RU2285683C2 - Method of treatment of the article for attaching the antipollution properties and the article having the glazed layer; the article made out of the reinforced ceramics and the method of its manufacture; the article having the glazed layer and the method of its manufacture - Google Patents

Abstract

FIELD: ceramics production; methods of manufacture and treatment of the articles made out of the reinforced ceramics with the glazed layers.

SUBSTANCE: the invention is pertaining to the articles with the glazed layer, such as tableware, kitchen accessories, the decorative tile, the sanitary ware and the industrial equipment, etc. The technical result of the invention is manufacture of the hardware products possessing excellent antibacterial effect at the low manufacture costs. On the surface of the billet they form the first glazed layer and on the outer surface of the first layer form the second glazed layer containing the silver compound. The ratio of the dimensions in thickness of the first and the second glazed layers is in the interval from 10/1 up to 30/1. The second glazed layer contains the bigger amount of potassium and the smaller amount of sodium, and also possesses the smaller coefficient of the linear thermal expansion, than the first glazed layers, and after melting has the greater viscosity, than the layer of the first glazed material.

EFFECT: the invention ensures manufacture of the hardware products possessing excellent antibacterial effect at the low manufacture costs.

29 cl, 19 dwg, 16 ex, 5 tbl

Description

FIELD OF TECHNOLOGY

The first invention relates to a processing method for imparting resistance to pollution and to an article having a glazed layer. The second invention relates to a reinforced ceramic product and a method for its manufacture. A third invention relates to an article having a glazed layer and a method for its manufacture.

BACKGROUND

It is known that antibacterial metals, for example Ag, Cu, Zn, etc., have antibacterial activity. Therefore, if it is necessary to manufacture an article having a glazed layer, for example, a ceramic article, an enamelled article, and the like, having antibacterial activity, a process for treating this article to impart resistance to contamination is carried out, which includes an antibacterial treatment step to impart antibacterial properties to the base surface articles, for example, glass molded products, ceramic molded products, metal molded products, etc. The antibacterial processing step of the treatment method to confer resistance to contamination includes a preparatory step of preparing a glaze material suitable for forming a glazed layer containing an antibacterial metal, and a glass transition step of forming a layer of glaze material on the surface of the article and melting the glaze material to form glazed layer.

According to a processing method, in order to confer resistance to contamination, an article is obtained which comprises a base with a glazed layer containing glaze material. In an article having a glazed layer obtained in this way, the antibacterial metal contained in the glazed layer can affect bacteria by killing them or inhibiting their reproduction.

A typical ceramic product contains a ceramic base and a glazed layer formed on the surface of the ceramic base.

A ceramic product is made approximately as follows. At the preparatory stage, material is prepared for the manufacture of the ceramic base of the product and the glaze material for forming a glazed layer on the surface of the ceramic base. In the glazing step, a layer of glaze material is formed on the surface of the base material. After that, in the calcining step, the base material and the layer of glaze material are calcined to obtain a ceramic product containing a ceramic base and a glazed layer.

In the ceramic product obtained by the described method, the glazed layer provides surface finish, giving it smoothness and a fine-grained structure, and also makes the surface resistant to damage and gives it water-repellent properties.

In addition, ceramic materials used for products such as tableware, kitchen utensils, decorative products, ceramic tiles, sanitary equipment, electrical equipment, physical and chemical equipment, industrial equipment, roof tiles, ceramic pipes, etc., consist of ceramic preform as a base and a glazed layer formed on the surface of the ceramic preform. The enameled product consists of a metal billet as a base and a glazed layer formed on the surface of the metal billet. In addition, part of the glass products consists of a glass preform as a base and a glazed layer formed on the glass preform.

Among the above-mentioned products having a glazed layer, a ceramic product is made, for example, as follows. At the preparatory stage, a base material is prepared that is suitable for forming a ceramic workpiece, and a glaze material that is suitable for forming a glazed layer on the surface of the ceramic workpiece. At the glazing stage, a layer of glaze material containing glaze material is formed on the surface of the base material. After that, at the stage of firing, the base material and a layer of glaze material are fired to obtain a ceramic product consisting of a ceramic billet and a glazed layer. The glazed layer is finished to obtain a smooth and fine-grained surface, on which crack formation is difficult, and which has water-repellent properties.

SUMMARY OF THE INVENTION

First invention

Since in the known processing method for imparting resistance to contamination only one glazed layer is formed on the surface of the substrate, it is naturally assumed that an antibacterial effect with respect to bacteria will take place on the surface of the glazed layer. However, the antibacterial metal is scattered throughout the entire thickness of the glazed layer. Therefore, in an article having a glazed layer thus obtained, the antibacterial effect is small, except when the concentration of the antibacterial metal is increased. Accordingly, in the processing method for imparting resistance to contamination in order to achieve a good antibacterial effect, a large amount of the antibacterial metal is consumed, which leads to an increase in production costs.

The first invention is the development of known solutions of the prior art, and the task is to manufacture an article having a glazed layer and low cost, as well as having excellent antibacterial action.

The treatment method for conferring resistance to contamination according to the first invention is a treatment method for conferring resistance to contamination, comprising a step of antibacterial treatment to impart an antibacterial effect to the substrate surface.

The method is characterized in that the antibacterial treatment step includes a preparatory step of preparing a base, a first glaze material suitable for forming a first glazed layer on a surface of the base, and a second glaze material suitable for forming a second glaze layer containing an antibacterial metal on the surface of the base. The method further comprises a glass transition step comprising forming a layer of a first glaze material containing a first glaze material on a surface of a base, and on a surface of a layer of a first glaze material, a layer of a second glaze material containing a second glaze material, and a melting step of a layer of the first glaze material and a layer a second glaze material to form a first glazed layer and a second glazed layer.

The layer of the second glaze material after melting has a higher viscosity than the layer of the first glaze material.

In the processing method for imparting resistance to contamination according to the first invention, during the preparatory stage of the antibacterial treatment, a base is prepared, a first glaze material suitable for forming a first glazed layer on the surface of the substrate, and a second glaze material suitable for forming a second glazed layer on the surface of the substrate containing antibacterial metal. In the glass transition step of the antibacterial treatment step, a layer of a first glaze material containing a first glaze material is formed on the surface of the base, and a layer of a second glaze material containing a second glaze material is formed on the surface of this layer. Then, the layer of the first glaze material and the layer of the second glaze material are melted to obtain a first glazed layer and a second glazed layer.

Moreover, since after melting the viscosity of the layer of the second glazing material is higher than the viscosity of the layer of the first glazing material, the antibacterial metal diffuses poorly from the second glazed layer on the outer surface into the first glazed layer, and remains almost completely in the second glazed layer. In the processing method for imparting resistance to contamination, even if a large amount of the antibacterial metal is not consumed, the antibacterial metal contained in the second glazed layer acts on the bacteria as expected, i.e. there is a good antibacterial effect.

In addition, in the processing method for imparting resistance to contamination according to the first invention, a layer of the first glaze material containing the first glaze material is formed, and on the outer surface of this layer is a layer of the second glaze material containing the second glaze material. The layer of the first glaze material and the layer of the second glaze material are then melted to form the first glazed layer and the second glazed layer. In the resulting product, the second glaze material penetrates into the layer of the first glaze material, therefore, the first glazed layer and the second glazed layer are tightly interconnected. In this way, the formation of cracks occurring at the interface between the layers can be prevented. In addition, the firing stage of both layers can be carried out simultaneously, thereby ensuring a reduction in production costs.

Therefore, in accordance with a processing method for imparting resistance to contamination, the manufacture of an article can be carried out with low manufacturing costs, and an article having a glazed layer with excellent antibacterial effect can be obtained.

The article with a glazed layer according to the first invention is obtained as described above. According to the first invention, an article having a glazed layer consists of a base with a glazed layer, which contains a first glazed layer containing the first glazing material, and a second glazed layer formed on the outer surface of the first glazed layer and containing the second glazing material, which contains an antibacterial metal and different from the first glaze material.

In the case of manufacturing a glass product with a glazed layer, a glass molded product can be used as a base. In the manufacture of a ceramic product, for example, a sanitary ceramic product, tiles, etc., a ceramic molded product can be used as a base; and in the case where an enameled product is manufactured, a metal molded product can be used.

As the antibacterial metal contained in the second glaze material, Ag, Cu, Zn and the like can be used. Specific examples include organic silver or copper compounds and inorganic compounds containing silver or copper, and

1) silver, copper and an alloy of silver and copper;

2) silver phosphate, silver nitrate, silver chloride, silver sulfide, silver oxide, silver sulfate, silver citrate and silver lactate;

3) copper (I) phosphate, copper (II) phosphate, organic copper compounds, copper (I) chloride, copper (II) chloride, copper (I) sulfide, copper (I) oxide, copper (II) oxide, copper sulfide (II) copper (I) sulfate, copper (II) sulfate, copper citrate and copper lactate; etc.

As for zinc, similar examples are organic zinc compounds and zinc-containing inorganic compounds. You can also use zinc, zinc oxide, zinc chloride, zinc sulfide, zinc sulfate, zinc lactate, etc. These antibacterial metals can be elemental substances or alloys, and can also be part of the compounds.

According to the first invention, in an article having a glazed layer, the thickness ratio of the first glazed layer and the second glazed layer is preferably in the range from 10/1 to 30/1. Even if the second glazed layer has a poor appearance, for example, due to the inclusion of antibacterial metals such as Ag and the like, a surface is obtained whose appearance does not practically differ from the appearance of the surface if only the first glazed layer is formed. Thus, it is possible to obtain a product having a surface with excellent appearance.

According to the results of the experiments of the authors in the product having a glazed layer, according to the first invention, the second glazed layer should contain more potassium and less sodium than the first glazed layer. Potassium has a larger ionic radius than sodium. Therefore, it is assumed that during the formation of the glazed layer on the product, the sodium ions contained in the second glazed layer undergo ion exchange for potassium ions contained in the first glazed layer, which leads to the appearance of compressive stress in the second glazed layer, thereby increasing its strength.

Furthermore, according to the first invention, in the treatment method for imparting resistance to contamination, it is preferable that the second glazing material contain a phosphoric acid compound. In an article having a glazed layer thus obtained, a phosphoric acid compound, for example P ₅ O ₅ and the like, is contained in the second glazed layer, and therefore the antibacterial effect inherent in the antibacterial metal is enhanced. It is also preferred that a boric acid compound is contained in the second glazing material. The boric acid compound, for example B ₂ O ₃ and the like, is contained in the second glazed layer, and therefore the antibacterial effect inherent in the antibacterial metal is enhanced.

According to the first invention, the treatment method for imparting resistance to pollution preferably includes a step of imparting water-repellent properties, comprising the step of treating the surface of the second glazed layer with a hydrophobic substance. The surfaces of the second glazed layer give both antibacterial and water repellent properties, and therefore, even when water containing a large amount of contaminating components gets onto it, that is, when the effect of resistance to pollution is insufficiently provided by one antibacterial action , pollution is poorly retained on the surface due to its water-repellent effect, due to which the effect of resistance to pollution is significantly enhanced.

In this case, the processing step for imparting water-repellent properties can be performed by forming a film consisting of a treatment fluid for imparting water-repellent properties containing silicon-containing functional groups that are combined with hydroxyl groups present on the surface of the second glazed layer as a result of a dehydration reaction or reaction dehydrogenation. When the treatment is carried out, the silicon-containing functional groups are combined with hydroxyl groups (-OH) present on the surface of the second glazed layer as a result of the dehydration or dehydrogenation reaction and screen the hydroxyl groups. Therefore, when water containing a large amount of metal ions, such as soluble silicon and the like, is used, hydroxyl groups are inactivated and do not bind to metal ions, and therefore they do not bind to components such as human excrement. In particular, when water containing soluble silicon as a metal ion is used, it is not deposited on the surface in the form of silicic acid, which forms a network structure, or its deposition is difficult, and therefore pollution is difficult to penetrate into it. Therefore, if the liquid used for processing to impart water-repellent properties contains silicon-containing functional groups, it is difficult for contaminants such as human excrement and the like to combine with a product used simultaneously with water containing a large amount of metal ions, for example, soluble silicon , and therefore it is easy to clean.

In this case, the treatment fluid for imparting water-repellent properties is preferably a fluid having no silicon-containing functional groups interconnected. As the results of the experiments of the authors have shown, the effects of resistance to pollution are enhanced, namely, resistance to scaling, resistance to contamination with hair dyes, wear resistance and alkali resistance. If the silicon-containing functional groups of the treatment fluid to impart water-repellent properties are interconnected, the amount of silicon increases, which leads to the deposition of silicic acid, which forms a network structure in the film, and contamination can penetrate into it.

The treatment fluid for imparting water-repellent properties preferably has fluorocarbon groups at the ends of the molecules associated with silicon-containing functional groups. As the results of the experiments of the authors showed, if fluorocarbon groups are included in this way, the water-repellent properties are significantly enhanced due to the small critical surface tension created by the fluorocarbon groups. At the same time, significant effects were obtained with respect to resistance to scaling, resistance to contamination by hair dyes, and resistance to alkalis.

In this work, the fluorocarbon group may be a group -C _n F2 _{n + 1} (n is a natural number from 1≤n≤12). As the results of the experiments of the authors showed, since the number of fluorine atoms becomes large and fluorosilane is voluminous, significant effects have been obtained with respect to resistance to scum contamination, resistance to contamination by hair dyes, wear resistance and alkali resistance.

The treatment fluid for imparting water-repellent properties may be a fluid formed by mixing the first reagent and the second reagent, the first reagent being the product of co-hydrolysis in a hydrophilic solvent of an organic silicon compound containing a perfluoroalkyl group and a methyl polysiloxane compound containing a hydrolyzable group, and the second reagent is a mixture of organopolysiloxane and a strong acid. In this case, the organic silicon compound containing the perfluoroalkyl group and the methyl polysiloxane compound containing the hydrolyzable group present in the first reagent are combined with hydroxyl groups present on the surface of the glazed layer as a result of a dehydration reaction or a dehydrogenation reaction, so that the first reagent can be used in as a component containing silicon-containing functional groups to protect hydroxyl groups.

The reason that an organic silicon compound containing a perfluoroalkyl group is used as a component of the first reagent is that the significant effect of resistance to pollution also manifests itself in the form of a water-repellent effect due to the high critical surface tension of the fluorocarbon groups, so that significant stability effects are provided to scale pollution, resistance to contamination by hair dyes and resistance to alkalis. The reason that a methyl polysiloxane compound containing a hydrolyzable group is used as a component of the first reagent is to achieve significant effects of resistance to scale contamination, hair dye contamination and alkali resistance.

The second reagent is a mixture of organopolysiloxane and a strong acid. The reason why organopolysiloxane is used as a component of the second reagent is that due to the small critical surface tension of the alkyl groups, pollution resistance effects, such as lipstick contamination resistance and wear resistance, occur. The reason that a strong acid is used as a component of the second reagent is that if the treatment for imparting resistance to contamination is carried out using a treatment fluid for imparting water-repellent properties prepared by the method according to the first invention, the strong acid effectively acts as a catalyst for binding an organic silicon compound containing a perfluoroalkyl group to a methyl polysiloxane compound containing a hydrolyzable group is components of the first reagent, with hydroxyl groups on the surface of the glazed layer.

It is believed that when the first reagent and the second reagent are mixed, the silanol groups of the co-hydrolysis product react with organopolysiloxane and a strong acid to form siloxane bonds (Si-O-Si) as a result of the dehydration reaction, so that an addition product consisting of many molecules is formed, interconnected in a complex way. Therefore, it is believed that the treatment fluid for imparting water-repellent properties resulting from the mixing of the first reagent and the second reagent does not consist of individual molecules of an organic silicon compound containing a perfluoroalkyl group, a methyl polysiloxane compound containing a hydrolyzable group, an organopolysiloxane, etc., but the product of the addition resulting from the combination of these molecules in a complex way, that is, from a certain type of polymer. In addition, the product of accession and the surface of the base are firmly bonded through chemical bonds.

According to a first invention, an article having a glazed layer has a water-repellent layer comprising a water-repellent component on the surface of the second glazed layer. Since the thickness of the water-repellent layer is extremely small, and the water-repellent layer is associated only with the hydroxyl groups of the surface of the second glazed layer, it is believed that the antibacterial effect can be realized through the drainage layer.

Second invention

There is a possibility that defects can form on the surface of a conventional ceramic product, and the hardness of its surface is insufficient, since it has one glazed layer. Therefore, it has the disadvantage that, due to the presence of defects, there is the possibility of cracking and the like. in the glazed layer after impact. In particular, in the case of a ceramic product whose surface is given an antibacterial effect by impregnating the glazed layer with an antibacterial metal such as Ag and the like, this trend can be expected to be pronounced, since it is believed that the antibacterial metal contributes to the development of cracks. The product also has the disadvantage that there is a possibility of adhesion of contamination with defects.

The second invention is the development of solutions known from the prior art, and the achieved goal is to provide a product of reinforced ceramic, on the surface of which the formation of defects is difficult.

The reinforced ceramic product of the second invention consists of a ceramic preform and a glazed layer formed on the surface of the preform. The product is characterized in that the glazed layer contains a first glazed layer containing the first glazed material, and a second glazed layer containing the second glazed material, which is formed on the outer surface of the first glazed layer and has a lower coefficient of linear thermal expansion than the first glazed layer.

In the reinforced ceramic product of the second invention, due to the fact that the coefficient of linear thermal expansion of the second glazed layer is less than the coefficient of linear thermal expansion of the first glazed layer, the second glazed layer experiences compressive stress due to shrinkage of the first glazed layer during the melting of the layers of the first and second glaze materials and in the process of cooling the first and second glazed layers at the stage of firing. Therefore, the second glazed layer is compacted and acquires high surface hardness, and defects are difficult to form on the surface of the glazed layer. Therefore, in the reinforced ceramic product of the second invention, crack formation in the glazed layer and the like is difficult due to defects. The adhesion of contamination to defects is also difficult, since the formation of defects is difficult.

The reinforced ceramic product of the second invention may have three or more glazed layers on the ceramic blank. For example, in the case where it has three glazed layers, the lowermost layer corresponds to the first glazed layer, the intermediate layer corresponds to the second glazed layer and at the same time corresponds to the first glazed layer with respect to the upper layer, and the upper layer corresponds to the second glazed layer.

In the reinforced ceramic product of the second invention, it is preferable that the ceramic preform has a greater coefficient of linear thermal expansion than the first glazed layer. In this case, not only the second glazed layer experiences compressive stress from the first glazed layer, but the first glazed layer experiences compressive stress from the ceramic preform during sintering of the preform material, during the melting of the layers of the glaze material, and during the cooling of the ceramic preform and glazed layers at the stage of firing, due to which not only the second glazed layer is compacted, but also the first glazed layer. Therefore, in the reinforced ceramic product of the second invention, cracking and the like are difficult in the glazed layer.

In the reinforced ceramic product of the second invention, it is preferable that the difference between the linear thermal expansion coefficients of the first glazed layer and the second glazed layer is in the range from 1 × 10 ^-7 to 1 × 10 ^-6 / ° C. In the case where the difference between the linear thermal expansion coefficients of the first glazed layer and the second glazed layer is less than the lower boundary of the specified interval, it is impossible to obtain the desired surface hardness. On the other hand, when it is greater than the upper boundary of the indicated interval, the compressive stress experienced by the second glazed layer under the action of the first glazed layer becomes too large and creates the possibility of destruction of the second glazed layer. In particular, according to the results of the experiments of the authors, it is advisable that the difference between the coefficients of linear thermal expansion of the first glazed layer and the second glazed layer be in the range from 2 × 10 ^-7 to 5 × 10 ^-7 .

In this case, it is preferable that the size ratio of the thickness of the first glazed layer and the second glazed layer is in the range from 10/1 to 30/1. Even if the appearance of the second glazed layer is poor due to the inclusion of an antibacterial metal, for example, Ag, etc., it is possible to obtain a surface that is practically no different in appearance from the surface when only the first glazed layer is formed. Accordingly, it is possible to obtain a reinforced ceramic product having an excellent appearance.

By controlling the composition and thickness of the second glazed layer, it is possible to interfere with light interference at the interface with the first glazed layer, and therefore, iridescence can be prevented. In addition, depending on the composition of the second glazed layer, it is formed in the form of a crystallized glassy material, as a result of which it becomes opaque.

Preferably, the difference between the linear thermal expansion coefficients of the ceramic preform and the first glazed layer is in the range from 1 × 10 ⁻⁷ to 1 × 10 ⁻⁶ / ° C. In the case where the difference between the linear thermal expansion coefficients of the ceramic workpiece and the first glazed layer is less than the lower boundary of the specified interval, it is impossible to obtain the desired strength. On the other hand, when the difference exceeds the upper limit of the indicated interval, the compressive stress experienced by the first glazed layer under the action of the ceramic preform becomes too large and creates the possibility of destruction of the first glazed layer. In particular, according to the results of the experiments of the authors, it is advisable that the difference between the coefficients of linear thermal expansion of the ceramic workpiece and the first glazed layer be in the range from 2 × 10 ^-7 to 5 × 10 ^-7 .

According to the results of the experiments of the authors in the product of reinforced ceramics according to the second invention, the second glazed layer should contain more potassium and less sodium than the first glazed layer. Potassium has a larger ionic radius than sodium. Therefore, it is assumed that when the glazed layer is formed on the ceramic product according to the second invention, the sodium ions contained in the second glazed layer are ion-exchanged for potassium ions contained in the first glazed layer, which leads to the appearance of compressive stress in the second glazed layer, due to which its strength increases.

In the event that an antibacterial metal is distributed in one of the glazed layers to give the ceramic product antibacterial properties, it is likely that the antibacterial metal will loosen the glassy material, which will lead to cracking. Therefore, the reinforced ceramic product of the second invention has better properties if the antibacterial metal is contained in the second glazed layer. Since the second glazed layer containing the antibacterial metal is sealed, it is possible to prevent the development of cracks in the second glazed layer due to the inclusion of the antibacterial metal. In the reinforced ceramic product of the second invention, since the antibacterial metal of all the glazed layers is contained only in the second glazed layer, the concentration of the antibacterial metal on the outer surface can be increased even with a smaller amount of the antibacterial metal than in a conventional product, whereby more can be achieved. antibacterial effect. In addition, unnecessary consumption of the antibacterial metal can be prevented.

In this case, metals similar to those of the first invention can be used as an antibacterial metal.

Furthermore, in the reinforced ceramic product of the second invention, it is preferable that a water-repellent layer comprising a water-repellent component is formed on the outer surface of the second glazed layer. Even if water containing a large amount of contaminating components enters a surface having a small number of defects, contamination of the surface of the product is difficult due to the water-repellent effect and a significant effect of resistance to contamination takes place.

In this case, the same processing step can be carried out to impart water-repellent properties as in the first invention.

A method of manufacturing a reinforced ceramic product according to the second invention includes a preparatory stage, which consists in preparing a base material suitable for forming a ceramic product preform, and a glaze material suitable for forming a glazed layer on the surface of a ceramic product preform, a glazing stage, which consists in forming a layer of glaze material containing glaze material on the surface of the workpiece, and the firing stage, which consists in firing the base material and the layer of glaze about the material to obtain a ceramic product, consisting of a ceramic workpiece and a glazed layer. The method is characterized in that the glaze material contains a first glaze material that is applied to the surface of the base material, and which forms the first glazed layer, and a second glaze material that is applied to the outer surface of the first glaze material, and which forms a second glazed layer having a lower coefficient linear thermal expansion than the first glaze layer. The reinforced ceramic product of the second invention can be manufactured by the manufacturing method of the second invention.

In the method of manufacturing a reinforced ceramic product of the second invention, a layer of a first glaze material containing a first glaze material can be formed at the glazing stage, and then a layer of a second glaze material containing a second glaze material can be formed on the surface of the layer of the first glaze material. In the reinforced ceramic product of the second invention, thus obtained, the first glaze material penetrates the surface of the base material since the first glaze material is applied to the base material to form a layer of the first glaze material. The first glaze material penetrated into the base material also forms the first glazed layer inside the ceramic product molded from the base material. Therefore, the first glazed layer is firmly connected to the ceramic blank. In addition, in a reinforced ceramic product, since the second glaze material is applied to the layer of the first glaze material to form a layer of the second glaze material, the second glaze material penetrates the layer of the first glaze material, whereby the first glazed layer and the second glazed layer are tightly adhered between by itself, and it is also possible to prevent the formation of cracks that occur on the surface of their separation. The firing stage of both layers can be carried out simultaneously, and due to this, production costs can be reduced.

In addition, in the method for manufacturing the reinforced ceramic product of the second invention, it is preferred that the first glazing material contains potassium and the second glazing material contains sodium. Since the radius of the potassium ion is larger than the radius of the sodium ion, when using such first and second glaze materials, the sodium ions contained in the second glaze material undergo ion exchange for potassium ions contained in the first glaze material. Accordingly, it is possible to obtain a reinforced ceramic product according to the second invention, which has a second glazed layer containing more potassium and less sodium than the first glazed layer.

In the method for manufacturing a reinforced ceramic product of the second invention, the second glazing material may comprise an antibacterial metal. Thus, it is possible to obtain a product of reinforced ceramics with antibacterial action.

In addition, in the method of manufacturing a reinforced ceramic product according to the second invention, it is permissible that the second glazing material after melting, i.e. in the molten state, had a higher viscosity than the first glaze material. Degassing during firing occurs evenly, due to which it is possible to prevent the formation of bubbles in the reinforced ceramic product, as well as to reduce the diffusion rate of the antibacterial metal from the second glazed layer to the first glazed layer during firing, in order to produce a reinforced ceramic product having a concentration of antibacterial metal on the surface maintained at a high level.

Further, the method of manufacturing a reinforced ceramic product according to the second invention may include a processing step to impart water-repellent properties, comprising the step of processing the surface of the glazed layer to impart water-repellent properties to it. Thus, such a product can be made of reinforced ceramic, on which the formation of contaminants is difficult.

Third invention

In the case of a conventional product having a glazed layer, it is likely that defects will form on its surface. The surface hardness of such a product is insufficient, since the glazed layer is a single layer. Therefore, it has the disadvantage that there is a possibility of formation of cracks in the glazed layer under the influence of impact, etc. due to defects. It is also characterized by such a drawback that pollution can adhere to defects. Therefore, the possibility of using a glazed layer consisting of several layers was analyzed. However, it was found that for the product, which simply applied a glazed layer consisting of several layers, the formation of defects is still characteristic, and the surface hardness is still insufficient. Accordingly, the product has the disadvantage that it does not show resistance to contamination.

The third invention is the development of solutions known from the prior art, and the goal is to obtain an article having a glazed layer, on the surface of which defects would be difficult to form, and which would certainly exhibit excellent resistance to contamination.

An article having a glazed layer according to the third invention consists of a base and a glazed layer formed on the surface of the base. The product is characterized in that the glazed layer contains a first glazed layer containing the first glazed material, and a second glazed layer containing the second glazed material, which is formed on the outer surface of the first glazed layer and has a lower coefficient of linear thermal expansion than the first glazed layer. Small solid particles are scattered on the surface of the second glazed layer.

In an article having a glazed layer according to the third invention, since the coefficient of linear thermal expansion of the second glazed layer is less than the coefficient of linear thermal expansion of the first glazed layer, the second glazed layer experiences compressive stress due to shrinkage of the first glazed layer during the melting of the layers the first and second glaze materials and in the process of cooling the layers of the first and second glaze materials at the stage of firing. Therefore, the second glazed layer is compacted to form a surface of high hardness, where the formation of defects is difficult. In addition, the formation of cracks and the like in the glazed layer is difficult, which may occur in the presence of defects. Therefore, the formation of contaminants that are mainly adhered to defects and cracks is difficult on the product of the third invention, and excellent resistance to contamination can be achieved.

In particular, if the product of the third invention is exposed to external factors that damage the surface of the second glazed layer, the fine solid particles present on the surface prevent mechanical damage to the surface of the second glazed layer. Therefore, even if these factors affect the surface of the second glazed layer, the exposure time is short and the formation of serious defects is difficult. Therefore, the formation of contaminants on the product of the third invention is difficult, and excellent resistance to contamination is provided.

In the product of the third invention, since the coefficient of linear thermal expansion of the second glazed layer is less than the coefficient of linear thermal expansion of the first glazed layer, it is difficult to form pores in the second glazed layer. Therefore, the product has great smoothness and exhibits excellent resistance to contamination.

An article having a glazed layer may be based on three glazed layers or more. For example, in the case where it has three glazed layers, the intermediate layer corresponds to the first glazed layer, and the top layer corresponds to the second glazed layer.

As small solid particles used in an article having a glazed layer, small metal particles and small particles of inorganic material, such as small particles of silicon nitride and the like, can be used. Fine solid particles preferably have an average particle size of from 0.8 to 20 microns. Thus, it provides resistance to the formation of defects, and maintains a good appearance of the product having a glazed layer.

In accordance with the results of the experiments of the authors, it is preferable to use small particles of zircon. Small particles of zircon are harder than substances and objects that create defects on the surface of the second glazed layer. Such substances and objects are, for example, brushes and abrasive cleaners. Small particles of zircon interact with these substances and objects, and therefore the formation of defects on the surface of the second glazed layer is difficult.

Small particles of zircon provide resistance to the formation of defects, as described above, on the other hand, they reduce the smoothness of the surface of the second glazed layer and affect the color of the second glazed layer, depending on their amount contained in the second glazed layer. Therefore, the proportion of small particles of zircon contained in the second glazed layer should preferably be from 0.5 to 2 wt. percent.

In an article having a glazed layer, it is preferred that the base of the article has a greater coefficient of linear thermal expansion than the first glazed layer. Thus, not only the second glazed layer is subjected to compressive force from the first glazed layer, but also the first glazed layer is subjected to compressive force from the base of the ceramic product during sintering of the base material, during the melting of the layers of the glaze materials and in the process of cooling the base of the ceramic product and the glazed layers at the firing stage. This compacts not only the second glazed layer, but also the first glazed layer. Therefore, in an article having a glazed layer, it is difficult to form cracks in the glazed layer, which is caused by defects.

In the product having a glazed layer, it is preferable that the difference between the linear thermal expansion coefficients of the first glazed layer and the second glazed layer is in the range from 1 × 10 ^-7 to 1 × 10 ^-6 / ° C. In the case where the difference between the linear thermal expansion coefficients of the first glazed layer and the second glazed layer is less than the lower boundary of the specified interval, it is impossible to obtain the desired surface hardness, on the other hand, if it is greater than the upper boundary of the specified interval, the compressive stress experienced by the second glazed layer under the action of the first glazed layer, it becomes too large and creates the possibility of destruction of the second glazed layer. In particular, according to the results of the experiments of the authors, it is advisable that the difference between the coefficients of linear thermal expansion of the first glazed layer and the second glazed layer be in the range from 2 × 10 ^-7 to 5 × 10 ^-7 .

In this case, it is preferable that the size ratio of the thickness of the first glazed layer and the second glazed layer is in the range from 10/1 to 30/1. Thus, even if the appearance of the second glazed layer is poor due to the inclusion of an antibacterial metal, for example, Ag, etc. in the second layer, it is possible to obtain a surface that is almost identical in appearance to the surface in when only the first glazed layer is formed. As a result, a product having a glazed layer with excellent appearance can be obtained.

By adjusting the composition and thickness of the second glazed layer, it is possible to interfere with light interference at the interface with the first glazed layer, thus iridescence can be prevented. In addition, depending on the composition of the second glazed layer, the second glazed layer may be formed as a crystallized glassy material, so that it becomes opaque.

Preferably, the difference between the linear thermal expansion coefficients of the base of the product and the first glazed layer is in the range from 1 × 10 ^-7 to 1 × 10 ^-6 / ° C. In the case where the difference between the linear thermal expansion coefficients of the base and the first glazed layer is less than the lower boundary of the specified interval, it is impossible to obtain the desired strength. On the other hand, if it is greater than the upper boundary of the indicated interval, the compressive stress experienced by the first glazed layer under the action of the substrate becomes too large and creates the possibility of destruction of the first glazed layer. In particular, according to the results of the experiments of the authors, it is advisable that the difference between the coefficients of linear thermal expansion of the first glazed layer and the second glazed layer be in the range from 2 × 10 ^-7 to 5 × 10 ^-7 .

According to the results of the experiments of the authors in the product having a glazed layer, the second glazed layer should contain more potassium and less sodium than the first glazed layer. Potassium has a larger ion radius than sodium. Therefore, it is assumed that upon the formation of glazed layers on an article having a glazed layer, the sodium ions contained in the second glazed layer undergo ion exchange for potassium ions contained in the first glazed layer, which leads to the appearance of compressive stress in the second glazed layer, due to which increases the strength of the second glazed layer.

An article having a glazed layer exhibits a greater effect of resistance to contamination if the second glazed layer contains an antibacterial metal. In particular, in an article having a glazed layer, since the antibacterial metal is contained from all the glazed layers only in the second glazed layer, the concentration of the antibacterial metal on the outer surface can be increased even when using a smaller amount of the antibacterial metal than in a conventional product, whereby greater antibacterial effect. In addition, unnecessary consumption of the antibacterial metal can be prevented.

In this case, metals similar to the metals of the first and second inventions can be used as an antibacterial metal.

In addition, in an article having a glazed layer, it is preferable that a water-repellent layer comprising a water-repellent component is formed on the outer surface of the second glazed layer. Thus, even if water containing a significant amount of contaminants enters a surface having a small number of defects, the deposition of contaminants is difficult due to the water-repellent effect, and an excellent effect of resistance to contamination takes place.

In this case, the same processing step can be carried out to impart water-repellent properties as in the first and second inventions.

In an article having a glazed layer, the base may be a blank of ceramic mass. In this case, the product is a ceramic product, for example, a toilet bowl, a sink, and the like. These ceramic products in particular should have the indicated effects, since they are often washed with a brush using a detergent containing water and an abrasive.

According to a third invention, a method for manufacturing an article having a glazed layer includes a preparatory step comprising preparing a base and a glaze material suitable for forming a glazed layer on the surface of the base, a glazing step consisting of forming a layer of glaze material containing the glaze material on the surface of the base, and a firing step, comprising firing the base material and a layer of glaze material to form an article consisting of a base and a glazed layer. The method is characterized in that the glaze material contains a first glaze material that is applied to the surface of the base and which forms the first glazed layer, and a second glaze material that is applied to the outer surface of the first glaze material, and which forms the second glazed layer. This second layer has a lower coefficient of linear thermal expansion than the first glazed layer, and small solid particles are scattered on its surface. An article having a glazed layer according to the third invention can be manufactured by the method according to the third invention.

According to a third invention, in a method of manufacturing an article having a glazed layer, a layer of a first glazing material containing a first glazing material can be formed in the glazing step, and then a layer of a second glazing material containing a second glazing material can be formed on the surface of the layer of the first glazing material. In the thus obtained product having a glazed layer, the first glaze material penetrates the surface of the base material, since the first glaze material is applied to the base material to form a layer of the first glaze material. The first glaze material penetrated into the base material also forms the first glazed layer inside the base. Therefore, the first glazed layer is tightly connected to the base of the product. In addition, in the product, since the second glaze material is applied to the layer of the first glaze material to form a layer of the second glaze material, the second glaze material penetrates the layer of the first glaze material, whereby the first glazed layer and the second glazed layer are tightly adhered to each other, and it is also possible to prevent the formation of cracks occurring on their interface. Thus, both layers can be fired at the same time, thereby reducing production costs.

In addition, in the manufacturing method of an article having a glazed layer, it is preferred that the first glazing material contains potassium and the second glazing material contains sodium. Since the radius of the potassium ion is larger than the radius of the sodium ion, when using such first and second glaze materials, the sodium ions contained in the second glaze material undergo ion exchange for potassium ions contained in the first glaze material. Accordingly, it is possible to obtain an article having a glazed layer, which has a second glazed layer containing more potassium and less sodium than the first glazed layer.

In the method for manufacturing an article having a glazed layer according to the third invention, it is possible for the second glazing material to contain an antibacterial metal. Thus, it is possible to obtain a product having a glazed layer, which is given antibacterial properties.

In addition, in the method for manufacturing an article having a glazed layer according to the third invention, it is permissible for the second glazing material to have a higher viscosity after melting, i.e. in a molten state than the first glaze material. Thus, the aggregation of small solid particles dispersed in the second glazed layer can be prevented, and therefore, small solid particles will be properly distributed over the surface. In addition, degassing during firing occurs evenly, due to which it is possible to prevent the formation of bubbles in the ceramic product, as well as to reduce the diffusion rate of the antibacterial metal from the second glazed layer into the first glazed layer during firing, in order to produce an article having a glazed layer with a concentration of antibacterial metal on a surface that remains high.

Further, the manufacturing method of an article having a glazed layer according to the third invention may include a processing step for imparting water-repellent properties, comprising processing the surface of the glazed layer to impart water-repellent properties thereto. According to the configuration, such an article may be manufactured having a glazed layer on which the formation of contaminants is hindered.

BRIEF LIST OF FIGURES OF DRAWINGS

Figure 1 is a cross-section of the base and the layer of the first glaze material from Example related to the first invention.

Figure 2 is a cross-section of the base, the layer of the first glaze material and the layer of the second glaze material from Example related to the first invention.

Figure 3 is a cross-section of the base, the first glazed layer and the second glazed layer of Example related to the first invention.

Figure 4 is a cross-section of the base, the first glazed layer, the second glazed layer and the water-repellent layer of Example related to the first invention.

5 is a cross section of the base and glazed layer of comparative Examples 1 and 2 related to the first invention.

6 is a cross-sectional view of a base material and a layer of a first glaze material from Example related to the second invention.

Fig. 7 is a cross-sectional view of a base material, a layer of a first glaze material, and a layer of a second glaze material from Example relating to the second invention.

Fig. 8 is a cross-sectional view of a ceramic base, a first glazed layer and a second glazed layer of Example relating to the second invention.

Fig.9 is a cross-section of the base of the ceramic product, the first glazed layer, the second glazed layer and the water-repellent layer of Example related to the second invention.

Figure 10 is a cross-section of the base of a ceramic product and the glazed layer of comparative Example related to the second invention.

11 represents the result of a surface analysis for potassium content by EPMA for a cross-section of a sample from Example related to the second invention.

12 is a cross-sectional view of a base material and a layer of a first glaze material from Examples 1-7 related to the third invention.

13 is a cross-sectional view of a base material, a layer of a first glaze material, and a layer of a second glaze material of Examples 1-7 related to the third invention.

Fig. 14 is a cross-sectional view of a ceramic base, a first glazed layer and a second glazed layer of Examples 1-7 related to the third invention.

Fig. 15 is a cross-sectional view of the sample of Examples 1-7. relating to the third invention.

Fig.16 is a top view of the sample of Examples 1-7 related to the third invention.

17 is a cross-sectional view of a sample of comparative Examples 1 and 2 related to the third invention.

Fig. 18 is a cross-sectional view of a sample of comparative Examples 3 and 4 related to the third invention.

19 is a surface analysis of potassium content by EPMA for a cross section of a sample of Examples 1-7 related to the third invention.

INTELLIGENCE. SUMMARY OF THE INVENTION

First invention

An example embodiment of the first invention and comparative Examples 1 and 2 will be described below with reference to figures 1-5.

"Preparatory stage" "stage of antibacterial treatment"

The basis for the ceramic tiles of the composition below is made in the form of a molded ceramic product. The base for tiles is cut into squares with a side of 50 ± 2 mm (thickness: 10 mm or less), which are designated as base 1, shown in figure 1 and figure 2.

The proportions of the mixture for the material of the base of the tiles (mass%) Feldspar 28,2 Quartz sand 11.8 Sericite 15.0 Clay 45.0

A first glaze material and a second glaze material are prepared having the following compositions.

The proportions of the mixture for the first glaze material (mass%) Feldspar 35.0 Quartz sand 46.9 Lime 15.9 Clay 2.2

The first glaze material contains 2 wt.% K ₂ O.

The proportions of the mixture for the second glaze material (mass%) Quartz sand 31,0 Lime 6.0 Clay 13.0 Antibacterial 50,0

The antibacterial agent has the following composition (in mass%).

Ag ₂ O 25.88 P ₂ O ₅ 4.98 CaO 0.01 SiO ₂ 56.84 Al ₂ O ₃ 9.36 Fe ₂ O ₃ 0.10 K ₂ O 0.43 Na ₂ O 0.06 Sro 0.01 Loss on ignition 2,34

The second glaze material contains 2 wt.% Na ₂ O.

"Glass transition step" "antibacterial treatment step"

As shown in FIG. 1, the first glaze material is applied to the surface of the base 1 to form a layer of the first glaze material 2. Then, as shown in FIG. 2, the second glaze material is applied to the outer surface of the layer of the first glaze material 2 to form a layer of the second glaze material 3.

The base 1 having a layer of the first glaze material 2 and a layer of the second glaze material 3 is fired at 1210 ° C. The layer of the first glaze material 2 and the layer of the second glaze material 3 are melted to form the first glazed layer 4 and the second glazed layer 5 on the basis of 1, as shown in Fig.3.

In this case, since the layer of the second glaze material 3 in the molten state has a higher viscosity than the layer of the first glaze material 2, most of the silver compound 6 is added to the second glaze material, so that the antibacterial metal remains in the second glazed layer 5. In addition, the first the glazed layer 4 and the second glazed layer 5 have a thickness ratio of 20/1.

"Processing step for imparting water-repellent properties"

After this, a processing step is carried out to impart water-repellent properties to the surface of the second glazed layer 5.

The first reagent is prepared, which consists of

C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃

as an organic compound of silicon containing a perfluoroalkyl group, and

Si (CH ₃ O) ₃ CH ₂ CH ₂ - (Si- (CH ₃ ) ₂ O) ₁₀ -Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

as a polymethylsiloxane compound containing a hydrolyzable group, which is subjected to joint hydrolysis in a hydrophilic solvent containing a 0.1N aqueous solution of hydrochloric acid, tert-butanol and hexane. It is believed that they respectively contain silanol (Si-OH) groups.

A mixture of polyorganosiloxane (HO- (Si (CH ₃ ) ₂ O) ₃₀ -Si (CH ₃ ) ₂ OH) and methanesulfonic acid as a strong acid is prepared as the second reagent.

5 ml of the second reagent is added to 5 ml of the first reagent and mixed to form a treatment liquid to impart water-repellent properties. A treatment fluid to impart water-repellent properties is applied to the surface of the second glazed layer 5 to form a film. After that, it is left for about 10 minutes to dry. Then the surface is washed with ethanol and dried.

As a result of the above procedures, as shown in FIG. 4, a sample is obtained which consists of a base 1, a first glazed layer 4 containing the first glaze material and formed on the basis of 1, a second glazed layer 5 containing a second glaze material, which is different from the first a glaze material containing an antibacterial metal and formed on the outer surface of the first glazed layer 4, and a water-repellent layer 7 containing a water-repellent component and formed on the surface of the second 5th glazed layer.

In the sample from this Example, since the first glazed layer 4 and the second glazed layer 5 have a thickness ratio of 20/1, a surface is obtained that does not differ significantly in appearance from the surface obtained when only the first is applied glazed layer 4. The resulting surface has an excellent appearance, despite the fact that the second glazed layer itself has a poor appearance due to the inclusion of a silver compound 6.

Comparative Example 1

As shown in FIG. 5, a glaze material having the composition below is applied to the same base material as in the Example to form a layer of glaze material.

The proportions of the mixture for the glaze material (mass%) Feldspar 53.7 Quartz sand 9.8 Lime 12.3 Dolomite 4.8 Clay 5.1 Zinc White 2.0 Zircon 10.1 Silicate frit 2.2

To the mixture to obtain the glaze material add 0.5 wt.% (Of the total amount) of powdered silver with a purity of 99% or more and an average particle size of 10 μm.

The base 1 coated with a layer of glaze material is fired at 1210 ° C. When this layer of glaze material melts with the formation of a glazed layer 8 on the surface of the base 1, as shown in Fig.5. As a result, a sample was obtained, which consists of a base 1 and a glazed layer 8 containing an antibacterial metal and glazing material. This layer is formed on the surface of the base 1.

Comparative Example 2

A glaze material was used with a silver powder concentration of 5.0 wt.%, That is, 10 times greater than in comparative Example 1. Everything else, that is, the processing process to impart resistance to contamination and the composition of the sample, are the same as in comparative Example 1.

Rating

Three samples were prepared from Example and comparative Examples 1 and 2, which were analyzed for antibacterial effectiveness by a film method. The results are shown in Table 1.

TABLE 1 Nutrient concentration Escherichia coli (IFO3972) Staphylococcus aureus (IFO12732) medium (PB - nutrient broth) Example Comparative Example 1 Comparative Example 2 Example Comparative Example 1 Comparative Example 2 1/500 PB 5.5 2,8 4.0 4.8 2,3 3.2 1/200 PB 4.2 1.4 2,5 3,7 1,1 2.1 1/50 PB 2.7 0,0 0.2 2,3 0,0 0.1

From Table 1 it is clear that, if we analyze the antibacterial effect on both types of bacteria, then in Example, the average change in the rate of reproduction of bacteria, equal to 2.0 or more, is maintained even when the concentration of the nutrient medium increases, while in comparative Example 1 the average change in the rate of bacterial reproduction, equal to 2.0 or more, is preserved only in the case of a concentration of 1/500 PB or less, and in comparative Example 2, only in the case of 1/200 PB or less. Therefore, it is clear that in Example there is a good effect of resistance to pollution, in comparison with comparative Examples 1 and 2, even though the Example used a smaller amount of powdered silver than in comparative Examples 1 and 2.

From the foregoing, it is clear that since in the Example, the silver compound 6 is present in the second glazed layer 5 on the outer surface, its concentration on the surface increases with the same amount of silver compound 6, compared with the cases when the antibacterial metal is distributed over the entire thickness of the glazed layer, as in comparative Examples 1 and 2, due to which there is a good antibacterial effect, and unnecessary expenditure of the antibacterial metal can also be prevented. In particular, since the Example contains a phosphoric acid compound in the second glaze material, the likelihood of an antibacterial effect due to the antibacterial metal is increased. In addition, since in the Example a water-repellent layer 7 is formed on the surface of the second glazed layer 5, there is both an antibacterial and a water-repellent effect. Therefore, even if water containing a large number of polluting components is used, so that the pollution resistance cannot be realized due to a single antibacterial effect, the sedimentation of the pollution is difficult due to the water-repellent effect, so that the pollution resistance is fully realized.

Therefore, it is clear that in accordance with the processing method for imparting resistance to pollution according to Example, it is possible to obtain such an article having a glazed layer that can be manufactured at low production costs, and which can have good antibacterial properties.

In addition, in the processing method for imparting resistance to pollution according to Example, uniform degassing during firing is possible, thereby preventing the formation of bubbles in the sample.

Second invention

An embodiment of the second invention and a comparative example will be described below.

Example

"Preparatory stage"

The base material for tiles 1, prepared from the composition below, is cut into squares with a side of 50 ± 2 mm, a thickness of 10 mm or less.

The proportions of the mixture for the base material 1 (mass%) Feldspar 28,2 Quartz sand 11.8 Sericite 15.0 Clay 45.0

A first glaze material and a second glaze material are prepared having the following compositions.

The proportions of the mixture for the first glaze material (mass%) Feldspar 35.0 Quartz sand 46.9 Lime 15.9 Clay 2.2

The first glaze material contains 2 wt.% K ₂ O.

The proportions of the mixture for the second glaze material (mass%) Quartz sand 31,0 Lime 6.0 Clay 13.0 Antibacterial 50,0

The antibacterial agent has the following composition (in mass%).

Ag ₂ O 25.88 P ₂ O ₅ 4.98 Cao 0.01 SiO ₂ 56.84 Al ₂ O ₃ 9.36 Fe ₂ O ₃ 0.10 K ₂ O 0.43 Na ₂ O 0.06 Sro 0.01 Loss on ignition 2,34

The second glaze material contains 2 wt.% Na ₂ O.

"Stage of glazing"

As shown in FIG. 6, the first glaze material is applied to the surface of the base material 1 to obtain a layer of the first glaze material 2, and then, as shown in FIG. 7, the second glaze material is applied to the outer surface of the layer of the first glaze material 2 to obtain a second layer glaze material 3.

"Stage of firing"

The base material 1, having a layer of the first glaze material 2 and a layer of the second glaze material 3, is fired at 1210 ° C. In this case, the base material is sintered, and the layer of the first glaze material 2 and the layer of the second glaze material 3 are melted to form the first glazed layer 4 and the second glazed layer 5 based on 1 ceramic product, as shown in Fig. 8.

In this case, the second glazed layer 5 has a lower coefficient of linear thermal expansion than the coefficient of linear thermal expansion of the first glazed layer 4, and the difference between the coefficients is 3 × 10 ^-7 / ° C. In addition, the first glazed layer 4 has a lower coefficient of linear thermal expansion than the coefficient of linear thermal expansion of the base 1 of the ceramic product, and the difference between the coefficients is 4 × 10 ^-7 / ° C. In addition, the first glazed layer 4 and the second glazed layer 5 have a thickness ratio of 20/1. The second glazed layer 5 contains a dispersed silver compound 6 as an antibacterial metal.

"Processing step for imparting water-repellent properties"

After this, a processing step is carried out to impart water-repellent properties to the surface of the second glazed layer 5.

The first reagent is prepared, which consists of

C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃

as an organic compound of silicon containing a perfluoroalkyl group, and

Si (CH ₃ O) ₃ CH ₂ CH ₂ - (Si- (CH ₃ ) ₂ O) ₁₀ -Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

as a polymethylsiloxane compound containing a hydrolyzable group, which is subjected to joint hydrolysis in a hydrophilic solvent containing a 0.1N aqueous solution of hydrochloric acid, tert-butanol and hexane. It is believed that they respectively contain silanol (Si-OH) groups.

A mixture of polyorganosiloxane (HO- (Si (CH ₃ ) ₂ O) ₃₀ -Si (CH ₃ ) ₂ OH) and methanesulfonic acid as a strong acid is prepared as a second reagent.

5 ml of the second reagent is added to 5 ml of the first reagent and mixed to obtain a treatment liquid to impart water-repellent properties. A treatment fluid to impart water-repellent properties is applied to the surface of the base 1 of a ceramic product having a first glazed layer 4 and a second glazed layer 5, and then dried, leaving it for about 10 minutes. Then the surface is washed with ethanol and dried.

As a result of the above procedures, as shown in Fig. 9, a sample is obtained which consists of a base 1 of a ceramic product, a first glazed layer 4 containing a first glaze material and formed on the basis of 1 ceramic product, a second glazed layer 5 containing a second glaze material, which differs from the first glaze material containing an antibacterial metal and formed on the outer surface of the first glazed layer 4, and a water-repellent layer 7 containing a water-repellent component and formed on the surface of the second glazed layer 5.

Comparative Example

As shown in FIG. 10, a glaze material having the composition below is applied to the same base material 1 as in the Example to form a layer of glaze material.

The proportions of the mixture for the glaze material (mass%) Feldspar 10.0 Kaolin 5,0 Silicate frit 85.0

The silicate frit in this case had the following composition (in mass%).

SiO ₂ 67.4 Al ₂ O ₃ 8.6 MgO 2.7 CaO 5.7 Sro 3.2 Na ₂ O 2,3 K ₂ O 3.2 B ₂ O ₃ 3,5 Zno 2,3 MoO ₃ 1,1

The base material 1 coated with a layer of glaze material is fired at 1210 ° C. When this layer of glaze material melts with the formation of a glazed layer 8 based on 1 ceramic products, as shown in Fig.10. In this way, a sample is obtained which consists of a base 1 of a ceramic product and a glazed layer 8 containing an antibacterial metal and glazing material. This layer is formed on the basis of 1.

Rating

Samples from Example and Comparative Example were prepared and subjected to the brushing test described below.

Brush Test

A commercially available toothbrush was used with an abrasive product commercially available on it. On the surface of the sample 20 times was carried out with a toothbrush with constant pressure. Then, the number of defects and the total length of the defects (mm) per 4 cm ^{2 were} determined.

The results are shown in Table 2.

TABLE 2 Number of defects total length 0.7 (mm) and 0.3-0.6 (mm) 0-0.2 (mm) defects (mm) more Comparative
Example 9 10 8 13.7 Example one four 2 2,8

From table 2 it is clear that in the sample from Example, the first glazed layer 4, the second glazed layer 5 and the base 1 of the ceramic product is difficult to damage, compared with the sample from comparative Example. It is believed that this is due to the following reasons.

1) In the Example, due to the fact that the coefficient of linear thermal expansion of the second glazed layer is less than the coefficient of linear thermal expansion of the first glazed layer 4, the second glazed layer 5 experiences compressive stress due to the shrinkage of the first glazed layer 4 during the melting of the layers of the first and second glaze materials 2 and 3 and in the process of cooling the first and second glazed layers 4 and 5 at the stage of firing. Therefore, the second glazed layer 5 is compacted and acquires a high surface hardness. It is clear that cracking and the like are difficult on the sample from Example. in the glazed layer, which is caused by the presence of defects, and also it is difficult to attach contaminants to it, which is also due to the presence of defects.

2) Since the base 1 of the ceramic product has a greater coefficient of linear thermal expansion than the first glazed layer 4, the first glazed layer 4 experiences compressive stress from this base, as a result of which it is compacted. Therefore, in the sample from Example it is difficult to propagate cracks and the like formed in the glazed layer.

3) In addition, it is clear that, as shown in FIG. 11, the X-ray hardness (frequency) of the potassium Kα-line in the Example is in the range from 198 to 331 Hz in the first glazed layer 4, and in the range from 331 to 463 Hz in the second glazed layer 5. Therefore, it can be said that in the Example, sodium ions having a small ionic radius and present in the second glazed layer 5 are replaced by potassium ions having a larger ionic radius and present in the first glazed layer 4. Ions potassium diffuse in the second glaze ny layer 5. Therefore, the second glazed layer 5 develops its own compressive stress, and it is hardened.

4) Since in the sample from Example the first glaze material is applied to the base material 1 to form a layer of the first glaze material 2, the first glaze material penetrates the surface of the base material 1. The first glaze material penetrated into the base material 1 also forms the first glazed layer 4 inside basics of 1 ceramic product. Therefore, the first glazed layer 4 is tightly connected to the base 1 of the ceramic product. A second glaze material 3 is applied to the layer of the first glaze material 2 to form a layer of the second glaze material 3 in this sample. The second glaze material penetrates into the layer of the first glaze material 2, whereby the first glazed layer 4 and the second glazed layer 5 are tightly adhered to each other, and thus the formation of cracks occurring at the interface between these layers can be prevented. In addition, both layers can be burned at the same time in order to reduce production costs.

Since the first glazed layer 4 and the second glazed layer 5 have a thickness ratio of 20/1, a surface is obtained that does not substantially differ in appearance from the surface when only the first glazed layer 4 is formed, even though that the second glazed layer 5 itself has a poor appearance due to the inclusion of a silver compound 6.

Since in the samples from Example and comparative Example the second glazed layer 5 or glazed layer 8 contains a silver compound 6 as a substance containing an antibacterial metal, they have an antibacterial effect. Since in the Example of all the glazed layers only the second glazed layer 5 contains a silver compound 6, the concentration of the silver compound 6 on the outer surface can be increased even if a smaller amount of the silver compound is used than in the comparative Example, so that a greater antibacterial effect can be achieved. You can also avoid unnecessary consumption of the silver compound 6. Since in the Example the second glaze material in the molten state has a higher viscosity than the first glaze material, degassing during melting occurs evenly, thereby preventing the formation of bubbles in the sample. Also, the diffusion rate of the silver compound 6 from the second glazed layer 5 to the first glazed layer 4 is reduced during firing, so that it is possible to produce a sample having a concentration of silver compound 6 on the surface that remains at a high level.

Since in the sample from Example on the surface of the second glazed layer 5 a water-repellent sludge 7 is formed, even if water containing a large number of contaminants enters the surface of the second glazed layer 5, which has a large number of defects, the deposition of contaminants on the surface is difficult due to its water-repellent effect that provides an excellent effect of resistance to pollution. In particular, since the Example contains a compound of phosphoric acid in the second glaze material, the antibacterial effect due to the compound of silver 6 is enhanced. Since in the Example a water-repellent layer 7 is formed on the surface of the second glazed layer 5, the product has both antibacterial and water-repellent properties. Therefore, in the case when water containing a large amount of polluting components is used, so that the effect of resistance to pollution due to a single antibacterial action cannot be achieved, the formation of pollution is difficult due to the water-repellent effect, due to which the effect of resistance to pollution is significantly increased.

Third invention

Below will be described Examples 1-7 of the implementation of the third invention and Comparative Examples 1-4.

Example 1

"Preparatory stage"

As shown in FIG. 12 and FIG. 13, the base material 1 for tiles is made of the following composition, cut into squares with a side of 50 ± 2 mm and a thickness of 10 mm or less.

The proportions of the mixture for the base material 1 (mass%) Feldspar 28,2 Quartz sand 11.8 Sericite 15.0 Clay 45.0

A first glaze material and a second glaze material are prepared having the following compositions.

The proportions of the mixture for the first glaze material (mass%) Feldspar 42,456 Frit 1,671 Lime 11,827 Dolomite 5,054 Zinc White 1,516 Clay 4,043 Alumina 1,769 Quartz sand 9,603 Muffler 6,368 Refractory fireclay material 15,163 Pigment 0.581

In this case, the frit has the following composition (in mass%).

SiO ₂ 49.3 Al ₂ O ₃ 11.1 Cao 0.2 Na ₂ O 19.1 K ₂ O 1,0 B ₂ O ₃ 19,2

The first glaze material contains 2 wt.% K ₂ O.

The proportions of the mixture for the second glaze material (mass%) Quartz sand 31,0 Lime 6.0 Clay 13.0 Antibacterial 50,0

The antibacterial agent has the following composition (in mass%).

Ag ₂ O 25.88 P ₂ O ₅ 4.98 Cao 0.01 SiO ₂ 56.84 Al ₂ O ₃ 9.36 Fe ₂ O ₃ 0.10 K ₂ O 0.43 Na ₂ O 0.06 Sro 0.01 Loss on ignition 2,34

The above composition for the formation of the second glaze material contains fine Za zircon solid particles, the mass content of which is 1 wt.% (In terms of the total amount), and the average particle diameter is 0.81 μm. The second glaze material contains 2 wt.% Na ₂ O.

"Stage of glazing"

As shown in FIG. 12, the first glaze material is applied to the surface of the base material 1 to form a layer of the first glaze material 2, and then, as shown in FIG. 13, the second glaze material is applied to the outer surface of the layer of the first glaze material 2 to form a second layer glaze material 3.

"Stage of firing"

The base material 1, having a layer of the first glaze material 2 and a layer of the second glaze material 3, is fired at 1210 ° C. In this case, the base material is sintered, and the layer of the first glaze material 2 and the layer of the second glaze material 3 are melted to form the first glazed layer 4 and the second glazed layer 5 based on 1 ceramic product, as shown in Fig. 14. Small particles of Zircon are scattered on the surface of the second glazed layer 5.

In this case, the coefficient of linear thermal expansion of the second glazed layer 5 is less than the coefficient of linear thermal expansion of the first glazed layer 4, and the difference between the coefficients is 3 × 10 ^-7 / ° C. In addition, the coefficient of linear thermal expansion of the first glazed layer 4 is less than the coefficient of linear thermal expansion of the base of the ceramic product 1, and the difference between them is 4 × 10 ^-7 / ° C. The first glazed layer 4 and the second glazed layer 5 have a thickness ratio of 20/1. The second glazed layer 5 contains a silver compound 6 as a substance containing an antibacterial metal dispersed in this layer.

"Processing step for imparting water-repellent properties"

Then carry out the processing stage to impart water-repellent properties to the surface of the second glazed layer 5. Prepare the first reagent, which consists of

C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃

as an organic compound of silicon containing a perfluoroalkyl group, and

Si (CH ₃ O) ₃ CH ₂ CH ₂ - (Si- (CH ₃ ) ₂ O) ₁₀ -Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃

as a polymethylsiloxane compound containing a hydrolyzable group, which is subjected to joint hydrolysis in a hydrophilic solvent containing a 0.1N aqueous solution of hydrochloric acid, tert-butanol and hexane. It is believed that they respectively contain silanol (Si-OH) groups.

A mixture of polyorganosiloxane (HO- (Si (CH ₃ ) ₂ O) ₃₀ -Si (CH ₃ ) ₂ OH) and methanesulfonic acid as a strong acid is prepared as a second reagent.

5 ml of the second reagent is added to 5 ml of the first reagent and mixed to obtain a treatment liquid to impart water-repellent properties. A treatment fluid to impart water-repellent properties is applied to the surface of the base 1 of a ceramic product having a first glazed layer 4 and a second glazed layer 5, and then dried, leaving it for about 10 minutes. Then the surface is washed with ethanol and dried.

As a result of the above procedures, as shown in Fig. 15, a sample is obtained which consists of a base 1 of a ceramic product, a first glazed layer 4 containing the first glaze material and formed on the basis of 1 ceramic product, a second glazed layer 5 containing the second glaze material, which is different from the first glaze material, and an antibacterial metal formed on the outer surface of the first glazed layer 4, and a water-repellent layer 7 containing a water-repellent component, formed on the surface of the second glazed layer 5. The sample also contains fine Za zircon particles located on the surface of the second glazed layer and the water-repellent layer 7.

Example 2

At the preparatory stage of Example 1, 2 weight percent (in terms of total amount) of small particles of zircon 3a according to Example 1 are added to the second glazing material. The remaining conditions are the same as in Example 1.

Example 3

In the preparatory step of Example 1, 1 weight percent (based on the total amount) of small zircon particles 3a having an average particle diameter of 1.55 μm is added as small solid particles to the second glaze material. The remaining conditions are the same as in Example 1.

Example 4

At the preparatory stage of Example 1, 2 weight percent (in terms of total amount) of small particles of zircon 3a according to Example 3 are added to the second glazing material. The remaining conditions are the same as in Example 1.

Example 5

In the preparatory step of Example 1 1, the weight percent (based on the total amount) of small zircon particles 3a having an average diameter of 20 μm is added as small solid particles to the second glaze material. The remaining conditions are the same as in Example 1.

Example 6

At the preparatory stage of Example 1, 2 weight percent (in terms of total amount) of small particles of zircon 3a according to Example 5 are added to the second glazing material. The remaining conditions are the same as in Example 1.

Example 7

At the preparatory stage of Example 1, 4 weight percent (in terms of total amount) of small particles of zircon 3a according to Example 5 are added to the second glazing material. The remaining conditions are the same as in Example 1.

Comparative Example 1

As shown in FIG. 17, a glaze material having the composition below is applied to a base material 1, the same as in Example 1, to form a layer of glaze material.

The proportions of the mixture for the glaze material (mass%) Feldspar 10.0 Kaolin 5,0 Silicate frit 85.0

Frit in this case had the following composition (in mass%).

SiO ₂ 67.4 Al ₂ O ₃ 8.6 MgO 2.7 CaO 5.7 Sro 3.2 Na ₂ O 2,3 K ₂ O 3.2 B ₂ O ₃ 3,5 Zno 2,3 MoO ₃ 1,1

The base material 1 coated with a layer of glaze material is fired at 1210 ° C. In this case, the layer of glaze material melts to form a glazed layer 8 based on 1 ceramic product. In this way, a sample is obtained which consists of a base 1 of a ceramic product and a glazed layer 8 containing glaze material and formed on the basis of 1.

Comparative Example 2

The glaze material having the composition below is applied to the base material 1 in the same manner as in Example 1 to form a layer of glaze material. The base material 1 coated with a layer of glaze material is fired at 1210 ° C to obtain a sample similar to the sample from comparative Example 1, shown in Fig.17.

The proportions of the mixture for the glaze material (mass%) Feldspar 42,456 Frit 1,617 Lime 11,827 Dolomite 5,054 Zinc White 1,516 Clay 4,043 Alumina 1,769 Quartz sand 9,603 Muffler 6,368 Refractory fireclay material 15,163 Pigment 0.581

The frit in this case is the same as in Example 1. In the above composition to obtain a glaze material contains 6.3 wt.% (In terms of the total number) of small particles of zircon having an average particle diameter of 1.55 μm.

Comparative Example 3

Prepare the same base material 1 as in Example 1, the first glaze material, which is the glaze material of comparative Example 2, and the second glaze material having the composition below. The base material 1 with a layer of the first glaze material deposited on it and a layer of the second glaze material is fired at 1210 ° C to obtain a sample. At the same time, as shown in Fig. 18, a ceramic base 1 is obtained, a first glazed layer 9 containing a first glaze material and formed on the basis of a ceramic product, and a second glazed layer 10 containing a second glaze material and formed on a glazed layer 9.

The proportions of the mixture for the second glaze material (mass%) Quartz sand 31,0 Lime 2,3 Clay 12,4 Zinc White 3.9 Frit 0.5 Antibacterial 50,0

The frit was the same as in comparative Example 1, and the antibacterial agent was the same as in Example 1.

Comparative Example 4

Prepare the same base material 1 as in Example 1, the first glaze material, which is the glaze material of comparative Example 2, and the second glaze material having the composition below. The base material 1 coated with a layer of the first glaze material and a layer of the second glaze material was fired at 1210 ° C to obtain a sample similar to the sample from comparative Example 3 shown in Fig. 18.

The proportions of the mixture for the second glaze material (mass%) Quartz sand 33.0 Lime 8.5 Alumina 7.0 Antibacterial 51,2

The antibacterial agent was the same as in Example 1.

Rating

Samples were prepared from Examples 1-7 and comparative Examples 1-4. To assess surface smoothness, the number of point defects on the surface was determined using a digital microscope. The results are shown in Table 3. In Table 3, samples with good surface smoothness are indicated by the letter A, and samples with insufficient smoothness are indicated by the letter B.

TABLE 3 Sample Smoothness Number of defects total length surface 0.7 (mm) and more 0.3-0.6 (mm) 0-0.2 (mm) defects (mm) one BUT one one 2 1.7 2 BUT 0 ABOUT 0 0,0 3 BUT 0 one 2 0.6 four BUT one one four 1.8 5 BUT 2 2 0 3.0 Example 6 BUT 0 one one 0.7 7 BUT 0 0 0 0,0 Compares one B 9 10 8 13.7 spruce 2 B 0 one one 0.6 3 BUT 6 5 17 10.3 four BUT one four 2 2,8

From Table 3 it is clear that the samples from Examples 1-7 and comparative Examples 3 and 4 have practically no point defects on the surface, and the surface itself has good smoothness. On the other hand, the samples from comparative Examples 1 and 2 have point defects on the surface, albeit in small numbers, and their surface smoothness is much worse. This is because the glazed layers in the samples of Examples 1-7 and comparative Examples 3 and 4 consist of a first glazed layer and a second glazed layer. Therefore, even if point defects are formed in the first glazed layer under the influence of the base material 1, the base material 1 is difficult to influence the second glazed layer, and the formation of point defects on the surface of the second glazed layer is difficult. Therefore, it is clear that the samples from Examples 1-7 and comparative Examples 3 and 4 have better surface smoothness and exhibit excellent resistance to contamination.

In the samples of Examples 1-7, the fine particles of Zircon are contained in such an amount that does not affect the color of the second glazed layer 5, and are dispersed so dispersed that they affect the smoothness of the surface of the second glazed layer 5. As a result, an excellent external view.

In addition, since the samples from Examples 1-7 have a water-repellent layer 7 on the outer surface of the second glazed layer 5, even when a large amount of contaminants enters the surface of the second glazed layer 5, which has a small number of defects, pollution is difficult to linger on the surface due to its water-repellent effect, due to which there is an excellent effect of resistance to pollution. In addition, in the samples of Examples 1-7, due to the fact that the second glazed layer 5 contains a silver compound 6 as a substance containing an antibacterial metal, it has an antibacterial effect, and an excellent effect of resistance to pollution is also provided due to this exposure.

Samples from Examples 1-7 and comparative Examples 1-4 were subjected to the brushing test described below.

Brush Test

A commercially available toothbrush was used with an abrasive product commercially available on it. On the surface of the sample twenty times was carried out with a toothbrush with constant pressure. Then, the number of defects and the total length of the defects (mm) per 4 cm ^{2 were} determined. The results are also shown in Table 3.

From Table 3 it is clear that on the samples from Examples 1-7 and comparative Examples 2 and 4, the formation of defects is difficult. This is due to the fact that in the samples from Examples 1-7 and comparative examples 2 and 4, the coefficient of linear thermal expansion of the second glazed layer is less than the coefficient of linear thermal expansion of the first glazed layer, and therefore the second glazed layer is compacted due to the compressive stress experienced by it, caused by the shrinkage of the first glazed layer, which leads to high surface hardness. In particular, large defects are not formed in the samples from Examples 1-7, since small particles of Zircon present on the surface of the water-repellent layer 7 prevent mechanical damage to the surface by the abrasive. Therefore, it can be understood that on the samples from Examples 1-7, contamination, formation which are caused by defects and cracks are poorly retained, due to which good resistance to pollution is achieved.

In addition, it is clear that, as shown in Fig. 19, the X-ray stiffness (frequency) of the potassium Kα-line in the samples of Examples 1-7 is in the range from 198 to 331 Hz in the first glazed layer 4, and in the range from 331 up to 463 Hz in the second glazed layer 5. Therefore, it can be said that in the samples of Examples 1-7, sodium ions having a small ion radius and present in the second glazed layer 5 are replaced by potassium ions having a large ion radius and are present in the ion exchange process in the first glazed layer 4. Potassium ions diffuse in the second glazed layer 5. Therefore, in the second glazed layer 5, an intrinsic compressive stress develops, which leads to its strengthening.

Antibacterial Test

Three samples were prepared from Examples 1-7 and Comparative Examples 1-4 and were analyzed for antibacterial properties by a film method. The average changes in the rate of reproduction for Escherichia coli (IFO3972) at the corresponding concentrations of the nutrient medium are shown in Table 4. The average changes in the rate of reproduction for Staphylococcus aureus (IFO12732) at the corresponding concentrations of the nutrient medium are shown in Table 5. In Tables 4 and 5, there is no antibacterial effect with the average change in breeding rate is less than 2.0.

TABLE 4 Nutrient concentration Example Comparative Example environment one 2 3 four 5 6 7 one 2 3 four 1/500 PB 5.5 5.5 5.5 5.5 5.5 5.5 5.5 2,4 2,4 5.5 5.5 1/200 PB 4.2 4.2 4.2 4.2 4.2 4.2 4.2 1,2 1,2 4.2 4.2 1/50 PB 2.7 2.7 2.7 2.7 2.7 2.7 2.7 0,0 0,0 2.7 2.7

TABLE 5 Nutrient concentration
environment Example Comparative Example one 2 3 four 5 6 7 one 2 3 four 1/500 PB 4.8 4.8 4.8 4.8 4.8 4.8 4.8 2.2 2.2 4.8 4.8 1/200 PB 3,7 3,7 3,7 3,7 3,7 3,7 3,7 0,0 0,0 3,7 3,7 1/50 PB 2,3 2,3 2,3 2,3 2,3 2,3 2,3 0,0 0,0 2,3 2,3

From Table 4 and Table 5 it is clear that in relation to the antibacterial effect on both types of bacteria, the samples from Examples 1-7 retain an average change in the rate of reproduction equal to 2.0 or more, even when the concentration of the nutrient medium increases, while in samples from comparative Examples 1 and 2, the average change in the rate of reproduction, equal to 2.0 or more, is preserved only if the concentration of the nutrient medium is 1/500 PB or less. Therefore, it is understood that the samples from Examples 1-7 have excellent resistance to pollution compared to samples from Comparative Examples 1 and 2. It is also clear that since the silver compound 6 used as a substance containing an antibacterial metal from all the glazed layers in samples from Examples 1-7 is contained only in the second glazed layer 5, the concentration of silver compound 6 on the outer surface can be increased even when using a smaller amount of antibacterial agents than in ordinary In this case, due to which a stronger antibacterial effect can be achieved. In addition, it is understood that in the samples of Examples 1-7, unnecessary expenditure of an antibacterial agent can be avoided.

It is clear that the samples from Examples 1-7 show average changes in the rate of bacterial reproduction at a level similar to the samples from comparative Examples 3 and 4. The samples in Fig. 15 from Examples 1-7 can have excellent resistance to contamination, which is equivalent to samples from comparative Examples 3 and 4, despite the fact that they have fine Zircon particles scattered on the surface of the water-repellent layer 7 above the second glazed layer 5.

Therefore, the samples from Examples 1-7 have a surface of good smoothness, on which the formation of defects is difficult. Therefore, these samples are highly resistant to contamination.

Examples and Comparative Examples The above examples are merely illustrative, and the invention may be carried out in other examples in which various changes can be made without departing from the spirit of the invention.

In accordance with the proposed processing method to give resistance to pollution according to the first invention, the product can be manufactured at low production costs. The manufactured product has a significant antibacterial effect.

In the reinforced ceramic product of the second invention, defects are impeded on the surface of the glazed layer.

In an article having a glazed layer according to the third invention, defects are formed on the surface, which provides high resistance to contamination.

Claims (32)

1. The product having a glazed layer, consisting of a molded ceramic billet having a glazed layer, which contains a first glazed layer containing the first glazing material, and a second glazed layer formed on the outer surface of the said first glazed layer and containing the second glazing material, which contains an antibacterial metal and a phosphoric acid compound and differs from the first glazed material, characterized in that the thickness ratio of said said first glazed layer and said second glazed layer is in the range of from 10/1 to 30/1 and said second glazed layer contains a larger amount of potassium and less sodium than said first glazed layer. 2. A reinforced ceramic product, consisting of a ceramic product preform and a glazed layer formed on the surface of said preform, characterized in that said glazed layer contains a first glazed layer containing a first glazing material and a second glazed layer containing a second glazing material, which formed on the outer surface of said first glazed layer, contains an antibacterial metal and has a lower coefficient of linear thermal expansion, it said first glazed layer. 3. The product according to claim 2, characterized in that the coefficient of linear thermal expansion of said ceramic blank is greater than the coefficient of linear thermal expansion of the first glazed layer. 4. The product according to claim 2 or 3, characterized in that the difference in the coefficients of linear thermal expansion of the aforementioned first glazed layer and the second glazed layer is in the range from 1 · 10 ^-7 to 1 · 10 ^-6 / ° C. 5. The product according to claim 4, characterized in that the difference in the coefficients of linear thermal expansion of the aforementioned first glazed layer and the second glazed layer is in the range from 2 · 10 ^-7 to 5 · 10 ^-7 / ° C. 6. The product according to claim 4, characterized in that the ratio of the thicknesses of the aforementioned first glazed layer to the second glazed layer is in the range from 10/1 to 30/1. 7. The product according to claim 3, characterized in that the difference in the coefficients of linear thermal expansion of the said ceramic workpiece and the first glazed layer is in the range from 1 · 10 ^-7 to 1 · 10 ^-6 / ° C. 8. The product according to claim 7, characterized in that the difference in the coefficients of linear thermal expansion of the said ceramic workpiece and the first glazed layer is in the range from 2 · 10 ^-7 to 5 · 10 ^-7 / ° C. 9. The product according to claim 2 or 3, characterized in that said second glazed layer contains more potassium and less sodium than said first glazed layer. 10. The product according to claim 2 or 3, characterized in that on the outer surface of said second glazed layer, a water-repellent layer comprising a water-repellent component is formed. 11. A method of manufacturing a reinforced ceramic product, comprising a preparatory step for preparing a base material suitable for forming a ceramic product preform and a glaze material suitable for forming a glazed layer on the surface of said preform, a glazing step consisting in forming a layer of glaze material containing said glaze material, on the surface of said base material, and a firing step, comprising firing said base material and a layer of glaze material to produce a ceramic product consisting of said preform and a glazed layer, characterized in that said glazed material contains a first glazed material capable of forming a first glazed layer and a second glazed material capable of forming a second glazed layer that forms on the outer surface of the first the glazed layer and contains an antibacterial metal, the second glazed layer having a coefficient of linear thermal expansion less than the coefficient of the line thermal expansion of said first glazed layer. 12. The method according to claim 11, characterized in that said first glazing material contains potassium, and said second glazing material contains sodium. 13. The method according to claim 11 or 12, characterized in that said second glazing material in a molten state has a higher viscosity than said first glazing material. 14. The method according to claim 11, characterized in that it includes a processing step for imparting water-repellent properties, consisting in that the surface of said glazed layer is subjected to a treatment to impart water-repellent properties. 15. An article having a glazed layer consisting of a ceramic preform and a glazed layer formed on the surface of said preform, characterized in that said glazed layer comprises a first glazed layer containing the first glazing material and a second glazed layer containing the second glazing material, which is formed on the outer surface of said first glazed layer, contains an antibacterial metal and has a lower coefficient of linear thermal expansion than said first glazed layer, wherein said second surface of the glazed layer dispersed fine solid particles to prevent the propagation of cracks. 16. The product according to item 15, wherein the said small solid particles are small particles of zircon. 17. The product according to clause 15 or 16, characterized in that the coefficient of linear thermal expansion of said billet made of ceramic material is greater than the coefficient of linear thermal expansion of said first glazed layer. 18. The product according to item 15 or 16, characterized in that the difference in the coefficients of linear thermal expansion of the aforementioned first glazed layer and the second glazed layer is in the range from 1 · 10 ^-7 to 1 · 10 ^-6 / ° C. 19. The product according to p. 18, characterized in that the difference in the coefficients of linear thermal expansion of the aforementioned first glazed layer and the second glazed layer is in the range from 2 · 10 ^-7 to 5 · 10 ^-7 / ° C. 20. The product according to clause 15 or 16, characterized in that the ratio of the thicknesses of the aforementioned first glazed layer and the second glazed layer is in the range from 10/1 to 30/1. 21. The product according to 17, characterized in that the difference in the coefficients of linear thermal expansion of the said ceramic workpiece and the first glazed layer is in the range from 1 · 10 ^-7 to 1 · 10 ^-6 / ° C. 22. The product according to item 21, characterized in that the difference in the coefficients of linear thermal expansion of the said ceramic workpiece and the first glazed layer is in the range from 2 · 10 ^-7 to 5 · 10 ^-7 / ° C. 23. The product according to item 15 or 16, characterized in that the said second glazed layer contains more potassium and less sodium than the first glazed layer. 24. The product according to item 15 or 16, characterized in that on the outer surface of said second glazed layer, a water-repellent layer comprising a water-repellent component is formed. 25. A method of manufacturing an article having a glazed layer, comprising a preparatory step for preparing a ceramic workpiece and a glaze material suitable for forming a glazed layer on the surface of a ceramic workpiece, a glazing step comprising forming a layer of glaze material containing said glaze material on the surface of said preforms of a ceramic product, and a firing step, comprising firing said ceramic preform and a glaze layer material to obtain an article consisting of said preform and a glazed layer, characterized in that said glaze material comprises a first glaze material forming a first glazed layer that is deposited on the surface of said ceramic preform and a second glaze material forming a second glazed layer which is deposited on the outer surface of the first glaze material and contains an antibacterial metal, the second glazed layer having a lower coefficient of linear lovogo expansion than said first glazed layer and contains dispersed over the surface of small solid particles to prevent the development of cracks. 26. The method according A.25, characterized in that at the said stage of glazing form a layer of the first glaze material containing the first glaze material, and then on the surface of the said layer of the first glaze material form a layer of the second glaze material containing the second glaze material. 27. The method according A.25 or 26, characterized in that said first glazing material contains potassium, and said second glazing material contains sodium. 28. The method according to item 27, wherein said second glazing material in a molten state has a higher viscosity than said first glazing material. 29. The method according A.25 or 26, characterized in that it includes a processing step for imparting water-repellent properties, comprising the fact that the surface of said glazed layer is subjected to processing to impart water-repellent properties. Priority on points: 10.19.2000 according to claim 1 is established by application JP 2000-318845; 10/19/2000 according to claims 2-14 is set by application JP 2000-318846; November 17, 2000 according to claims 15-29 is established by the application of JP 2000-351687.

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