ceramic products. A ceramic product comprising a ceramic substrate, a glassy glaze layer formed on at least a part of the substrate surface, and a crystal that is deposited on the glaze layer to form a pattern,
In the base material, a plurality of agglomerates containing the same type of metal as the metal contained in the precipitated crystals are scattered,
A ceramic product characterized in that the pattern spreads radially around the contact point between the granule in contact with the glaze layer in the substrate and the glaze layer, or the vicinity thereof. 6. The ceramic product according to claim 5, wherein the metal contained in the precipitated crystal is zinc, and a main component of the crystal is willemite (2ZnO.SiO ₂ ).