KR102352357B1 - Manufacturing method of ceramic tile using the glaze composition for forming glaze layer having high contact angle and excellent hardness properties - Google Patents

Abstract

The present invention provides a glaze composition for forming the glaze layer in a porcelain tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the engobe layer, ceria (CeO ₂ ) and neodymium A glaze composition comprising 0.1 to 10% by weight of at least one oxide powder selected from the group consisting of oxides (Nd ₂ O ₃ ), 88 to 98% by weight of a glass frit powder, and 1 to 10% by weight of a kaolin powder; It relates to a method of manufacturing a ceramic tile using the same. According to the present invention, a glaze layer capable of self-cleaning can be formed due to a high contact angle characteristic and a glaze layer having excellent hardness characteristics can be formed.

Description

The manufacturing method of ceramic tile using the glaze composition for forming a glaze layer having high contact angle and excellent hardness properties

The present invention relates to a glaze composition and a method for manufacturing a porcelain tile using the same, and more particularly, to form a glaze layer capable of self-cleaning due to a high contact angle characteristic and to form a glaze layer having excellent hardness characteristics The present invention relates to a glaze composition that can be used and a method for manufacturing self-cleaning ceramic tiles using the same.

Ceramic tiles are widely used as interior and exterior materials for buildings due to their excellent durability and aesthetics through surface control.

Glazed ceramic tiles with a glaze layer on the surface can be manufactured into various functional ceramic tiles by controlling the composition and microstructure of the glaze.

Since ceramic tiles are used as interior and exterior materials of buildings, cleanliness is a very important indicator, and therefore, self-cleaning functional tiles are constantly in demand.

In self-cleaning of ceramic tiles, many studies have been conducted in the past to secure a hydrophilic surface through _{TiO 2 coating to remove foreign substances from the surface.} However, in _{the case of the TiO 2} hydrophilic coating, a coating layer is prepared through an additional process after product firing, and there is a disadvantage in that UV irradiation (Ultraviolet ray irradiation) is required. In particular, it is a big problem that the durability of the _{TiO 2 hydrophilic coating layer is weak.}

Another strategy for self-cleaning is to conveniently remove foreign substances such as dust from the hydrophobicity surface through the flow of water droplets.

The surface glaze of architectural ceramic tiles containing silica (SiO2) as the main component has hydrophilicity, and the water repellency through fluorine-based water-repellent coating agent treatment does not have durability as an outdoor ceramic tile. In addition, there is a problem of cost increase due to the addition of the coating process.

Republic of Korea Patent Publication No. 10-2015-0030733

The problem to be solved by the present invention is a glaze composition capable of forming a glaze layer capable of self-cleaning due to a high contact angle characteristic and a glaze layer having excellent hardness characteristics, and self-cleaning ceramic using the same To provide a method for manufacturing a tile.

The present invention provides a glaze composition for forming the glaze layer in a porcelain tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the engobe layer, ceria (CeO ₂ ) and neodymium A glaze composition comprising 0.1 to 10% by weight of at least one oxide powder selected from the group consisting of oxides (Nd ₂ O ₃ ), 88 to 98% by weight of glass frit powder, and 1 to 10% by weight of kaolin powder to provide.

The glaze composition may further include 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material.

The glaze composition may further include 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material.

The kaolin powder may be formed of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported.

In addition, the present invention provides the steps of forming an engobe layer on the upper part of the molded and primary fired base layer, applying and drying a glaze composition on the upper engobe layer to form a glaze layer, and the resultant of the glaze layer being formed. and a second firing step, wherein the glaze composition comprises 0.1 to 10% by weight of at least one oxide powder selected from the group consisting of _{ceria (CeO 2} ) and neodymium oxide (Nd ₂ O _{3 ), and 88 to 98 glass frit powder} It provides a method for producing a ceramic tile, characterized in that it comprises a glaze raw material containing 1 to 10% by weight of kaolin powder and by weight.

The glaze composition may further include 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material.

The glaze composition may further include 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material.

The kaolin powder may be formed of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported.

The kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported is a kaolin mixed solution by adding kaolin raw powder and acid to a first solvent to adjust the pH to between 0.1 and 2.5. Forming a metal precursor, dissolving a metal precursor in a second solvent to form a metal precursor mixed solution, mixing the metal precursor mixed solution and the kaolin mixed solution, and adding a basic material to adjust the pH between 4.0 and 8.0 Forming a metal precursor-kaolin mixed solution, removing the solvent and washing the metal precursor-kaolin mixed solution using an evaporator to obtain powders, and drying the washed powders and heat-treating the dried powder in a reducing gas atmosphere to obtain a kaolin powder on which metal nanoparticles are supported.

The metal precursor may include at least one salt selected from the group consisting of Cu nitrate, Cu sulfate, Ni nitrate, and Ni sulfate.

Preferably, the Cu precursor mixed solution is mixed with the kaolin mixed solution so that the metal precursor comprises 5 to 20 parts by weight based on 100 parts by weight of the kaolin raw material powder.

According to the glaze composition of the present invention, it has a high contact angle property, has excellent durability, and can form a glaze layer without the need for a process such as UV irradiation (ultraviolet ray irradiation), and the glaze layer is self-cleaning due to the high contact angle property -cleaning) may be possible.

Further, according to the glaze composition of the present invention, a glaze layer having excellent hardness properties can be formed.

According to the method for manufacturing a porcelain tile of the present invention, a glaze layer having a high contact angle characteristic is formed on the surface, so that self-cleaning is possible.

1 is a diagram illustrating a structure of a ceramic tile according to an example.
2 is a photograph showing the contact angle characteristics with respect to the glaze layer of the porcelain tile prepared according to Experimental Example 2.
3 is a photograph showing the contact angle characteristics with respect to the glaze layer of the porcelain tile prepared according to Experimental Example 3. Referring to FIG.
4 is a photograph showing the contact angle characteristics with respect to the glaze layer of the porcelain tile prepared according to Experimental Example 1. Referring to FIG.

Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings. However, the following examples are provided so that those of ordinary skill in the art can fully understand the present invention, and can be modified in various other forms, and the scope of the present invention is limited to the examples described below it is not going to be

When it is said that any one component "includes" another component in the detailed description or claims of the invention, it is not construed as being limited to only the component, unless otherwise stated, and other components are further added. It should be understood as being able to include

Hereinafter, nano is used to mean a size of 1 to 1000 nm as a size in nanometers, and nanopowder is used to mean a powder having a size of 1 to 1000 nm.

A glaze composition according to a preferred embodiment of the present invention is a glaze composition for forming the glaze layer on a porcelain tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the engobe layer. , ceria (CeO ₂ ) and neodymium oxide (Nd ₂ O ₃ ) 0.1 to 10% by weight of at least one oxide powder selected from the group consisting of, 88 to 98% by weight of glass frit powder and 1 to 10% by weight of kaolin powder Contains glaze raw materials.

The glaze composition may further include 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material.

The glaze composition may further include 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material.

The kaolin powder may be formed of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported.

A method of manufacturing a porcelain tile according to a preferred embodiment of the present invention comprises the steps of forming an engobe layer on an upper portion of a molded and primary fired base layer, and lubricating and drying a glaze composition on the upper portion of the engobe layer to form a glaze layer. and secondary firing of the resultant glaze layer formed thereon, wherein the glaze composition is at least one oxide powder selected from the group consisting of _{ceria (CeO 2} ) and neodymium oxide (Nd ₂ O _{3 ) 0.1 to 10} % by weight, glass frit powder in an amount of 88 to 98 wt%, and kaolin powder in an amount of 1 to 10 wt%.

The glaze composition may further include 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material.

The glaze composition may further include 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material.

The kaolin powder may be formed of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported.

The kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported is a kaolin mixed solution by adding kaolin raw powder and acid to a first solvent to adjust the pH to between 0.1 and 2.5. Forming a metal precursor, dissolving a metal precursor in a second solvent to form a metal precursor mixed solution, mixing the metal precursor mixed solution and the kaolin mixed solution, and adding a basic material to adjust the pH between 4.0 and 8.0 Forming a metal precursor-kaolin mixed solution, removing the solvent and washing the metal precursor-kaolin mixed solution using an evaporator to obtain powders, and drying the washed powders and heat-treating the dried powder in a reducing gas atmosphere to obtain a kaolin powder on which metal nanoparticles are supported.

The metal precursor may include at least one salt selected from the group consisting of Cu nitrate, Cu sulfate, Ni nitrate, and Ni sulfate.

Preferably, the Cu precursor mixed solution is mixed with the kaolin mixed solution so that the metal precursor comprises 5 to 20 parts by weight based on 100 parts by weight of the kaolin raw material powder.

Hereinafter, a glaze composition according to a preferred embodiment of the present invention will be described in more detail.

Porcelain tiles are generally used for building interiors, and are divided into wall tiles and floor tiles.

Porcelain tile is an eco-friendly building material made of soil, and has excellent strength and durability by firing at a high temperature of 1000℃ or higher.

Among porcelain tiles, wall tiles can not only maintain cleanliness by preventing contamination, but also add aesthetics and various functions by forming a glaze layer on the surface by applying the glaze composition. Accordingly, wall tiles are widely used as interior materials for living environments such as kitchens and floors as well as bathrooms.

1 is a view showing the structure of a ceramic tile.

Referring to FIG. 1 , the ceramic tile has a structure in which a base layer 110 , an engobe layer 120 , and a glaze layer 130 are sequentially stacked. A glaze composition according to a preferred embodiment of the present invention is a glaze composition for forming the glaze layer 130 on a ceramic tile.

Porcelain tile is glazed by mixing and molding a base material such as clay, and applying the engobe composition on the first fired base layer 110 to form the engobe layer 120, and apply the glaze composition on the engobe layer 120 to apply the glaze. After forming the layer 130, it is manufactured through secondary firing. In the case of manufacturing floor tiles from among ceramic tiles, the first firing process may not be performed.

The engobe layer 120 serves as an intermediate layer that can hide the color of the base layer 110 and control the thermal expansion of the base layer 110 and the glaze layer 130 . The engobe layer 120 preferably has a thickness of about 50 to 300 μm.

The glaze layer 130 serves to strengthen (protect) the surface of the porcelain tile, and to decorate (Decoration). The glaze layer 130 preferably has a thickness of about 100 to 200 μm. By making the glaze layer 130 have a high contact angle characteristic, self-cleaning may be possible. In the formation of the glaze layer 130 of the ceramic tile, it is possible to form the glaze layer 130 having a high contact angle characteristic by controlling the composition.

Since ceramic tiles are used as interior and exterior materials of buildings, cleanliness is a very important indicator, and therefore, self-cleaning functional tiles are constantly in demand.

In self-cleaning of ceramic tiles, many studies have been conducted in the past to secure a hydrophilic surface through _{TiO 2 coating to remove foreign substances from the surface.} However, there is a drawback that requires plastic products (secondary firing) be a hydrophilic coating TiO ₂ prepared by further processing and then, irradiated UV (Ultraviolet ray irradiation) In the case of TiO _2, a hydrophilic coating. In particular, it is a big problem that the durability of the _{TiO 2 hydrophilic coating layer is weak.}

Recently, research on the implementation of a hydrophobic coating layer of lotus petals and securing self-cleaning properties through this is being conducted. In general, products that realize hydrophobicity by coating a polymer material on the glaze surface of ceramic tiles have been published, but these products have a problem in durability.

Therefore, it is very important to maximize the hydrophobicity without additional processing by controlling the microstructure of the porcelain tile surface glaze, and to implement the formation of such a hydrophobic glaze layer by applying the porcelain tile mass production process (rapid firing process) as it is.

The inventors of the present invention added ceria (CeO ₂ ) and neodymium oxide (Nd ₂ O ₃ ), which are rare earth oxides, to the surface glaze of building porcelain tile, so as to have hydrophobicity even after high-temperature sintering process for porcelain tile production of 1000°C or higher. Additionally, a porcelain tile glaze with high surface hardness was developed.

A glaze composition according to a preferred embodiment of the present invention is a glaze composition for forming the glaze layer on a porcelain tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the engobe layer. , ceria (CeO ₂ ) and neodymium oxide (Nd ₂ O ₃ ) 0.1 to 10% by weight of at least one oxide powder selected from the group consisting of, 88 to 98% by weight of glass frit powder and 1 to 10% by weight of kaolin powder Contains glaze raw materials.

The glaze composition may further include 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material. The Zn powder preferably has an average particle diameter of 30 nm to 10 μm, more preferably 50 nm to 5 μm. When Zn powder is added to the glaze raw material, the contact angle can be increased by securing the hydrophobicity of the glaze, and also the whiteness (L ^* ) can be increased. When Cu powder or Ni powder is added, the color of the glaze layer shows metallic luster such as green or brown, so the white color of the glaze layer cannot be maintained. However, when Zn powder is added, the white color of the glaze layer is maintained. while increasing the whiteness.

The glaze composition may further include 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material. The Cu nanopowder preferably has an average particle diameter of 10 to 300 nm. The Ni powder preferably has an average particle diameter of 1 to 10 μm. Preferably, the Cu nanopowder constitutes 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder. When the glaze layer 130 is formed using a glaze composition in which Cu nanopowder-coated Ni powder is mixed, a high contact angle characteristic may be exhibited.

The kaolin powder may be formed of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported. By impregnating one or more metal nanoparticles selected from the group consisting of Cu and Ni in kaolin, which is a raw material for the glaze, it is possible to control the flatness, that is, roughness, and improve the surface hardness of the surface glaze, and at the same time, antifouling properties can be maintained. In addition, it is possible to improve the workability of the glaze application process on the green surface of the ceramic tile by improving the dispersion stability problem that occurs during the glaze manufacturing process due to the large difference in specific gravity from the existing glaze raw material.

According to the glaze composition of the present invention, it has a high contact angle property, has excellent durability and hardness properties, and can form the glaze layer 130 without the need for UV irradiation (ultraviolet ray irradiation), and the glaze layer 130 is Self-cleaning may be possible due to a high contact angle characteristic.

Hereinafter, a method for manufacturing a ceramic tile according to a preferred embodiment of the present invention will be described in more detail.

The ceramic tile has a structure in which a base layer 110 , an N solid layer 120 , and a glaze layer 130 are sequentially stacked. Porcelain tile is glazed by mixing and molding a base material such as clay, and applying the engobe composition on the first fired base layer 110 to form the engobe layer 120, and apply the glaze composition on the engobe layer 120 to apply the glaze. After forming the layer 130, it is manufactured through secondary firing. In the case of manufacturing floor tiles from among ceramic tiles, the first firing process may not be necessary.

In order to manufacture the porcelain tile having the above-described structure, first, a base material is mixed to form a base composition. The base material constitutes the basic skeleton of the ceramic tile. For example, the base material may include 8 to 15% by weight of limestone, 20 to 25% by weight of clay, 40 to 45% by weight of ceramics, 10 to 15% by weight of pyrophyllite, and 5 to 15% by weight of kaolin. For the mixing, various methods such as a ball mill, a planetary mill, and an attrition mill may be used.

Hereinafter, the mixing process by the ball mill method is demonstrated concretely. The base material is charged and mixed in a ball milling machine. The raw material is uniformly mixed by rotating it at a constant speed using a ball mill. The balls used in the ball mill may be made of ceramics such as alumina or zirconia, and all of the balls may be of the same size or may be used together with balls having two or more sizes. The size of the ball, the milling time, the rotation speed per minute of the ball mill, etc. are adjusted and mixed while grinding to the desired particle size. For example, in consideration of the particle size, the size of the ball may be set in the range of about 1 mm to 50 mm, and the rotational speed of the ball mill may be set in the range of about 100 to 500 rpm. The ball mill is preferably carried out for 1 to 48 hours in consideration of the size of the target particles.

The body composition may form a slurry (slurry), and in the body composition, the base material is dispersed in a solvent to form a solid content. In this case, it is preferable to contain 30 to 80 parts by weight of the solvent based on 100 parts by weight of the solid content in the body composition.

The body composition may be made of a granular powder for the body comprising 8 to 15% by weight of limestone, 20 to 25% by weight of clay, 40 to 45% by weight of ceramic stone, 10 to 15% by weight of pyrophyllite, and 5 to 15% by weight of kaolin have.

The body composition obtained by the above-described method is molded into a desired shape. The molding may use various methods, such as generally known pressure molding, injection molding, and the like. In addition, before the molding, a process of de-ironizing the base composition, a process of classifying and filtering, etc. may be additionally performed.

The molded result is first fired. The molded result is charged into a furnace such as an electric furnace, and a primary firing process is performed. It is preferable to keep the pressure inside the furnace constant during the primary firing. The primary firing is preferably made at a temperature of about 1000 to 1250 ℃. If the primary firing temperature is less than 1000°C, the thermal or mechanical properties of the ceramic tile may be poor due to incomplete firing, and if it exceeds 1250°C, energy consumption is high, which is uneconomical. The primary firing is preferably carried out in an oxidizing atmosphere (eg, oxygen (O ₂ ) or air (air) atmosphere). In the case of manufacturing floor tiles from among ceramic tiles, the primary firing process is not performed.

The engobe composition is applied on the upper portion of the base layer 110 formed by primary firing and dried to form the engobe layer 120 . An engobe composition is prepared to form the engobe layer 120 on the surface of the base layer 110 , and the engobe composition is applied to the surface of the molded and first fired base layer 110 and dried. The engobe composition is in a slurry state including a solid content such as clay and a solvent, and it is preferable that the solvent be contained in the engobe composition in an amount of 30 to 80 parts by weight based on 100 parts by weight of the solid content. For example, the solid content includes 45 to 75% by weight of glass frit, 2 to 15% by weight of feldspar powder, 10 to 30% by weight of silicate powder, 10 to 25% by weight of kaolin powder, and 0.1 to 10% by weight of zircon powder can do. The specific gravity of the engobe composition is preferably about 1.4 to 1.8, more preferably about 1.5 to 1.7. The engobe layer 120 is preferably formed to a thickness of about 50 to 300 μm. The engobe layer 120 serves as an intermediate layer that can hide the color of the base layer 110 and control the thermal expansion of the base layer 110 and the glaze layer 130 .

The glaze composition is applied on the engobe layer 120 and dried to form the glaze layer 130 . A glaze composition is prepared to form the glaze layer 130 on the engobe layer 120 , and the glaze composition is applied to the surface of the engobe layer 120 and dried. The glaze composition is in a slurry state including a solid content and a solvent, and it is preferable that the solvent be contained in the glaze composition in an amount of 30 to 80 parts by weight based on 100 parts by weight of the solid content. The glaze composition is a glaze composition for forming the glaze layer in a porcelain tile including a base layer, an engobe layer provided on the base layer, and a glaze layer provided on the engobe layer, ceria (CeO ₂ ) and Neodymium oxide (Nd ₂ O ₃ ) Contains 0.1 to 10% by weight of at least one oxide powder selected from the group consisting of, 88 to 98% by weight of glass frit powder, and 1 to 10% by weight of kaolin powder.

The glaze composition may further include 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material. The Zn powder preferably has an average particle diameter of 30 nm to 10 μm, more preferably 50 nm to 5 μm. When Zn powder is added to the glaze raw material, the contact angle can be increased by securing the hydrophobicity of the glaze, and also the whiteness (L ^* ) can be increased. When Cu powder or Ni powder is added, the color of the glaze layer exhibits metallic luster such as green or brown, and thus the white color of the glaze layer cannot be maintained. Whiteness can be increased while maintaining whiteness.

The glaze composition may further include 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material. The Cu nanopowder preferably has an average particle diameter of 10 to 300 nm. The Ni powder preferably has an average particle diameter of 1 to 10 μm. Preferably, the Cu nanopowder constitutes 0.1 to 25 parts by weight based on 100 parts by weight of the Ni powder. When the glaze layer 130 is formed using a glaze composition in which Cu nanopowder-coated Ni powder is mixed, a high contact angle characteristic may be exhibited.

The kaolin powder may be formed of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported.

The kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported may be prepared as follows.

A kaolin mixed solution is formed by adding kaolin raw material powder and acid to the first solvent to adjust the pH to between 0.1 and 2.5. The acid may be nitric acid, hydrochloric acid, sulfuric acid, acetic acid, a mixture thereof, or the like. The first solvent may be water (H ₂ O) or the like.

The metal precursor is dissolved in a second solvent to form a metal precursor mixed solution. The metal precursor may include at least one salt selected from the group consisting of Cu nitrate, Cu sulfate, Ni nitrate, and Ni sulfate. The second solvent may be water (H ₂ O) or the like.

The metal precursor mixed solution and the kaolin mixed solution are mixed, and a basic material is added to adjust the pH to between 4.0 and 8.0 to form a metal precursor-kaolin mixed solution. Preferably, the Cu precursor mixed solution is mixed with the kaolin mixed solution so that the metal precursor comprises 5 to 20 parts by weight based on 100 parts by weight of the kaolin raw material powder. The basic material may be NaOH, KOH, a mixture thereof, or the like.

The metal precursor-kaolin mixed solution is removed by using an evaporator to remove the solvent and washed to obtain powders. The washing may be performed using water (H ₂ O) or the like.

Dry the washed powders. The drying is preferably performed at a temperature of about 40 to 150 ℃.

The dried powder is heat-treated in a reducing gas atmosphere to obtain a kaolin powder on which metal nanoparticles are supported. The reducing gas atmosphere may be an H ₂ gas atmosphere or a gas atmosphere in which Ar gas and H ₂ gas are mixed. The heat treatment is preferably performed at a temperature of about 300 to 550 °C. It serves as a source for the formation of metal nanoparticles, which are metal precursors, and the metal precursor is changed into metal nanoparticles by the heat treatment.

By impregnating one or more metal nanoparticles selected from the group consisting of Cu and Ni in kaolin, which is a raw material for the glaze, it is possible to control the flatness, that is, roughness, and improve the surface hardness of the surface glaze, and at the same time, antifouling properties can be maintained. In addition, it is possible to improve the workability of the glaze application process on the green surface of the ceramic tile by improving the dispersion stability problem that occurs during the glaze manufacturing process due to the large difference in specific gravity from the existing glaze raw material.

The glaze layer 130 forms a vitreous film on the surface of the porcelain tile where micropores are present, thereby inducing enhancement of strength and reduction of absorption, and expressing unique color and texture. The lubrication method can be performed in various ways, for example, dipping the resultant product on which the engobe layer 120 is formed in the glaze composition, applying the glaze composition with a tool such as a brush, or spraying the glaze composition with a spray device, etc. may be used. can

The glaze layer 130 is preferably formed to a thickness of about 100 to 200㎛, more preferably about 120 to 150㎛. The thickness of the glaze layer 130 can be controlled by adjusting the glazing time, the number of lubrication, and the like of the glaze composition. According to the experimental example, the contact angle characteristics were also changed depending on the thickness of the glaze layer 130 , and in particular, when the glaze layer 130 had a thickness of about 100 to 150 μm, the contact angle characteristics were very excellent.

The resultant glaze layer 130 is formed by secondary firing to prepare the base layer 110, the engobe layer 120 provided on the base layer 110, and the glaze layer 130 provided on the engobe layer 120. To obtain a ceramic tile containing The resulting glaze layer 130 is charged into a furnace such as an electric furnace, and a secondary firing process is performed. It is preferable to keep the pressure inside the furnace constant during the secondary firing. The secondary firing is preferably made at a temperature of about 1000 to 1200 ℃. If the secondary firing temperature is less than 1000°C, the thermal or mechanical properties of the ceramic tile may be poor due to incomplete firing, and if it exceeds 1200°C, energy consumption is high, which is uneconomical. The secondary firing is preferably performed in an oxidizing atmosphere (eg, oxygen (O ₂ ) or air (air) atmosphere).

The glaze layer of the porcelain tile manufactured in this way may exhibit high contact angle characteristics. In addition, the glaze layer may exhibit a hardness higher than 7.0 GPa.

Hereinafter, experimental examples according to the present invention are specifically presented, and the present invention is not limited to the experimental examples presented below.

<Experimental Example 1>

In order to manufacture the base layer of ceramic floor tiles, 12 wt% of limestone, 23 wt% of clay, 42 wt% of ceramics, 13 wt% of pyrophyllite and 10 wt% of kaolin are mixed as raw materials, and after loading into a metal mold, 250 kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing under a pressure of cm 2 . The molded specimen was prepared to have a diameter of 30 mm. The molded specimen was first fired. The primary firing was performed as a rapid firing process in which a furnace was passed in a car-carriing manner. The maximum temperature of the primary firing was 1150° C., and the time of feeding was 50 minutes. The primary firing was performed in an air atmosphere.

In order to form the engobe layer, 60 wt% of glass frit, 5 wt% of feldspar, 17 wt% of silica, 15 wt% of kaolin and 3 wt% of zircon were prepared as raw materials. A 10 mm alumina ball is put in a ball mill container, and the raw material for forming the engobe layer and deionized water are charged, and then ball milling is performed at 300 rpm for 24 hours to wet mixing. After that, it was aged for 3 hours at room temperature to remove air bubbles (and left to stand) to form an engobe composition. The engobe composition was formed by mixing with the distilled water to form a solid content of 60%. The Ngobe composition was lubricated on the first calcined specimen using Belsee oil and dried for 6 hours.

A glaze composition was prepared by mixing 95% by weight of glass frit and 5% by weight of kaolin as glaze raw materials to form a glaze layer on the engobe layer. Put an alumina ball of 10 mm in a ball mill container, and charge the glaze raw material and deionized water so that the _{solid content (frit, kaolin and CeO 2 powder) is 60% by weight, then at 300rpm} After wet mixing by ball milling for 24 hours, the glaze composition was formed by aging (leaving it alone) at room temperature for 3 hours to remove air bubbles.

The composition of the glass frit used as a raw material for the glaze to form the glaze layer is shown in Table 1 below.

SiO ₂ Al ₂ O ₃ CaO Na ₂ O K ₂ O MgO TiO ₂ SrO B ₂ O ₃ Etc wt% 57.79 8.30 11.40 3.30 2.46 0.67 8.28 1.72 5.86 0.22

The glaze composition was spray-applied on the surface to which the Engobe composition was applied and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

Secondary firing was performed on the resultant glaze composition applied to obtain ceramic tiles. A porcelain tile was obtained by performing a rapid firing process in which the resultant glaze composition was applied through a furnace in a car-carrier manner. The maximum temperature of the secondary firing was 1050 ℃, and the time of feeding was 40 minutes. The secondary firing was performed in an air atmosphere.

<Experimental Example 2>

In order to manufacture the base layer of ceramic floor tiles, 12 wt% of limestone, 23 wt% of clay, 42 wt% of ceramics, 13 wt% of pyrophyllite and 10 wt% of kaolin are mixed as raw materials, and after loading into a metal mold, 250 kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing under a pressure of cm 2 . The molded specimen was prepared to have a diameter of 30 mm. The molded specimen was first fired. The primary firing was performed as a rapid firing process in which a furnace was passed in a car-carriing manner. The maximum temperature of the primary firing was 1150° C., and the time of feeding was 50 minutes. The primary firing was performed in an air atmosphere.

In order to form the engobe layer, 60 wt% of glass frit, 5 wt% of feldspar, 17 wt% of silica, 15 wt% of kaolin and 3 wt% of zircon were prepared as raw materials. A 10 mm alumina ball is put in a ball mill container, and the raw material for forming the engobe layer and deionized water are charged, and then ball milling at 300 rpm for 24 hours to wet mixing. After that, it was aged for 3 hours at room temperature to remove air bubbles (and left to stand) to form an engobe composition. The engobe composition was formed by mixing with the distilled water to form a solid content of 60%. The Ngobe composition was lubricated on the first calcined specimen using Belsee oil and dried for 6 hours.

A glaze composition was prepared by mixing 90% by weight of glass frit having the composition shown in Table 1, 5% by weight of kaolin, and _{5% by weight of CeO 2 powder as raw materials for glaze to form a glaze layer on the engobe layer.} The CeO ₂ powder had an average particle size of 2.1 μm. Put an alumina ball of 10 mm in a ball mill container, and charge the glaze raw material and deionized water so that the _{solid content (frit, kaolin and CeO 2 powder) is 60% by weight, then at 300rpm} After wet mixing by ball milling for 24 hours, the glaze composition was formed by aging (leaving it alone) at room temperature for 3 hours to remove air bubbles.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

Secondary firing was performed on the resultant glaze composition applied to obtain ceramic tiles. A porcelain tile was obtained by performing a rapid firing process in which the resultant glaze composition was applied through a furnace in a car-carrier manner. The maximum temperature of the secondary firing was 1050 ℃, and the time of feeding was 40 minutes. The secondary firing was performed in an air atmosphere.

<Experimental Example 3>

In order to manufacture the base layer of ceramic floor tiles, 12 wt% of limestone, 23 wt% of clay, 42 wt% of ceramics, 13 wt% of pyrophyllite and 10 wt% of kaolin are blended as raw materials, and after loading into a metal mold, 250 kgf/ A disk-shaped molded specimen was prepared by uniaxial pressing under a pressure of cm 2 . The molded specimen was prepared to have a diameter of 30 mm. The molded specimen was first fired. The primary firing was performed in a rapid firing process in which a furnace was passed in a car-carriing manner. The maximum temperature of the primary firing was 1150° C., and the time of feeding was 50 minutes. The primary firing was performed in an air atmosphere.

In order to form the engobe layer, 60 wt% of glass frit, 5 wt% of feldspar, 17 wt% of silica, 15 wt% of kaolin and 3 wt% of zircon were prepared as raw materials. A 10 mm alumina ball is put in a ball mill container, and the raw material for forming the engobe layer and deionized water are charged, and then ball milling at 300 rpm for 24 hours to wet mixing. After that, the engobe composition was formed by aging (leaving it) for 3 hours at room temperature to remove air bubbles. The engobe composition was formed by mixing with the distilled water to form a solid content of 60%. The Ngobe composition was lubricated on the first calcined specimen using Belsee oil and dried for 6 hours.

A glaze composition was prepared by mixing 90% by weight of glass frit having the composition shown in Table 1, 5% by weight of kaolin, and _{5% by weight of Nd 2} O _{3 powder as glaze raw materials to form a glaze layer on top of the engobe layer.} As the Nd ₂ O ₃ powder, an average particle diameter of 2.6 μm was used. Put an alumina ball of 10 mm in a ball mill container, and charge the glaze raw material and deionized water so that the _{solid content (frit, kaolin and CeO 2 powder) is 60% by weight, then at 300rpm} After wet mixing by ball milling for 24 hours, the glaze composition was formed by aging (leaving it alone) at room temperature for 3 hours to remove air bubbles.

The glaze composition was spray-applied on the surface to which the Engobe composition was applied and dried for 6 hours. The thickness of the glaze layer was controlled by controlling the time and frequency of spray application of the glaze composition.

Secondary firing was performed on the resultant glaze composition applied to obtain ceramic tiles. A porcelain tile was obtained by performing a rapid firing process in which the resultant glaze composition was applied through a furnace in a car-carrier manner. The maximum temperature of the secondary firing was 1050 ℃, and the time of feeding was 40 minutes. The secondary firing was performed in an air atmosphere.

The contact angles of the glaze layers of the ceramic tiles prepared according to Experimental Examples 1 to 3 were measured, and are shown in Table 2 below. This is the case in which the thickness of the glaze layer after secondary firing is about 100 to 150 μm by controlling the time and number of glazing of the glaze composition.

Experimental Example 2
(Added _{CeO 2)} Experimental Example 3
(Nd ₂ O ₃ added) Experimental Example 1
contact angle ( ^O ) 106.5 104.2 32.4

2 is a photograph showing the contact angle characteristics of the ceramic tile prepared according to Experimental Example 2 with respect to the glaze layer, FIG. 3 is a photograph showing the contact angle characteristics of the ceramic tile prepared according to Experimental Example 3 with respect to the glaze layer, and FIG. 4 is a photograph showing the contact angle characteristics of the glaze layer of the ceramic tile prepared according to Experimental Example 1.

Referring to Table 2 and FIGS. 2 to 4, according to Experimental Example 1, when _{the glaze layer was formed using a glaze composition in which no CeO 2} powder or Nd ₂ O ₃ powder was added and only glass frit and kaolin were mixed, the contact angle This was a very low value as 32.4°. According to Experimental Example 2, when _{the glaze layer was formed using a glaze composition in which CeO 2} powder was mixed with glass frit and kaolin, the contact angle was 106.5°, which was very high. In addition, even when the glaze layer was formed using a glaze composition in which _{Nd 2} O ₃ powder was mixed with glass frit and kaolin according to Experimental Example 3, the contact angle was 104.2°, indicating a very high value.

The hardness, glossiness, and roughness of the glazed layers of the ceramic tiles prepared according to Experimental Examples 1 to 3 were measured and shown in Table 3 below. This is the case in which the thickness of the glaze layer after secondary firing is about 100 to 150 μm by controlling the time and number of glazing of the glaze composition.

Experimental Example 2
(Added CeO2) Experimental Example 3
(Added Nd2O3) Experimental Example 1
Hardness
(GPa) 7.91 7.22 4.20 Glossiness (GU60) 45.25 43.08 45.01 Roughness (mm) 0.136 0.148 0.140

Referring to Table 3, when the glaze layer was formed using a glaze composition in which only glass frit and kaolin were mixed without adding _{CeO 2} powder or Nd ₂ O ₃ powder according to Experimental Example 1, the hardness was 4.20 GPa, which was a low value. was shown. According to Experimental Example 2, when the glaze layer was formed using a glaze composition in which _{CeO 2 powder was mixed with glass frit and kaolin, the hardness was 7.91 GPa, which was very high.} In addition, even when the glaze layer was formed using the glaze composition in which _{Nd 2} O ₃ powder was mixed with glass frit and kaolin according to Experimental Example 3, the hardness was 7.22 GPa, which was very high.

It was found that there was no significant difference in glossiness and roughness of the glaze layers of the ceramic tiles prepared according to Experimental Examples 1, 2 and 3, respectively.

As mentioned above, although preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various modifications are possible by those skilled in the art.

110: possession layer
120: Enkobe layer
130: glaze layer

Claims (11)

delete delete delete delete forming an engobe layer on the formed and primary fired base layer;
forming a glaze layer by applying and drying a glaze composition on the engobe layer; and
Secondary firing the resultant glaze layer is formed,
The glaze composition comprises:
Ceria (CeO ₂ ) comprising 0.1 to 10% by weight of powder, 88 to 98% by weight of glass frit powder, and 1 to 10% by weight of kaolin powder;
The kaolin powder consists of a kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported,
The kaolin powder on which one or more metal nanoparticles selected from the group consisting of Cu and Ni are supported,
forming a kaolin mixed solution by adding kaolin raw material powder and acid to the first solvent to adjust the pH to between 0.1 and 2.5;
dissolving a metal precursor in a second solvent to form a metal precursor mixed solution;
forming a metal precursor-kaolin mixed solution by mixing the metal precursor mixed solution and the kaolin mixed solution, and adjusting the pH between 4.0 and 8.0 by adding a basic material;
removing the solvent and washing the metal precursor-kaolin mixed solution using an evaporator to obtain powders;
drying the washed powders; and
A method of manufacturing a porcelain tile, characterized in that the dried powder is heat-treated in a reducing gas atmosphere to obtain a kaolin powder on which metal nanoparticles are supported.
The method of claim 5, wherein the glaze composition further comprises 0.01 to 10 parts by weight of Zn powder based on 100 parts by weight of the glaze raw material.
The method of claim 5, wherein the glaze composition further comprises 0.01 to 10 parts by weight of Ni powder coated with Cu nanopowder based on 100 parts by weight of the glaze raw material.
delete delete The method of claim 5, wherein the metal precursor comprises at least one salt selected from the group consisting of Cu nitrate, Cu sulfate, Ni nitrate, and Ni sulfate. A method of manufacturing a ceramic tile, characterized in that
The method according to claim 5, wherein the Cu precursor mixed solution is mixed with the kaolin mixed solution so that the metal precursor comprises 5 to 20 parts by weight based on 100 parts by weight of the kaolin raw material powder.

Images