JP2000302574A - Tile and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tile having the feature that dirt fixed on the surface of the tile can be easily removed by such a cleaning process that the surface is softly wiped with a cloth impregnated with a cleaning agent and water without strongly rubbing with a scrubbing brush or a brush. SOLUTION: The tile has a grazed layer formed on its porcelain base surface, and an Ag-component is impregnated in the grazed layer. It is preferable that the Ag-component is ion-exchanged with a Na- or a K-component to exhibit self-cleaning function with respect to oily dirt by allowing a material containing the Na- and/or K-component to act on the grazed layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an interior tile usable in kitchens, bathrooms, toilets, etc., which can be easily removed by wiping with a fatty acid-based stain, and a hydrocarbon-based stain. The present invention relates to exterior tiles and mosaic tiles that are difficult to be removed and can be easily removed by wiping with a cloth.

[0002]

BACKGROUND OF THE INVENTION Keeping the surface of tiles clean and keeping their aesthetics high over the long term requires that tiles are commonly used in living spaces such as kitchens, bathrooms, toilets, and building exterior walls. It is a characteristic required from. As a method for keeping the tile surface hygienic and aesthetically pleasing in ordinary households since ancient times, a method of applying a detergent or abrasive such as a surfactant, an acid or an alkali to a scourer or a brush and rubbing it strongly is used. Has been taken.

[0003]

However, according to this method, labor for scrubbing with a scourer or a brush is required every time dirt adheres. Particularly, in a kitchen bag or the like, there is a problem that the fatty acid-based oil strongly adheres and the dirt is not easily removed.

Therefore, an object of the present invention is to make it possible to easily remove stains on the tile surface by lightly rubbing with a cloth soaked with a detergent and water without rubbing strongly with a scourer or a brush. The purpose is to provide tiles.

[0005]

According to the present invention, in order to solve the above-mentioned problems, an embodiment of the present invention is a ceramic in which a glaze layer is formed on the surface of a ceramic body, wherein the glaze layer contains Ag. Provided is an easy-to-clean tile characterized by containing a component. The Ag component is preferably 0.1% in terms of oxide relative to all metal components in the glaze layer.
It is preferably at least 0.5% by weight, more preferably at least 0.5% by weight, most preferably at least 1% by weight in terms of oxide, based on all metal components in the glaze layer. A that is not lost by firing
By containing the g component, self-cleaning against dirt adhering to the surface can be achieved by simply gently wiping with a cloth containing Na and / or K, more preferably an anionic surfactant and water, on the tile surface. Functions can be provided. This will be described in detail below. When an anionic surfactant is allowed to act on the surface of the glaze layer containing the Ag component, monovalent Ag ions in the glass component of the glaze and cations such as Na ions in the anionic surfactant are first ionized. Replace (Figure 1). By the way, the attached stains brought on the tile surface include, for example, cooking oil (fatty acid) and water scale on the interior wall of the kitchen, metal soap (soap scum), fatty acid, fatty acid ester, protein, Amino acids, scales, etc., and the main deposits are oily stains and scales containing carboxyl end groups. Therefore, for example, when an oily soil containing a carboxyl terminal group is brought to the tile surface, if there is a Na component or the like remaining after ion exchange, the Na component is preferentially added to the oily soil by a substitution reaction, Or it is adsorbed. Thereby, the affinity of the dirt with water is improved, and when the dirt is a low molecular weight, the dirt is made water-soluble (saponified). Thus, the affinity of the dirt with water is higher than the affinity of the dirt with the tile surface, and the dirt is easily removed by the water (FIG. 2). Also, Ag
The amount of the component is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and most preferably 1% by weight or more based on the total metal components in the glaze layer in terms of oxide. By doing so, the easy-cleaning function is remarkably improved, possibly due to an increase in the amount of ion exchange with the cation in the substance containing Na and / or K or the anionic surfactant.

In a preferred aspect of the present invention, in the above-mentioned configuration, the surface roughness Ra of the glaze layer surface is set to 0.0 by a stylus type surface roughness measuring device (JIS-B0651).
It should be less than 7 μm, preferably less than 0.05 μm, more preferably less than 0.03 μm. By doing so, it becomes difficult for dirt to adhere to the unevenness on the surface, and the cleanability is significantly improved.

[0007] In a preferred aspect of the present invention, in the above configuration, the glaze layer is made of a substantially amorphous component. By making the glaze layer substantially composed of an amorphous component (preferably a glass component), Ag can be increased by +
It is easy to exist in a state exchangeable with monovalent ions, and N
The cleaning property after the action of a substance containing a and / or K or an anionic surfactant is improved.

[0008] In a preferred aspect of the present invention, in the above structure, the glaze layer is made of a substantially hydratable substance. The glaze layer is made of a hydratable substance, so that only a simple cleaning such as wiping with a substance containing Na and / or K or an anionic surfactant can be used to remove the oily substance adhering to the tile surface. Adhesive dirt such as dirt and scale is more easily removed. This will be described in detail below. When, for example, an anionic surfactant is applied to the surface of the glaze layer containing the Ag component, monovalent Ag ions in the glass component of the glaze and N in the anionic surfactant are added.
First, ion exchange is performed with a cation such as an a ion. By the way, the attached stains brought on the tile surface include, for example, cooking oil (fatty acid) and water scale on the interior wall of the kitchen, metal soap (soap scum), fatty acid, fatty acid ester, protein, Amino acids, scales, etc., and the main deposits are oily stains and scales containing carboxyl end groups. Accordingly, the oily soil containing the carboxyl terminal group attached to the tile surface is firstly added to the oily soil by a substitution reaction due to the presence of Na ions and the like in the anionic surfactant. Or adsorbed. Thereby, the affinity of the dirt with water is improved, and when the dirt is a low molecular weight, the dirt is made water-soluble (saponified). Here, if the glaze layer is made of a hydratable substance, the saponified dirt can move quite freely as an electrolyte in the hydratable substance (FIG. 1). Therefore, on a surface where the tile surface is inclined in the direction of gravity, the oily dirt moves in the direction of gravity without being particularly washed with water, and the dirt is automatically removed (FIG. 2).

[0009] In a preferred aspect of the present invention, in the above-described configuration, the zeta potential on the surface of the glaze layer is negative. By making the zeta potential of the surface of the glaze layer negative, it is possible to impart a disinfecting effect when water is brought into contact with the tile surface. About this,
Details will be described below. Fungi such as Escherichia coli are generally known to be negatively charged in water. Therefore, by making the zeta potential of the tile surface negative, the tile surface and the fungi are electrically repelled in a state where the water is in contact with the water, and the adhesion of the fungi can be prevented.

In another embodiment of the present invention, a first glaze layer having coloring is formed on the surface of the ceramic body, and a second glaze layer is formed on the surface of the first glaze layer. In the second glaze layer, the Ag component is 0.1% by weight or more, more preferably 0.5% by weight, in terms of oxide, based on all metal components in the glaze layer. that's all,
Most preferably, an easy-cleaning tile characterized by containing 1% by weight or more is provided. With the above configuration, the second glaze layer forming the outermost layer does not contain a pigment or an emulsifier, so that the second glaze layer is substantially composed of only a glass component, and Ag has a +1 valence. It is likely to be present in a state where it can be exchanged for ions, and the cleanability after the action of a substance containing Na and / or K or an anionic surfactant is improved. Furthermore, since the second glaze layer forming the outermost layer does not contain a pigment or an emulsifier, the surface smoothness is improved, so that dirt is less likely to adhere to the surface irregularities, and the cleaning property is improved. Is improved.

[0011] In a preferred aspect of the present invention, in the above configuration, the surface roughness Ra of the surface of the second glaze layer is measured by a stylus type surface roughness measuring device (JIS-B0651).
The thickness is less than 0.07 μm, preferably 0.05 μm or less, more preferably 0.03 μm or less. By doing so, it becomes difficult for dirt to adhere to unevenness on the surface,
Cleanability is significantly improved.

[0012] In a preferred aspect of the present invention, in the above configuration, the second glaze layer is made of a substantially amorphous component. By making the second glaze layer substantially composed of an amorphous component (preferably a glass component), Ag can easily exist in a state that can be exchanged with + 1-valent ions, and Na and / or K can be removed. The cleaning property after the contained substance and the anionic surfactant act is improved.

[0013] In a preferred aspect of the present invention, in the above configuration, the second glaze layer is made of a substantially hydratable substance. By making the second glaze layer of a hydratable material, the surface of the tile can be easily cleaned only by wiping with a material containing Na and / or K or an anionic surfactant. Oily dirt,
Adhesive stains such as water stains are more easily removed. Dirt attached to the tile surface is easily removed in the direction of gravity.

In a preferred aspect of the present invention, in the above configuration, the glaze layer surface has a negative zeta potential. By making the zeta potential of the surface of the glaze layer negative, it is possible to impart a disinfecting effect when water is brought into contact with the tile surface. About this,
Details will be described below. Fungi such as Escherichia coli are generally known to be negatively charged in water. Therefore, by making the zeta potential of the tile surface negative, the tile surface and the fungi are electrically repelled in a state where the water is in contact with the water, and the adhesion of the fungi can be prevented.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In one embodiment of the present invention,
As shown in FIG. 3, an easy-cleaning tile in which a glaze layer is formed on a ceramic body surface, wherein the glaze layer contains an Ag component. In another embodiment of the present invention, as shown in FIG. 4, a first colored glaze layer is formed on the surface of the ceramic body, and a second transparent glaze is formed on the surface of the first glaze layer. An easy-cleaning tile having a layer formed thereon, wherein the second glaze layer contains an Ag component.

In general, the glaze layer contains Si as a main component, a trivalent metal component such as Al, a divalent metal component such as Ca, Mg and Zn, and an alkali metal component such as Na and K.
In the embodiments of FIGS. 3 and 4, an Ag component is additionally contained.

As the hydratable substance, a substance (for example, silica, silicate, etc.) containing a SiO ₄ network structure having non-bridging oxygen through which water molecules can pass through the structure can be used.

One method of manufacturing the tile of the embodiment of FIG. 3 is, for example, to prepare a frit glaze containing Ag, grind it if necessary, apply it to a ceramic molding substrate, Firing at a temperature of Another method of manufacturing the tile of the embodiment of FIG. 3 is, for example, to prepare a glaze obtained by adding a salt containing Ag to a usual coloring glaze raw material, pulverize as needed, and then form the glaze on a ceramic molding substrate. It is applied and baked at a temperature of 1200 to 1400 degrees. FIG.
Other methods of manufacturing the tiles of the embodiments include, for example, after applying a normal colored glaze to a ceramic molding substrate,
Further, a glaze obtained by adding a salt containing an Ag component to a usual coloring glaze raw material is applied thereon, and baked at a temperature of 1200 to 1400 degrees.

Another method of manufacturing the tile of the embodiment of FIG. 4 is, for example, to apply a usual coloring glaze on a ceramic molding substrate, and further apply a pigment or an emulsifier containing an Ag component thereon. Apply frit free glaze, 1200
Bake at a temperature of ~ 1400 degrees.

Examples of the anionic surfactant which can be used in the present invention include, for example, sodium polyoxyethylene alkyl phenyl ether sulfonate, sodium soap fatty acid, californic acid fatty acid, sodium dioctyl sulfosuccinate, alkyl sulfate soda salt, alkyl ether sulfate. Soda salt, polyoxyethylene alkyl ether sulfate soda salt, 2-ethylhexylalkyl sulfate sodium salt, sodium acylmethyltaurate, sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate,
Lauryl sulfosuccinate disodium, polyoxyethylene lauryl disulfosuccinate disodium, sulfo FA
Na salt or K salt such as ester sodium salt; sulfonic acid polyoxyethylene alkyl phenyl ether ammonium salt, alkyl sulfate, alkyl ether sulfate, polyoxyethylene alkyl ether sulfate, alkyl sulfate TEA salt, polyoxyethylene alkyl ether sulfate TEA salt; Polycarboxylic acid, oleoyl sarcosine, amide ether sulfate, lauroyl sarcosine and the like can be suitably used.

A chelating agent may be added to the anionic surfactant. As the chelating agent, EDTA, edetate and the like are preferably used. Chelating agents are generally added to detergents as sequestering agents (which combine with Ca ions and Mg ions in water to prevent the formation of metal soaps), and are used with anionic surfactants for glazes containing Ag. When used at the same time, the effect of trapping Ag ions is enhanced, and the action of ion exchange by the surfactant can be enhanced.

[0022]

(Comparative Example 1) ₂ kg of # 1 glaze raw material (excluding Ag component) composed of a composition mainly composed of SiO ₂ and Al ₂ O ₃ , 1 kg of water and 4 kg of cobblestone, were added in a volume of 6 liters. It was placed in a pot made of earthenware and ground by a ball mill for about 18 hours. The glaze slurry obtained here is designated as glaze A. When the particle size of the glaze A obtained after the pulverization was measured using a laser diffraction type particle size distribution meter, 65% was 10 μm or less, and the 50% average particle size (D50) was 5.8 μm. Further, a glaze base material (excluding the Ag component) having a composition obtained by removing the emulsifier and the pigment from the above # 1 glaze raw material was melted at 1300 to 1400 ° C. using an electric furnace, and rapidly cooled in water. To obtain a glass frit. This was pulverized by a stamp mill, and 600 g of the obtained powder, 400 g of water and 1 kg of alumina balls were put into a 2 liter pottery pot, and pulverized by a ball mill for about 18 hours. The glaze slurry obtained here is designated as glaze B. When the particle size of the glaze B obtained after the pulverization was measured using a laser diffraction type particle size distribution meter, 68% and 50% were found to be 10 μm or less.
The average particle size (D50) was 6.0 μm. Next, a 100 × 100 mm plate-shaped test piece was prepared by wet press molding using a tile base slurry prepared using silica sand, feldspar, clay and the like as raw materials. On this molded body, glaze A is spray-coated as a lower layer, and then glaze B is spray-coated as an upper layer.
A sample was obtained by firing at 0 ° C. The obtained sample was not washed at all, and the appearance of the glaze layer was visually evaluated, a stain resistance test in water and a stain resistance test in the air due to simulated stains assumed to be used for interior tiles, and a glaze layer surface Was subjected to an antibacterial test. As for the appearance of the glaze layer, defects such as cracks were not visually observed, and there was no problem as a tile. In an anti-fouling test in water by artificial stains assumed to be used for interior tiles, first, artificial stains composed of 200 parts by weight of oleic acid, 1 part by weight of engine oil, and 1 part by weight of oil black were prepared. Here, oleic acid is a main component of edible oil which is a main cause of kitchen stains, and engine oil and oil black are additives for making the oil easily visible. Next, about 270 cc of distilled water is put into a 300 cc beaker.
I put cc. The plate-shaped sample was immersed in the beaker, and the time required for oil stains adhering to the glaze layer surface at the time of sample settling to separate in water was measured. As a result, an oil film remained on a part of the glaze surface even after 5 minutes. In addition, the contamination resistance test in the air due to the pseudo dirt showed that the above components had a pseudo dirt of 0.3%.
cc was dropped at the center of the plate sample placed horizontally, and then
When 5 minutes had passed after tilting vertically, the residual state of the pseudo stain on the glaze surface was visually evaluated. As a result, an oil film having a large width in the vertical direction remained in a belt shape.

For the antibacterial test, Escherichia coli (Esch
ericia coli (IFO3972). That is, 70 vol%
0.2 ml of bacterial solution (the number of bacteria: 1 × 10 ^{5 to} 5 ×) was sterilized with ethanol and dried on the glaze layer surface of the sample.
10 ⁵ ) were dropped, covered with a 45 × 45 mm polyethylene film and adhered closely, and allowed to stand in an atmosphere at a temperature of 37 ± 1 ° C. and a relative humidity of 90% or more for 24 hours. afterwards,
Peel the film, stamp with NA medium, temperature 35 ±
The cells were cultured in a 1 ° C. environment for 16 to 20 hours, and the number of viable cells was measured. At the same time, a blank sample without antibacterial activity (control product)
By comparing the number of bacteria tested and cultured in the above with the number of bacteria tested and cultured on the sample (test sample), the bacteria reduction rate and the growth inhibition rate were calculated, and the antibacterial activity was determined. The sterilization rate is
It is calculated by the following equation. Bacterial reduction rate (%) = 100 × ([count of surviving bacteria of control product] − [number of surviving bacteria of test sample]) / [number of surviving bacteria of control product] The growth inhibition rate is calculated by the following formula. Is done. Growth inhibition rate = log ([control product surviving cell count] / [test sample surviving cell count]) The criteria for judging the presence or absence of the antibacterial effect is that the above-mentioned sterilization rate is 99%.
% Or the growth inhibition rate is 2.0 or more, it is judged that "there is an antibacterial effect", and when it is less than that, it is judged that "there is no antibacterial effect".
As a result, the sterilization rate of the sample of Comparative Example 1 was 30%, and the growth inhibition rate was 0.16, which was determined to be "no antibacterial effect".

(Comparative Example 2) The glaze base prepared in Comparative Example 1 was prepared so as to contain an Ag component (the weight of Ag ₂ O was 0 with respect to the total weight of the glass component). 0.5% by weight) using an electric furnace at 1300 to 1%.
It was melted at 400 ° C. and quenched in water to obtain a glass frit. This was pulverized by a stamp mill to obtain 600 g of the obtained powder, 400 g of water and 1 kg of cobblestone alumina balls.
Was placed in a 2 liter pottery pot and ground by a ball mill for about 18 hours. The glaze slurry obtained here is designated as glaze C. When the particle size of the glaze C obtained after the pulverization was measured using a laser diffraction type particle size distribution meter, 68% was found to be 10 μm or less, and 50% average particle size (D50).
Was 6.0 μm. Next, a 100 × 100 mm plate-like test piece was prepared by wet press molding using a tile base slurry prepared using silica sand, feldspar, clay, or the like as a raw material. The formed body was spray-coated with glaze A as a lower layer, subsequently spray-coated with glaze C as an upper layer, and then fired at 1200 to 1300 ° C. to obtain a sample. The obtained sample was not subjected to any washing or the like, and was evaluated in the same manner as in Comparative Example 1. As a result, the appearance of the glaze layer showed no defects such as cracks by visual observation.
There was no problem as a tile. Regarding the anti-fouling test in water due to pseudo-fouling, an oil film remained on a part of the glaze surface even after 5 minutes. In the contamination resistance test in the air due to the pseudo dirt, a wide oil film in the vertical direction remained in a strip shape. The results of the antibacterial test show that the sterilization rate is 99.9995.
%, The growth inhibition rate was 5.3, and it was determined that "there was an antibacterial effect".

Example 1 A plate test piece of 100 × 100 mm was prepared by wet press molding using a tile base slurry prepared using silica sand, feldspar, clay and the like as raw materials. On this molded product, the glaze A prepared in Comparative Example 1 was spray-coated as a lower layer, then the glaze C prepared in Comparative Example 2 was spray-coated as an upper layer, and then fired at 1200 to 1300 ° C. I got Using a commercially available cellulose sponge impregnated with Neogen S-20 (a component is sodium linear dodecylbenzenesulfonate) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., an anionic surfactant was applied to the glaze layer surface of the sample. Was applied, ultrasonically washed in distilled water, and used for various evaluations.
After the above pretreatment, evaluation was performed in the same manner as in Comparative Example 1. As a result, the appearance of the glaze layer did not show any defects such as cracks visually, and there was no problem as a tile. In the test for resistance to contamination in water caused by artificial stains, the oil film on the glaze surface was almost completely separated 60 seconds after immersion in water. In the anti-fouling test in the air due to pseudo-fouling, although a very small amount of oil droplets were present on the glaze layer surface, the dropped oil-fouling almost completely flowed down. As a result of the antibacterial test, the sterilization rate was 83% and the growth inhibition rate was 0.76, and it was determined that there was no antibacterial effect.

(Example 2) Ag powder was added to the glaze slurry B prepared in Comparative Example 1 (the weight of Ag ₂ O was 0.5% by weight based on the total weight of the glass components), and about 1 hour Stirred. The glaze slurry obtained here is designated as glaze D. The particle size of the glaze D obtained after stirring was measured using a laser diffraction type particle size distribution meter,
The 8% and 50% average particle size (D50) was 6.0 μm. Next, using a tile base slurry prepared from silica sand, feldspar, clay, or the like as a raw material, a wet press molding method was used to form 10 tiles.
A 0x100 mm plate-shaped test piece was prepared. The glaze A prepared in Comparative Example 1 was spray-coated as a lower layer on the molded body, and the glaze D was spray-coated as an upper layer, and then fired at 1200 to 1300 ° C to obtain a sample. Using a commercially available cellulose sponge impregnated with Kanebo Naive Body Soap (including edetate in addition to the surfactant), apply an anionic surfactant to the glaze layer surface of the sample. After the application, it was subjected to ultrasonic cleaning in distilled water and used for various evaluations.
After the above pretreatment, evaluation was performed in the same manner as in Comparative Example 1. As a result, the appearance of the glaze layer did not show any defects such as cracks visually, and there was no problem as a tile. In the test for resistance to contamination in water caused by artificial stains, the oil film on the glaze surface was almost completely peeled off 40 seconds after immersion in water. In the anti-fouling test in the air due to pseudo-fouling, although a very small amount of oil droplets were present on the glaze layer surface, the dropped oil-fouling almost completely flowed down. The antibacterial test result was a sterilization rate of 92% and a growth inhibition rate of 1.1, and was determined to be "no antibacterial effect".

[0027]

[Table 1]

Table 1 summarizes the evaluation results of the examples of the present invention. As described above, in the embodiment of the present invention, by cleaning with an anionic surfactant and water before use, the surface of the glaze layer is less likely to remain attached dirt in water and air. It is presumed that even in actual use as a tile, dirt is easily removed.

[0029]

According to the present invention, it is possible to easily remove stains on the tile surface by gently rubbing with a cloth soaked in detergent and water, without rubbing strongly with a scourer or a brush. .

[Brief description of the drawings]

FIG. 1 is a diagram showing a state in which a hydration layer is formed on a tile surface by ion exchange.

FIG. 2 is a view showing a state in which Na or the like is adsorbed and replaced by a stain molecule, and is rendered water-soluble.

FIG. 3 is a diagram showing one embodiment of the present invention.

FIG. 4 is a diagram showing another embodiment of the present invention.

[Explanation of symbols]

 1: Ceramic body 2: Colorable glaze layer 3: Transparent glaze layer

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[Procedure amendment]

[Submission date] April 21, 2000 (200.4.2
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: TILE AND METHOD FOR MANUFACTURING THE TILE

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0001

[Correction method] Change

[Correction contents]

[0001]

TECHNICAL FIELD The present invention relates to an interior tile usable in kitchens, bathrooms, toilets, etc., which can be easily removed by wiping with a fatty acid-based stain, and a hydrocarbon-based stain. TECHNICAL FIELD The present invention relates to an exterior tile, a mosaic tile , and a method of manufacturing the same, which are difficult to remove and can be easily removed by wiping.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

Therefore, an object of the present invention is to make it possible to easily remove stains on the tile surface by lightly rubbing with a cloth soaked with a detergent and water without rubbing strongly with a scourer or a brush. It is an object to provide a tile and a method for manufacturing the tile.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

In the present invention, in order to solve the above problems, as one embodiment , a glaze layer is formed on the surface of a ceramic body.
In the glaze layer, Ag component is contained.
The surface of the yl is made of a material containing Na and / or K, more preferably
Characterized by suitably treating with an anionic surfactant
Provided is a method for manufacturing an easy-cleaning tile . The Ag component is preferably 0.1% by weight or more in terms of oxide relative to all metal components in the glaze layer, and more preferably 0% in terms of oxide relative to all metal components in the glaze layer. 0.5% by weight
As described above, the content is most preferably 1% by weight or more. By containing an Ag component that is not lost by firing, and wiping gently with a cloth containing Na and / or K, more preferably an anionic surfactant and water , on the tile surface,
A self-cleaning function for adhering dirt can be provided on the surface. This will be described in detail below. When an anionic surfactant is allowed to act on the surface of the glaze layer containing the Ag component, monovalent Ag ions in the glass component of the glaze and cations such as Na ions in the anionic surfactant are first ionized. Replace (Figure 1). By the way, the attached stains brought on the tile surface include, for example, cooking oil (fatty acid) and water scale on the interior wall of the kitchen, metal soap (soap scum), fatty acid, fatty acid ester, protein, Amino acids, scales, etc., and the main deposits are oily stains and scales containing carboxyl end groups. Therefore, for example, when an oily soil containing a carboxyl terminal group is brought to the tile surface, if there is a Na component or the like remaining after ion exchange, the Na component is preferentially added to the oily soil by a substitution reaction, Or it is adsorbed. Thereby, the affinity of the dirt with water is improved, and when the dirt is a low molecular weight, the dirt is made water-soluble (saponified). Thus, the affinity of the dirt with water is higher than the affinity of the dirt with the tile surface, and the dirt is easily removed by the water (FIG. 2). Further, the amount of the Ag component is 0.1% by weight or more, more preferably 0.5% by weight or more, most preferably 1% by weight or more in terms of oxide relative to all the metal components in the glaze layer. By doing so, the easy-cleaning function is remarkably improved, possibly due to an increase in the amount of ion exchange with the cations in the substances containing Na and / or K or the anionic surfactant.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

In another aspect of the present invention, a first colored glaze layer is formed on the surface of the ceramic body, and a transparent second glaze layer is formed on the first glaze layer. You
And the second glaze layer contains an Ag component.
The tile surface is made of a material containing Na and / or K,
Preferably, it is treated with an anionic surfactant.
The present invention provides a method of manufacturing an easy-to-clean tile. With the above configuration, the second glaze layer forming the outermost layer does not contain a pigment or an emulsifier, so that the second glaze layer is substantially composed of only a glass component, and Ag has a +1 valence. It is likely to be present in a state where it can be exchanged for ions, and the cleanability after the action of a substance containing Na and / or K or an anionic surfactant is improved. Furthermore, since the second glaze layer forming the outermost layer does not contain a pigment or an emulsifier, the surface smoothness is improved, so that dirt is less likely to adhere to the surface irregularities, and the cleaning property is improved. Is improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) E04F 15/08 E04F 15/08 A (72) Inventor Masaaki Ito 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture No. 1 Toto Kikki Co., Ltd. (72) Inventor Masami Ando 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Tochi Kikai Co., Ltd. (72) Inventor Koichi Hayashi Kokura-Kita, Kitakyushu-shi, Fukuoka No. 2-1-1 Nakajima Totoki Kiki Co., Ltd. (72) Inventor Shin Hayakawa 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka F-term inside Totoki Kiki Co., Ltd. 2E110 AA70 AB04 AB05 AB22 AB23 AB42 AB43 BA13 GA34Z GB22Z GB28Z 4H003 AB19 BA12 BA27 DA05 DA06 DA08 DA17 DB02

Claims (35)

[Claims] 1. A tile having a glaze layer formed on the surface of a ceramic body, wherein the glaze layer contains an Ag component. 2. A tile having a glaze layer formed on a surface of a ceramic body, wherein the glaze layer contains an Ag component, and the glaze layer contains a material containing Na and / or K components. The Ag component and the Na
Alternatively, an easy-cleaning tile characterized in that the component K is ion-exchanged to exhibit a self-cleaning function for oily dirt. 3. A tile in which a glaze layer is formed on the surface of a ceramic body, wherein the glaze layer contains an Ag component, and the glaze layer is acted upon by an anionic surfactant. An easy-cleaning tile, wherein an Ag component and a cation component in the anionic surfactant are ion-exchanged to exhibit a self-cleaning function for oily stains. 4. The easy-cleaning method according to claim 1, wherein the Ag component is contained in an amount of 0.1% by weight or more in terms of oxide based on all metal components in the glaze layer. Sex tile. 5. The easy cleaning according to claim 1, wherein the Ag component is contained in an amount of 0.5% by weight or more in terms of oxide relative to all metal components in the glaze layer. Sex tile. 6. The easy-cleaning tile according to claim 1, wherein the Ag component is contained in an amount of 1% by weight or more in terms of oxide relative to all metal components in the glaze layer. . 7. The surface roughness Ra of the glaze layer surface is determined to be 0.1 by a stylus type surface roughness measuring device (JIS-B0651).
The easy-cleaning tile according to any one of claims 1 to 6, wherein the tile is less than 07 µm. 8. The surface roughness Ra of the surface of the glaze layer is determined by using a stylus type surface roughness measuring device (JIS-B0651).
The easy-cleaning tile according to any one of claims 1 to 6, wherein the tile is less than 05 µm. 9. The surface roughness Ra of the surface of the glaze layer is determined by a stylus type surface roughness measuring device (JIS-B0651).
The easy-cleaning tile according to claim 1, wherein the tile is less than 03 μm. 10. The easy-cleaning tile according to claim 1, wherein the glaze layer substantially comprises an amorphous component. 11. The easy-cleaning tile according to claim 1, wherein the glaze layer is substantially made of a hydratable substance. 12. The easy-cleaning tile according to claim 1, wherein the surface of the glaze layer has a negative zeta potential. 13. A tile in which a coloring first glaze layer is formed on a surface of a ceramic body, and a transparent second glaze layer is formed on the first glaze layer, The easy-cleaning tile, wherein the second glaze layer contains an Ag component. 14. A tile in which a first glaze layer having coloring property is formed on a surface of a pottery substrate, and a second glaze layer having transparency is formed on the surface of the first glaze layer, An Ag component is contained in the second glaze layer, and the Ag component and the Na or K component are ion-exchanged by allowing a substance containing Na and / or K component to act on the glaze layer. An easy-to-clean tile characterized in that it has a self-cleaning function against oily stains. 15. A tile in which a coloring first glaze layer is formed on a surface of a pottery substrate and a transparent second glaze layer is formed on the surface of the first glaze layer. The second glaze layer contains an Ag component, and the second glaze layer is treated with an anionic surfactant to act on the A component.
An easy-cleaning tile, wherein the g component and the cation component in the anionic surfactant are ion-exchanged so as to exhibit a self-cleaning function for oily stains. 16. The easy cleaning according to claim 13, wherein the Ag component is contained in an amount of 0.1% by weight or more in terms of oxide based on all metal components in the glaze layer. Sex sanitary ware. 17. The easy cleaning according to claim 13, wherein the Ag component is contained in an amount of 0.5% by weight or more in terms of an oxide with respect to all metal components in the glaze layer. Sex tile. 18. The easy-cleaning tile according to claim 13, wherein the Ag component is contained in an amount of 1% by weight or more in terms of oxide relative to all metal components in the glaze layer. . 19. The surface roughness Ra of the surface of the second glaze layer
Is less than 0.07 μm by a stylus type surface roughness measuring device (JIS-B0651).
The easy-to-clean tile according to 3 to 18. 20. The surface roughness Ra of the surface of the second glaze layer
Is less than 0.05 μm by a stylus type surface roughness measuring device (JIS-B0651).
The easy-to-clean tile according to 3 to 18. 21. Surface roughness Ra of the surface of the second glaze layer
Is less than 0.03 μm by a stylus type surface roughness measuring device (JIS-B0651).
The easy-to-clean tile according to 3 to 18. 22. The easy-cleaning tile according to claim 13, wherein the second glaze layer substantially comprises an amorphous component. 23. The easy-cleaning tile according to claim 13, wherein the second glaze layer is substantially made of a hydratable substance. 24. The easy-cleaning tile according to claim 13, wherein a zeta potential of the surface of the second glaze layer is negative. 25. The easy-cleaning tile according to claim 1, wherein the tile is an exterior tile. 26. The easy-to-clean tile according to claim 1, wherein the tile is an interior tile. 27. The easy-to-clean tile according to claim 1, wherein the tile is a mosaic tile. 28. A tile having a self-cleaning function for oily soil, which can be produced by treating the tile surface according to claim 1 with a substance containing Na and / or K. 29. A tile having a self-cleaning function for oily soil, which can be produced by treating the tile surface according to claim 1 with an anionic surfactant. 30. The method according to claim 1, wherein a portion of the tile to be cleaned is provided with a self-cleaning function for oily stains, wherein the tile portion to be cleaned is made of a substance containing Na and / or K. A method for imparting a self-cleaning function to tiles, wherein the tile is brought into contact with contained water. 31. The method according to claim 1, wherein a portion of the tile to be cleaned is provided with a self-cleaning function against oily stains, wherein the portion of the tile to be cleaned is immersed in water containing an anionic surfactant. A method for imparting a self-cleaning function to a tile, which is brought into contact with the tile. 32. The tile cleaning method according to claim 1, wherein a tile portion to be cleaned is brought into contact with water containing a substance containing Na and / or K. Method. 33. The method for cleaning a tile according to claim 1, wherein a tile portion to be cleaned is brought into contact with water containing an anionic surfactant. 34. A detergent for cleaning a tile according to claim 1, which comprises a substance containing Na and / or K and water. 35. A detergent for cleaning a tile according to claim 1, which comprises an anionic surfactant and water.