Method for stainproofing treatment and product having glass layer, reinforced pottery and method for production thereof, and product having glass layer and method for production thereof

[Technical Field] The present invention relates to a product having a glass layer.

[Background Technology] For example, antibacterial metals such as Ag, Cu, and Zn are known to have antibacterial properties. For this reason, conventionally, when manufacturing a product having a glass layer such as a ceramic product having an antibacterial function or an enamel product, the antibacterial function is imparted to the surface of a substrate such as a glass molded body, a ceramic molded body, or a metal molded body. An antifouling treatment method having an antibacterial treatment step can be performed. The antibacterial treatment step of this antifouling treatment method includes a preparatory step of preparing a glaze capable of forming a glass layer containing an antibacterial metal, and a glaze layer composed of the glaze is formed on the surface of a substrate, and the glaze layer is melted. It consists of a vitrification step of forming a glass layer.

[0003] By this antifouling treatment method, a product made of a substrate having a glass layer and the glass layer made of the glaze can be obtained. In the product having the glass layer thus obtained, the antibacterial metal in the glass layer acts on the bacteria to kill them or suppress their reproduction.

[0004] Further, a general ceramic is composed of a ceramic main body and a glass layer formed on the surface of the ceramic main body.

[0005] This earthenware is manufactured as follows. First, as a preparatory step, a base material capable of forming a ceramic body and a glaze capable of forming a glass layer on the surface of the ceramic body are prepared. Then, as a glaze step, a glaze layer made of glaze is formed on the surface of the base material. After that, as a firing step, the base material and the glaze layer are fired to obtain a ceramic composed of a ceramic body and a glass layer.

[0006] In the ceramics thus obtained, the glass layer finishes the surface smoothly and beautifully, makes the surface less likely to be scratched, and further imparts waterproofness.

[0007] Further, for example, ceramics as products such as food and drink, kitchen utensils, ornaments, tiles, sanitary supplies, electrical supplies, physics and chemistry supplies, industrial supplies, building tiles, roof tiles, ceramic pipes, etc. It is composed of a ceramic body as a substrate and a glass layer formed on the surface of the ceramic body. The enamel product is composed of a metal body as a substrate and a glass layer formed on the surface of the metal body. Further, some glass products are composed of a glass body as a substrate and a glass layer formed on the surface of the glass body.

[0008] Among the products having the glass layer as described above, for example, earthenware is manufactured as follows. First, as a preparatory step, a base material capable of forming a ceramic body and a glaze capable of forming a glass layer on the surface of the ceramic body are prepared. Then, as a glaze step, a glaze layer made of glaze is formed on the surface of the base material. After that, as a firing step, the base material and the glaze layer are fired to obtain a ceramic composed of a ceramic body and a glass layer. In this way, a product having a glass layer is manufactured. In the product, the glass layer finishes the surface smoothly and beautifully, makes the surface less likely to be scratched, and further imparts waterproofness and the like.

However, in the above-mentioned general antifouling treatment method, since only a single glass layer is formed on the surface of the substrate, the glass layer is essentially formed. While it is desired to exert an antibacterial function against bacteria on the surface, the antibacterial metal is dispersed in the glass layer. Then, in the product having the glass layer thus obtained, the effect is low unless the concentration of the antibacterial metal used is increased. Therefore, this antifouling treatment method consumes a large amount of antibacterial metal in order to exert an excellent antibacterial function, which leads to an increase in manufacturing cost.

[0010] Further, since the conventional ceramic has a single glass layer, the surface is still easily scratched and the surface hardness is not sufficient. Therefore, when an impact is applied, there is a problem that cracks are likely to occur in the glass layer or the like due to scratches. In particular, in ceramics in which an antibacterial metal such as Ag is cooked in the glass layer in order to impart an antibacterial function to the surface, it is considered that the antibacterial metal promotes the progress of cracks, and this tendency is expected to be large. To. In addition, there is a problem that dirt easily adheres to the scratches.

[0011] Further, in the conventional product having a glass layer, since the glass layer is a single layer, the surface is still easily scratched and the surface hardness is not sufficient. Therefore, when an impact is applied, there is a problem that cracks are likely to occur in the glass layer or the like due to scratches. In addition, there is a problem that dirt easily adheres to the scratches. Therefore, it is conceivable to adopt a plurality of glass layers. However, it was found that even in a product simply using a plurality of glass layers, the surface is still easily scratched and the surface hardness is not sufficient. For this reason, there is still a problem that the antifouling property is lacking.

[0012] The present invention has been made in view of the above-mentioned conventional circumstances, and the first invention is to produce a product having a glass layer capable of exhibiting an excellent antibacterial function while being inexpensive to produce. Is an issue to be solved. Further, the second invention is a problem to be solved to provide reinforced earthenware in which the surface of the glass layer is not easily scratched. Further, the third invention is a problem to be solved to provide a product having a glass layer which is hard to be scratched on the surface and which can surely exhibit excellent antifouling property.

[Means for Solving the Problems] The antifouling treatment method of the first invention is an antifouling treatment method having an antibacterial treatment step of imparting an antibacterial function to the surface of the substrate, wherein the antibacterial treatment step is the substrate. And a preparatory step of preparing a first glaze capable of forming a first glass layer on the surface of the substrate and a second glaze capable of forming a second glass layer containing an antibacterial metal on the surface of the substrate, and the substrate. A first glaze layer composed of the first glaze and a second glaze layer composed of the second glaze are formed on the surface of the surface, and the first glaze layer and the second glaze layer are melted. It has a first glass layer and a vitrification step for forming the second glass layer, and the second glaze layer is characterized by having a higher viscosity at the time of melting than the first glaze layer.

[0014] In the antifouling treatment method of the first invention, first, as a preparatory step for the antibacterial treatment step, a substrate, a first glaze capable of forming a first glass layer on the surface of the substrate, and an antibacterial metal on the surface of the substrate are included. Prepare a second glaze that can form a second glass layer. Then, as a vitrification step of the antibacterial treatment step, a first glaze layer made of the first glaze and a second glaze layer made of the second glaze are formed on the surface of the substrate, and the first glaze layer and the second glaze layer are formed on the surface side. The second glaze layer is melted to form the first glass layer and the second glass layer.

[0015] Here, since the second glaze layer has a higher viscosity at the time of melting than the first glaze layer, the antibacterial metal is difficult to diffuse from the second glass layer on the surface side into the first glass layer, and most of them are the second glass. Stay in the layer. Therefore, in this antifouling treatment method, the antibacterial metal in the second glass layer on the surface side, which is originally desired, acts on bacteria and exhibits an excellent antibacterial function without consuming a large amount of antibacterial metal. be able to.

[0016] Further, in the antifouling treatment method of the first invention, a first glaze layer made of a first glaze and a second glaze layer made of a second glaze are formed on the more surface side, and the first glaze layer and the first glaze layer are formed. 2 The glaze layer is melted to form the first glass layer and the second glass layer. Therefore, in the obtained product, the second glaze impregnates the first glaze layer, and the first glass layer and the second glass layer are formed. In addition to firmly adhering to each other, it is possible to prevent the occurrence of cracks that progress at their interfaces. Further, as a result, the firing process can be completed at one time, and the manufacturing cost can be reduced.

Therefore, according to this antifouling treatment method, it is possible to produce a product having a glass layer capable of exhibiting an excellent antibacterial function as well as being able to be produced at low cost.

[0018] In this way, the product having the glass layer of the first invention is obtained. The product having a glass layer of the first invention is made of a substrate having a glass layer, and the glass layer is formed of a first glass layer made of a first glaze and an antibacterial metal formed on the outer surface side of the first glass layer. It is composed of a second glass layer composed of a second glaze containing and different from the first glaze.

[0019] As the substrate, a glass molded body can be adopted when a glass product is manufactured as a product having a glass layer, and when a ceramic product such as sanitary ware or tile is manufactured, those ceramic moldings can be adopted. A body can be adopted, and when manufacturing an enamel product, the metal molded body can be adopted.

[0020] Further, Ag, Cu, Zn and the like can be adopted as the antibacterial metal contained in the second glaze. Specifically, it is an organic silver / copper compound or a silver / copper-supported inorganic compound, (1) silver, copper, silver-copper alloy, (2) silver phosphate, silver nitrate, silver chloride, silver sulfide, silver oxide, etc. Silver sulfate, silver citrate, silver lactate, (3) cuprous phosphate, cupric phosphate, organic copper compound, cuprous chloride, cupric chloride, cuprous sulfide, cuprous oxide, oxidation Copper cupric, cupric sulfide, cuprous sulfate, cupric sulfate, copper citrate, copper lactate and the like can be adopted. Similarly, zinc is an organic zinc compound or a zinc-supporting inorganic compound, and zinc, zinc oxide, zinc chloride, zinc sulfide, zinc sulfate, zinc lactate and the like can be adopted. These antibacterial metals may be simple substances, alloys, or compounds.

[0021] In the product having the glass layer of the first invention, it is preferable that the first glass layer and the second glass layer have a difference in thickness of 10: 1 to 30: 1. In this case, even if the second glass layer contains an antibacterial metal such as Ag and the appearance of the second glass layer is not good, the appearance is almost different from the case where only the first glass layer is formed. Since the surface is not present, it is possible to obtain a product having a surface having an excellent appearance in terms of design.

[0022] According to the test results of the inventors, in the product having the glass layer of the first invention, the second glass layer contains more potassium and less sodium than the first glass layer. ing. Potassium has a larger ionic radius than sodium. Therefore, when the glass layer according to the product of the first invention is formed, sodium ions in the second glass layer are ion-exchanged with potassium ions in the first glass, causing compressive stress in the second glass layer and second. It is considered that the strength of the glass layer increases.

[0023] Further, in the antifouling treatment method of the first invention, it is preferable that the second glaze contains a phosphoric acid compound. In the product having the glass layer of the first invention thus obtained, P is contained in the second glass layer.₂O₅Etc. are present, and the antibacterial function of the antibacterial metal is more likely to be exhibited. It is also preferable to include a boric acid compound in the second glaze. If this is the case, B in the second glass layer₂O₃And other boric acid compounds are present, and the antibacterial function of the antibacterial metal is more likely to be exhibited.

[0024] Further, the antifouling treatment method of the first invention preferably includes a water-repellent treatment step of treating the surface of the second glass layer with water-repellent treatment. In this case, both the antibacterial function and the water-repellent function are imparted to the surface of the second glass layer, and water containing a large amount of stain components is used so that the antibacterial function alone is insufficient for the antifouling effect. Even so, the water-repellent function makes it difficult for dirt to remain, and the antifouling effect can be sufficiently exhibited.

[0025] In this case, the water-repellent treatment step is to form a film composed of a water-repellent treatment liquid having a silicon-containing functional group that is bonded to a hydroxyl group existing on the surface of the second glass layer by a dehydration reaction or a dehydrogenation reaction. Can be done by. When this treatment is performed, the silicon-containing functional group is bonded to the hydroxyl group (-OH) existing on the surface of the second glass layer by a dehydration reaction or a dehydrogenation reaction to shield the hydroxyl group. Therefore, even if water containing many metal ions such as soluble silica is used, its hydroxyl group is no longer bound to those metal ions and does not bind to components such as human waste. In particular, even if water containing soluble silica is used as the metal ion, it does not precipitate as silicic acid forming a network structure, or it is difficult to precipitate, and it is difficult to take in dirt. In this way, if the water-repellent treatment liquid has this silicon-containing functional group, in a product that simultaneously uses water containing a large amount of metal ions such as soluble silica, dirt such as human waste is less likely to stick and cleaning thereof becomes easy.

[0026] Here, it is preferable that the water-repellent treatment liquid is one in which silicon-containing functional groups are not bonded to each other. According to the test results of the inventors, it is possible to enhance the antifouling effect on water stain resistance, hair dye stain resistance, abrasion resistance and alkali resistance. If the silicon-containing functional groups of the water-repellent treatment liquid are bonded to each other, it is considered that the amount of silicon increases and silicic acid forming a network structure is precipitated in the coating film, and dirt is easily taken in there.

[0027] Further, the water-repellent treatment liquid preferably has a terminal fluorocarbon group bonded to a silicon-containing functional group. According to the test results of the inventors, if the fluorocarbon group is present in this way, the water-repellent function is likely to be exhibited due to the small critical surface tension of the fluorocarbon group, and water-resistant stains, hair dye stains, and alkali resistance. The effect is great.

[0028] Here, the fluorocarbon group is -C._nF_{2n + 1}(n is a natural number of 1 n 12). According to the test results of the inventors, this increases the number of fluorines and makes fluorosilane bulky, so that it has a great effect on water stain resistance, hair dye stain resistance, abrasion resistance and alkali resistance.

[0029] The water-repellent treatment liquid is a mixture of a first agent and a second agent, and the first agent is hydrophilic of a perfluoroalkyl group-containing organosilicon compound and a hydrolyzable group-containing methylpolysiloxane compound. It is a co-hydrolyzate in a sex solvent, and the second agent can be a mixture of an organopolysiloxane and a strong acid. Here, the perfluoroalkyl group-containing organic silicon compound and the hydrolyzable group-containing methylpolysiloxane compound present in the first agent are bonded to the hydroxyl group existing on the surface of the glass layer by a dehydration reaction or a dehydrogenation reaction. It is prepared as a component having a silicon-containing functional group for shielding the hydroxyl group.

[0030] The reason why the perfluoroalkyl group-containing organosilicon compound is used as a constituent component in the first agent is that the antifouling effect also appears as a water-repellent function due to the large critical surface tension of the fluorocarbon group, and it is resistant to water stains and stains. This is because it is highly effective against hair dye stains and alkali resistance. The reason why the hydrolyzable group-containing methylpolysiloxane compound is used as a constituent component in the first agent is that it has a great effect on water stain resistance, hair dye stain resistance, and alkali resistance.

The second agent is a mixture of organopolysiloxane and a strong acid. The reason why organopolysiloxane is used as a constituent component in the second agent is that the antifouling effect also appears as lipstick stain resistance and abrasion resistance due to the small critical surface tension of the alkyl group. Further, the reason why the strong acid is used as a constituent component of the second agent is that when the antifouling treatment is performed using the water-repellent treatment liquid prepared by the method according to the first invention, perfluororo, which is a constituent component in the first agent, is used. This is because a strong acid effectively acts as a catalyst for binding the alkyl group-containing organosilicon compound and the hydrolyzable group-containing methylpolysiloxane compound to the hydroxyl group on the surface of the glass layer.

[0032] When the first agent and the second agent are mixed, the silanol group of the cohydrogenate reacts with organopolysiloxane and a strong acid to form a siloxane bond (Si-O-Si) by a dehydration reaction, and a plurality of silanol groups are formed. It is thought that the molecules become intricately intertwined addition compounds. Therefore, the water-repellent treatment liquid obtained by mixing the first agent and the second agent consists of only one molecule such as a perfluoroalkyl group-containing organic silicon compound, a hydrolyzable group-containing methylpolysiloxane compound, and an organopolysiloxane. It is considered that these multiple molecules are not composed but are bonded as an additional compound or a kind of polymer in which these multiple molecules are intricately entwined, and that the additional compound and the surface of the substrate are strongly chemically bonded. Be done.

[0033] In this way, a product having the glass layer of the first invention in which a water-repellent layer containing a water-repellent component is formed on the surface side of the second glass layer can be obtained. Since the water-repellent layer is very thin and the water-repellent layer is bonded only to the hydroxyl group portion on the surface of the second glass layer, it is considered that the antibacterial function permeates this drainage layer.

[0034] The reinforced porcelain of the second invention comprises a porcelain main body and a glass layer formed on the surface of the porcelain main body, and the glass layer is a first glass layer made of a first glaze and the first glass. It is characterized by having a second glass layer formed on the outer surface side of the layer and made of a second glaze having a coefficient of linear thermal expansion smaller than that of the first glass layer.

[0035] In the reinforced ceramic of the second invention, since the coefficient of linear thermal expansion of the second glass layer is smaller than the coefficient of linear thermal expansion of the first glass layer, the first and second glaze layers are melted and the first in the firing step. In the cooling process of the two glass layers, the second glass layer receives compressive stress due to the shrinkage of the first glass layer. Therefore, the second glass layer is densified to increase the surface hardness, and the surface of the glass layer is less likely to be scratched. Therefore, in the reinforced earthenware of the second invention, cracks are unlikely to occur in the glass layer or the like due to scratches. In addition, since it is hard to be scratched, dirt caused by the scratch is also hard to adhere.

[0036] The reinforced ceramics of the second invention may have three or more glass layers on the ceramic body. For example, when having three glass layers, the lowermost layer corresponds to the first glass layer, the middle layer corresponds to the second glass layer, and the upper layer corresponds to the first glass layer, and the upper layer corresponds to the second glass. Corresponds to a layer.

[0037] In the reinforced ceramics of the second invention, it is preferable that the ceramic body has a larger coefficient of linear thermal expansion than the first glass layer. In this case, not only the second glass layer receives compressive stress from the first glass layer but also the first in the sintering process of the base material in the firing process, the melting process of the glaze layer, and the cooling process of the ceramic body and the glass layer. The glass layer also receives compressive stress from the ceramic body, and not only the second glass layer but also the first glass layer is densified. Therefore, in the reinforced ceramics of the second invention, cracks generated in the glass layer and the like are unlikely to progress.

[0038] Further, in the reinforced earthenware of the second invention, the first glass layer and the second glass layer have a coefficient of linear thermal expansion of 1 × 10.^-7~1×10^-6It is preferable to have a difference of / ° C. If the difference in linear thermal expansion coefficient between the first glass layer and the second glass layer is smaller than this range, the desired surface hardness cannot be obtained, and conversely, if it is large, the second glass layer is from the first glass layer. This is because the compressive stress received becomes too large and the second glass layer may be destroyed. In particular, according to the test results of the inventors, the first glass layer and the second glass layer have a coefficient of linear thermal expansion of 2 × 10.^-7~5×10^-7It is practical to have a difference of / ° C.

[0039] In this case, it is preferable that the first glass layer and the second glass layer have a difference in thickness of 10: 1 to 30: 1. In this case, even if the second glass layer contains an antibacterial metal such as Ag and the appearance of the second glass layer is not good, the appearance is almost different from the case where only the first glass layer is formed. Since the surface is not present, it is possible to obtain a reinforced ceramic having a surface having an excellent appearance in terms of design.

[0040] Depending on the composition and thickness of the second glass layer, it is possible to make it difficult for light interference due to the interface with the first glass layer to occur, and thereby it is possible to prevent brilliance. Further, depending on the composition of the second glass layer, the second glass layer may be crystallized vitreous and opaque.

[0041] Further, the ceramic body and the first glass layer have a coefficient of linear thermal expansion of 1 × 10.^-7~1×10^-6It is desirable to have a difference of / ° C. If the difference in the coefficient of linear thermal expansion between the ceramic body and the first glass layer is smaller than this range, the desired strength cannot be obtained, and conversely, if it is large, the compression received by the first glass layer from the ceramic body. This is because the stress becomes too large and the first glass layer may be destroyed. In particular, according to the test results of the inventors, the coefficient of linear thermal expansion of the ceramic body and the first glass layer is 2 × 10.^-7~5×10^-7It is practical to have a difference of / ° C.

[0042] According to the test results of the inventors, in the reinforced earthenware of the second invention, the second glass layer contains more potassium and less sodium than the first glass layer. Potassium has a larger ionic radius than sodium. Therefore, when forming the glass layer according to the reinforced ceramics of the second invention, sodium ions in the second glass layer are ion-exchanged with potassium ions in the first glass, causing compressive stress in the second glass layer, and the second glass layer is generated. 2 It is considered that the strength of the glass layer increases.

[0043] In order to impart an antibacterial function to earthenware, when the antibacterial metal is dispersed over a single glass layer, the antibacterial metal easily isolates the glassy substance, so that cracks easily develop through the antibacterial metal. .. Therefore, the reinforced earthenware of the second invention is highly effective when the second glass layer contains an antibacterial metal. In this case, since the second glass layer containing the antibacterial metal is densified, it is easy to prevent the growth of cracks through the antibacterial metal in the second glass layer. Further, in the reinforced ceramic of the second invention, since the antibacterial metal is contained only in the second glass layer in the glass layer, the concentration of the antibacterial metal on the surface side should be increased even if a smaller amount of the antibacterial metal is used than before. And can realize higher antibacterial function. In addition, wasteful consumption of the antibacterial metal can be prevented.

[0044] Here, as the antibacterial metal, the same one as in the first invention can be adopted.

[0045] Further, in the reinforced earthenware of the second invention, it is preferable that a water-repellent layer containing a water-repellent component is formed on the surface side of the second glass layer. In this case, even if water containing a large amount of dirt components is used on the surface that has been scratched even slightly, the water-repellent function makes it difficult for dirt to remain, and an excellent antifouling effect is exhibited.

[0046] In this case, the same water repellent treatment step as in the first invention can be performed.

[0047] The method for producing reinforced ceramics of the second invention includes a preparatory step of preparing a base material capable of forming a ceramic body and a glaze capable of forming a glass layer on the surface of the ceramic body, and the surface of the base material. In a method for producing a ceramic having a glaze step of forming a glaze layer made of a glaze and a baking step of firing the base material and the glaze layer to obtain a ceramic composed of the ceramic body and the glass layer, the glaze is used. It is composed of a first glaze formed on the substrate side and forming the first glass layer, and a second glaze formed on the outer surface side and forming a second glass layer having a smaller linear thermal expansion coefficient than the first glass layer. It is a feature. The reinforced earthenware of the second invention can be manufactured by the manufacturing method of the second invention.

[0048] Further, in the method for producing reinforced porcelain of the second invention, after forming a first glaze layer made of a first glaze in a glaze step, a second glaze layer made of a second glaze is formed on the first glaze layer. Can be formed. In the reinforced earthenware of the second invention thus obtained, since the first glaze is applied to the base material to form the first glaze layer, the surface side of the base material is impregnated with the first glaze and the base material is impregnated. The first glaze that had been used also constitutes the first glass layer inside the ceramic body made of the base material. Therefore, the first glass layer is firmly adhered to the ceramic body. Further, in this reinforced earthenware, since the second glaze is applied on the first glaze layer to form the second glaze layer, the second glaze impregnates the first glaze layer, and the first glass layer and the second glaze layer. It is possible to firmly adhere to the glass layer and prevent the occurrence of cracks that progress at their interfaces. Further, as a result, the firing process can be completed at one time, and the manufacturing cost can be reduced.

[0049] Further, in the method for producing reinforced earthenware of the second invention, it is preferable that the first glaze contains potassium and the second glaze contains sodium. Since potassium has a larger ionic radius than sodium, the sodium ions in the second glaze are ion-exchanged with the potassium ions in the first glaze by using these first and second glazes. Therefore, the reinforced earthenware of the second invention having the second glass layer containing a large amount of potassium and a small amount of sodium as compared with the first glass layer can be obtained.

[0050] Further, in the method for producing reinforced porcelain of the second invention, the second glaze may contain an antibacterial metal. In this case, reinforced earthenware having an antibacterial function can be produced.

[0051] Further, in the method for producing the reinforced porcelain of the second invention, the second glaze can be made to have a higher viscosity at the time of melting than the first glaze. In this case, degassing during firing can be performed smoothly, prevention of blistering of reinforced earthenware can be prevented, and the rate at which antibacterial metal diffuses from the second glass layer into the first glass layer during firing is slow. Therefore, it is possible to manufacture reinforced earthenware in which the concentration of antibacterial metal on the surface is kept high.

[0052] Further, the method for producing reinforced earthenware of the second invention can include a water-repellent treatment step of treating the surface of the glass layer with water-repellent treatment. In this case, it is possible to manufacture reinforced earthenware in which dirt does not easily remain.

[0053] The product having the glass layer of the third invention is<u style="single">Ceramic body</u>And the<u style="single">Ceramic body</u>In a product having a glass layer composed of a glass layer formed on the surface of the above, the glass layer is formed on the outer surface side of the first glass layer made of the first glaze and the first glass layer.<u style="single">Contains antibacterial metal</u>It has a second glass layer made of a second glaze, and the surface of the second glass layer has a second glass layer.<u style="single">Zircon fine particles that prevent the growth of scratches</u>Is dispersed<u style="single">Re,</u><u style="single"> The average particle size of the zircon fine particles is 0.8 μm or more.</u>It is characterized by that.

【0054】<u style="single">No.</u>2 The coefficient of linear thermal expansion of the glass layer is smaller than the coefficient of linear thermal expansion of the first glass layer<u style="single">If</u>In the melting process of the first and second glaze layers and the cooling process of the first and second glass layers in the firing step, the second glass layer receives compressive stress due to the shrinkage of the first glass layer. Therefore, the second glass layer is densified to increase the surface hardness, and the surface of the glass layer is less likely to be scratched. In addition, cracks are unlikely to occur in the glass layer or the like due to scratches. Therefore, the product of the third invention is less likely to adhere to stains caused by scratches and cracks, and can exhibit excellent antifouling properties.

【0055】<u style="single">No.</u>3 inventions<u style="single">With a glass layer</u>In the product, if there is an external factor that scratches the surface of the second glass layer, it is present on the surface.<u style="single">Zircon</u>The fine particles prevent the surface of the second glass layer from sliding with its factors. Therefore, even if the factor slides on the surface of the second glass layer, the time is short and it is difficult to cause a large scratch. Therefore, the product of the third invention is less likely to be soiled and exhibits excellent antifouling properties.

Further, in the product of the third invention, the coefficient of linear thermal expansion of the second glass layer is smaller than the coefficient of linear thermal expansion of the first glass layer.<u style="single">If</u>, The second glass layer is less likely to cause pinholes. Therefore, this product has higher smoothness and can realize excellent antifouling property.

[0057] The product having the glass layer of the third invention is<u style="single">Ceramic body</u>It may have three or more glass layers on top. For example, when having three glass layers, the middle layer corresponds to the first glass layer and the upper layer corresponds to the second glass layer.

[0058] Used in the product having the glass layer of the third invention.<u style="single">Zircon</u>The average particle size of the fine particles is preferably 0.8 to 20 μm. In this case, the above-mentioned scratch resistance can be exhibited, and the aesthetic appearance of the product having the glass layer can be maintained.

【0059】<u style="single">The</u>Lucon fine particles have a harder property than the above-mentioned factors such as scratching the surface of the second glass layer. As such a factor, a brush or an abrasive used for removing stains can be considered. Since such a factor is caught in the zircon fine particles, the factor is less likely to be scratched on the second glass layer.

[0060] While the zircon fine particles exhibit scratch resistance as described above, depending on the proportion contained in the second glass layer, the smoothness of the surface of the second glass layer may be impaired, or the second glass layer may be present. It affects the color development of. Therefore, the ratio of zircon fine particles contained in the second glass layer is<u style="single">With the outer glaze of the second glaze</u>0.5~2<u style="single">quality</u>The amount is preferably%.

[0061] In the product having the glass layer of the third invention,<u style="single">Ceramic body</u>It is preferable that the coefficient of linear thermal expansion is larger than that of the first glass layer. If this is the case, in the firing process<u style="single">Ceramic body</u>In the sintering process, the melting process of the glaze layer, and the cooling process of the substrate and the glass layer, not only the second glass layer receives compressive stress from the first glass layer, but also the first glass layer.<u style="single">Ceramic body</u>Therefore, not only the second glass layer but also the first glass layer is densified. Therefore, in the product having the glass layer of the third invention, cracks generated in the glass layer and the like are unlikely to proceed.

[0062] Further, in the product having the glass layer of the third invention, the linear thermal expansion coefficient of the first glass layer and the second glass layer is 1 × 10.^-7~1×10^-6It is preferable to have a difference of / ° C. If the difference in linear thermal expansion coefficient between the first glass layer and the second glass layer is smaller than this range, the desired surface hardness cannot be obtained, and conversely, if it is large, the second glass layer is from the first glass layer. This is because the compressive stress received becomes too large and the second glass layer may be destroyed. In particular, according to the test results of the inventors, the first glass layer and the second glass layer have a coefficient of linear thermal expansion of 2 × 10.^-7~5×10^-7It is practical to have a difference of / ° C.

[0063] In this case, it is preferable that the first glass layer and the second glass layer have a difference in thickness of 10: 1 to 30: 1. In this case, even if the second glass layer contains an antibacterial metal such as Ag and the appearance of the second glass layer is not good, the appearance is almost different from the case where only the first glass layer is formed. Since the surface is not present, it is possible to obtain a product having a glass layer having a surface having an excellent appearance in terms of design.

[0064] Depending on the composition and thickness of the second glass layer, it is possible to prevent light interference at the interface with the first glass layer, and thereby prevent brilliance. Further, depending on the composition of the second glass layer, the second glass layer may be crystallized vitreous and opaque.

[0065] Also<u style="single">Ceramic body</u>And the first glass layer has a coefficient of linear thermal expansion of 1 × 10.^-7~1×10^-6It is desirable to have a difference of / ° C.<u style="single">Ceramic body</u>If the difference between the linear thermal expansion coefficient and the first glass layer is smaller than this range, the desired strength cannot be obtained, and conversely, if it is large, the first glass layer is<u style="single">Ceramic body</u>This is because the compressive stress received from the glass becomes too large and the first glass layer may be destroyed. In particular, according to the test results of the inventors,<u style="single">Ceramic body</u>And the first glass layer have a coefficient of linear thermal expansion of 2 × 10.^-7~5×10^-7It is practical to have a / ° C difference.

[0066] According to the test results of the inventors, in the product having the glass layer of the third invention, the second glass layer contains more potassium and less sodium than the first glass layer. .. Potassium has a larger ionic radius than sodium. Therefore, when forming the glass layer according to the product having the glass layer of the third invention, sodium ions in the second glass layer are ion-exchanged with potassium ions in the first glass, and compressive stress is applied to the second glass layer. It is considered that it occurs and the strength of the second glass layer increases.

[0067] The product having the glass layer of the third invention has a large antifouling effect when the second glass layer contains an antibacterial metal. In particular, in the product having the glass layer of the third invention, since the antibacterial metal is contained only in the second glass layer in the glass layer, the concentration of the antibacterial metal on the surface side can be increased even if a smaller amount of the antibacterial metal is used than before. It can be made higher, and a higher antibacterial function can be exhibited. In addition, wasteful consumption of the antibacterial metal can be prevented.

[0068] Here, as the antibacterial metal, the same ones as those in the first and second inventions can be adopted.

[0069] Further, in the product having the glass layer of the third invention, it is preferable that a water repellent layer containing a water repellent component is formed on the surface side of the second glass layer. In this case, even if water containing a large amount of dirt components is used on the surface that has been scratched even slightly, the water-repellent function makes it difficult for dirt to remain, and an excellent antifouling effect is exhibited.

[0070] In this case, the same water repellent treatment step as in the first and second inventions can be performed.

[0071] The product having the glass layer of the third invention<u style="single">, Feces</u>Ceramics such as vessels and washbasins. This is because these ceramics are particularly required to have the above-mentioned effects because they are often washed with a brush using a detergent containing an abrasive together with water.

[0072] The method for manufacturing a product having a glass layer according to the third invention is as follows.<u style="single">Ceramic body</u>And the<u style="single">Ceramic body</u>The preparatory step of preparing a glaze capable of forming a glass layer on the surface of the<u style="single">Ceramic body</u>The glaze process of forming a glaze layer composed of the glaze on the surface of the glaze, and the glaze<u style="single">Ceramic body</u>And the glaze layer is fired and said<u style="single">Ceramic body</u>In a method for producing a product having a glass layer, which comprises a firing step of obtaining a product composed of the glass layer and the glaze.<u style="single">Ceramic body</u>The first glaze formed on the side and forming the first glass layer and the first glaze formed on the outer surface side have a smaller coefficient of linear thermal expansion than the first glass layer and are on the surface.<u style="single">Zircon</u>It is characterized by being composed of a second glaze forming a second glass layer in which fine particles are dispersed.

[0073] According to the production method of the third invention, the product having the glass layer of the third invention can be produced.

[0074] Further, in the method for producing a product having a glass layer of the third invention, in the glaze process, a first glaze layer made of the first glaze is formed, and then a second glaze made of the second glaze is formed on the first glaze layer. A glaze layer can be formed. In the product having the glass layer of the third invention thus obtained,<u style="single">Ceramic body</u>Since the first glaze is applied to the glaze to form the first glaze layer,<u style="single">Ceramic body</u>The surface side of is impregnated with the first glaze,<u style="single">Ceramic body</u>The first glaze that was impregnated in<u style="single">Ceramic body</u>It constitutes the first glass layer inside. Therefore, the first glass layer<u style="single">Ceramic body</u>It is firmly attached to. Also this<u style="single">Ceramic body</u>Then, since the second glaze is applied on the first glaze layer to form the second glaze layer, the second glaze impregnates the first glaze layer, and both the first glass layer and the second glass layer are firmly formed. In addition to being in close contact with each other, it is possible to prevent the occurrence of cracks that progress to their interfaces. Further, as a result, the firing process can be completed at one time, and the manufacturing cost can be reduced.

[0075] Further, in the method for producing a product having a glass layer of the third invention, it is preferable that the first glaze contains potassium and the second glaze contains sodium. Since potassium has a larger ionic radius than sodium, the sodium ions in the second glaze are ion-exchanged with the potassium ions in the first glaze by using these first and second glazes. Therefore, a product having the glass layer of the third invention having the second glass layer containing a large amount of potassium and a small amount of sodium as compared with the first glass layer can be obtained.

[0076] Further, in the method for producing a product having a glass layer of the third invention, the second glaze may contain an antibacterial metal. In this case, a product having a glass layer imparted with an antibacterial function can be produced.

[0077] Further, in the method for producing a product having a glass layer of the third invention, the second glaze can have a higher viscosity at the time of melting than the first glaze. If this is the case, disperse it in the second glass layer.<u style="single">Zircon</u>It can prevent fine particles from agglomerating,<u style="single">Zircon</u>The fine particles can be present in a state of being suitably dispersed on the surface. In addition, degassing during firing is performed smoothly, it is possible to prevent blistering of products having a glass layer, and the rate at which antibacterial metal diffuses from the second glass layer into the first glass layer during firing is slow. Therefore, it is possible to manufacture a product having a glass layer in which the concentration of the antibacterial metal on the surface is kept high.

[0078] Further, the method for producing a product having a glass layer of the third invention can include a water repellent treatment step of treating the surface of the glass layer with water repellent treatment. In this case, it is possible to manufacture a product having a glass layer in which dirt does not easily remain.

[Embodiments of the Invention] {First Invention} Hereinafter, Examples and Comparative Examples 1 and 2 embodying the first invention will be described with reference to FIGS. 1 to 5. (Example) [0080] "Preparation process" of "antibacterial treatment process" First, a tile base material having the following composition is prepared as a ceramic molded body, and the tile base material is 50 ± 2 mm square (thickness within 10 mm). Cut into squares to obtain the substrate 1 shown in FIGS. 1 and 2.

[Mixing ratio (mass%) of base material for tiles&gt; Feldspar: 28.2 Silica sand: 11.8 Sericite: 15.0 Clay: 45.0 [0082] In addition, prepare a first glaze and a second glaze having the following composition.

[Mixing ratio of the first glaze (mass%)&gt; Feldspar: 35.0 Silica sand: 46.9 Lime: 15.9 Clay: 2.2 [0084] This first glaze contains K.₂Contains 2% by mass of O.

[Mixing ratio of second glaze (mass%)&gt; Silica sand: 31.0 Lime: 6.0 Clay: 13.0 Antibacterial agent: 50.0 Here, the antibacterial agent has the following composition (mass%). Ag₂O: 25.88 P₂O₅ : 4.98 CaO: 0.01SiO₂ : 56.84 Al₂O₃ : 9.36 Fe₂O₃ : 0.10 K₂O: 0.43 Na₂O: 0.06 SrO: 0.01 Igloss: 2.34 [0086] This second glaze is Na₂Contains 2% by mass of O.

"Vitrification step" of "antibacterial treatment step" As shown in FIG. 1, after the first glaze is applied to the surface of the substrate 1 to form the first glaze layer 2, as shown in FIG. The second glaze is applied to the surface side of the first glaze layer 2 to form the second glaze layer 3.

[0088] The substrate 1 having the first glaze layer 2 and the second glaze layer 3 is fired at 1210 ° C. As a result, the first glaze layer 2 and the second glaze layer 3 are melted, and as shown in FIG. 3, the first glass layer 4 and the second glass layer 5 are formed on the substrate 1.

[0089] Here, since the second glaze layer 3 has a higher viscosity at the time of melting than the first glaze layer 2, most of the silver compound 6 as an antibacterial metal added in the second glaze is the first. 2 Stay in glass layer 5. Further, the first glass layer 4 and the second glass layer 5 have a thickness difference of 20: 1.

Water-repellent treatment step After that, a water-repellent treatment step is performed on the surface of the second glass layer 5.

[0091] First, as a perfluoroalkyl group-containing organosilicon compound [0092] C₈F₁₇CH₂CH₂Si (OCH₃)₃[0093] and [0094] Si (CH) as a hydrolyzable group-containing methylpolysiloxane compound.₃O)₃CH₂CH₂-(Si (CH)₃)₂O)₁₀-Si (CH)₃)₂CH₂CH₂Si (OCH₃)₃[0095] A first agent is prepared by co-hydrolyzing these in a hydrophilic solvent composed of 0.1N hydrochloric acid water, t-butanol and hexane. Each of these is considered to have a silanol (Si-OH) group.

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

[0097] Then, 5 ml of the second agent is added to 5 ml of the first agent and mixed to obtain a water-repellent treatment liquid. This water-repellent treatment liquid is applied to the surface of the second glass layer 5 to form a film. After this, leave it for about 10 minutes to dry. After this, the surface is washed with ethanol and dried.

[0098] As shown in FIG. 4, the first glass layer 4 composed of the base 1 and the first glaze formed on the base 1 and the first glass layer 4 formed on the outer surface side of the first glass layer 4 are antibacterial. A sample composed of a second glass layer 5 containing a metal and a second glaze different from the first glaze and a water repellent layer 7 formed on the surface side of the second glass layer 5 and containing a water repellent component is obtained.

[0099] Here, in the sample of the example, since the first glass layer 4 and the second glass layer 5 have a difference in thickness of 20: 1, the second glass layer 5 itself contains the silver compound 6. Therefore, although the appearance is not good, the surface is almost the same as the case where only the first glass layer 4 is formed, and the surface has an excellent design. (Comparative Example 1) [0100] As shown in FIG. 5, a glaze having the following composition is glazed on a substrate 1 of the same type as that of the example to form a glaze layer.

[0101] &lt;Glazed blending ratio (mass%)&gt; Feldspar: 53.7 Silicic acid sand: 9.8 Lime: 12.3 Dolomite: 4.8 Glazed clay: 5.1 Zinc oxide: 2.0 Zircon: 10.1 Silicic acid-based frit: 2.2 Add 0.5% by mass of silver powder (purity 99% or more, average particle size 10 μm) to make a glaze.

[0102] The substrate 1 having the glaze layer is calcined at 1210 ° C. As a result, the glaze layer is melted to form the glass layer 8 on the substrate 1 as shown in FIG. In this way, a sample composed of the substrate 1 and the glass layer 8 formed on the substrate 1 and containing an antibacterial metal and made of a glaze is obtained. (Comparative Example 2) [0103] A glaze was used in which the concentration of silver powder in the glaze was 5.0% by mass, which was 10 times that of Comparative Example 1. Other antifouling treatment methods and sample composition are the same as in Comparative Example 1. (Evaluation) [0104] Three samples of each of the above Examples and Comparative Examples 1 and 2 were prepared, and an antibacterial performance test was conducted by the film method. The results are shown in Table 1.

[0105] [Table 1]<img file="JP4056877B2_D0001.tif" />[0106] From Table 1, regarding the antibacterial function against any of the bacteria, in the example, the average increase / decrease difference was maintained at 2.0 or more even if the nutrient concentration was increased, whereas in the comparative example 1, the average increase / decrease was maintained. It can be seen that the value difference is maintained at 2.0 or more when it is 1 / 500NB or less, and in Comparative Example 2 when it is 1 / 200NB or less. Therefore, although the amount of silver powder used in Examples is smaller than that in Comparative Examples 1 and 2, it can be seen that Examples are superior in antifouling effect to Comparative Examples 1 and 2.

[0107] From the above, since the silver compound 6 is present in the second glass layer 5 on the surface side in the examples, it is compared with the case where the antibacterial metal is dispersed in the entire glass layer 8 as in Comparative Examples 1 and 2. However, it can be seen that the same amount of silver compound 6 has a higher surface concentration, exhibits excellent antibacterial function, and can prevent wasteful consumption of antibacterial metal. In particular, in the examples, since the phosphoric acid compound was contained in the second glaze, the antibacterial function of the antibacterial metal is more likely to be exhibited. Further, in the embodiment, since the water-repellent layer 7 is formed on the surface of the second glass layer 5, both the antibacterial function and the water-repellent function are imparted, and the antibacterial function alone is insufficient for the antifouling effect. Even if water containing a large amount of stain components is used, the water-repellent function makes it difficult for stains to remain, and the antifouling effect can be sufficiently exhibited.

[0108] Therefore, it can be seen that according to the antifouling treatment method of the example, a product having a glass layer capable of exhibiting an excellent antibacterial function as well as being able to be produced at low cost can be produced.

[0109] Further, in the antifouling treatment method of the example, degassing during firing was smoothly performed, and blistering of the sample could be prevented. {Second Invention} [0110] Hereinafter, examples embodying the second invention will be described together with comparative examples. (Example) [0111] "Preparation step" First, a tile base 1 having the following composition cut into a square of 50 ± 2 mm square (thickness within 10 mm) is prepared.

[Mixing ratio of base material 1 (mass%)&gt; Feldspar: 28.2 Silica sand: 11.8 Sericite: 15.0 Clay: 45.0 [0113] In addition, prepare a first glaze and a second glaze having the following composition.

&lt;Mixing ratio of the first glaze (mass%)&gt; Feldspar: 35.0 Quartz sand: 46.9 Lime: 15.9 Clay: 2.2 This first glaze contains 2% by mass of K2O.

&lt;Mixing ratio of second glaze (mass%)&gt; Silica sand: 31.0 Lime: 6.0 Clay: 13.0 Antibacterial agent: 50.0 Here, the antibacterial agent has the following composition (mass%). Ag₂O: 25.88 P₂O₅ : 4.98 CaO: 0.01SiO₂ : 56.84 Al₂O₃ : 9.36 Fe₂O₃ : 0.10 K₂O: 0.43 Na₂O: 0.06 SrO: 0.01 Igloss: 2.34 [0116] This second glaze is Na₂Contains 2% by mass of O.

"Glazing Step" As shown in FIG. 6, after the first glaze is applied to the surface of the base material 1 to form the first glaze layer 2, the surface of the first glaze layer 2 is formed as shown in FIG. A second glaze is applied to the side to form the second glaze layer 3.

[Baking step] The base material 1 having the first glaze layer 2 and the second glaze layer 3 is fired at 1210 ° C. As a result, the base material 1 is sintered, the first glaze layer 2 and the second glaze layer 3 are melted, and as shown in FIG. 8, the first glass layer 4 and the second glass layer 5 are placed on the ceramic body 1. Form.

Here, the coefficient of linear thermal expansion of the second glass layer 5 is smaller than the coefficient of linear thermal expansion of the first glass layer 4, and the difference is 3 × 10.^-7/ ° C. The coefficient of linear thermal expansion of the first glass layer 4 is smaller than the coefficient of linear thermal expansion of the ceramic body 1, and the difference is 4 × 10.^-7/ ° C. Further, the first glass layer 4 and the second glass layer 5 have a thickness difference of 20: 1. Further, the silver compound 6 as an antibacterial metal is dispersed in the second glass layer 5.

[Water-repellent treatment step] Then, the following water-repellent treatment is applied to the surface of the second glass layer 5.<u style="single">Reason</u>gave.

[0122] First, as a perfluoroalkyl group-containing organosilicon compound [0122] C₈F₁₇CH₂CH₂Si (OCH₃)₃[0123] and [0124] Si (CH) as a hydrolyzable group-containing methylpolysiloxane compound.₃O)₃CH₂CH₂-(Si (CH)₃)₂O)₁₀-Si (CH)₃)₂CH₂CH₂Si (OCH₃)₃[0125] A first agent is prepared by co-hydrolyzing these in a hydrophilic solvent consisting of 0.1N hydrochloric acid water, t-butanol and hexane. Each of these is considered to have a silanol (Si-OH) group.

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

[0127] Then, 5 ml of the second agent is added to 5 ml of the first agent and mixed to obtain a water-repellent treatment liquid. After applying this water-repellent treatment liquid to the surface of the ceramic body 1 having the first glass layer 4 and the second glass layer 5, leave it for about 10 minutes to dry it. After this, the surface is washed with ethanol and dried.

[0128] As shown in FIG. 9, the ceramic body 1, the first glass layer 4 composed of the first glaze formed on the ceramic body 1, and the first glass layer 4 are formed on the outer surface side. A sample composed of a second glass layer 5 containing an antibacterial metal and a second glaze different from the first glaze, and a water repellent layer 7 formed on the surface side of the second glass layer 5 and containing a water repellent component. obtain. (Comparative Example) [0129] As shown in FIG. 10, a glaze having the following composition is glazed on a base material 1 of the same type as that of the example to form a glaze layer.

&lt;Mixing ratio of glaze (mass%)&gt; Feldspar: 10.0 Kaolin: 5.0 Silicic acid-based frit: 85.0 Here, the silicic acid-based frit has the following composition (mass%). SiO₂ : 67.4 Al₂O₃ : 8.6 MgO: 2.7 CaO: 5.7 SrO: 3.2 Na₂O: 2.3 K₂O: 3.2 B₂O₃ : 3.5 ZnO: 2.3 MoO₃ : 1.1 Bake base 1 with glaze layer at 1210 ° C. As a result, the glaze layer is melted to form the glass layer 8 on the ceramic body 1 as shown in FIG. In this way, a sample composed of the ceramic body 1 and the glass layer 8 formed on the ceramic body 1 and containing an antibacterial metal and made of a glaze is obtained. (Evaluation) [0131] Samples of the above Examples and Comparative Examples were prepared, and the brushing test shown below was performed.

&lt;Brushing test&gt; A commercially available toothbrush coated with a commercially available abrasive is prepared, and the surface of the sample is slid 20 times under a constant pressure by the toothbrush. This makes it 4 cm²The total number of scratches (scratches) and the length of the scratches (mm) were calculated. The results are shown in Table 2.

[0133] [Table 2]<img file="JP4056877B2_D0002.tif" />[0134] From Table 2, it can be seen that in the sample of the example, the first glass layer 4, the second glass layer 5, and the ceramic body 1 are less likely to be scratched than the sample of the comparative example. This is considered to be due to the following reasons (1) to (4).

(1) In the embodiment, since the coefficient of linear thermal expansion of the second glass layer 5 is smaller than the coefficient of linear thermal expansion of the first glass layer 4, the first and second glaze layers 2 and 3 are melted in the firing step. In the process and the cooling process of the first and second glass layers 4 and 5, the second glass layer 5 is subjected to compressive stress due to the shrinkage of the first glass layer 4. Therefore, the second glass layer 5 is densified and the surface hardness is increased. Therefore, it can be seen that in the sample of the example, cracks are unlikely to occur in the glass layer or the like due to scratches, and dirt due to scratches is also unlikely to adhere.

(2) Further, since the ceramic body 1 has a larger coefficient of linear thermal expansion than the first glass layer 4, the first glass layer 4 receives compressive stress from the ceramic body 1, and the first glass layer 4 is also dense. To become. Therefore, in the sample of the example, cracks generated in the glass layer or the like are unlikely to progress.

(3) Further, as shown in FIG. 11, the X-ray intensity of the Kα ray of potassium in the example is in a low range of 198 cps to 331 cps in the first glass layer 4, whereas it is in the second glass. It can be seen that the range is as high as 331 cps to 463 cps in layer 5. Therefore, in the embodiment, sodium ions having a small ionic radius existing in the second glass layer 5 are ion-exchanged with potassium ions having a large ionic radius in the first glass layer 4 during the firing process, and are present in the second glass layer 5. It can be said that potassium ions are diffused. Then, the second glass layer 5 itself generates compressive stress, and the second glass layer 5 is strengthened.

(4) Further, in the sample of the example, since the first glaze was applied to the base material 1 to form the first glaze layer 2, the surface side of the base material 1 was impregnated with the first glaze. The first glaze impregnated in the base material 1 also constitutes the first glass layer 4 in the ceramic body 1 made of the base material 1. Therefore, the first glass layer 4 is firmly adhered to the ceramic body 1. Further, in this sample, since the second glaze is applied on the first glaze layer 2 to form the second glaze layer 3, the second glaze impregnates the first glaze layer 2 and the first glass layer 4 And the second glass layer 5 can be firmly adhered to each other, and cracks can be prevented from progressing at their interfaces. Further, as a result, the firing process can be completed at one time, and the manufacturing cost can be reduced.

[0139] Further, since the first glass layer 4 and the second glass layer 5 have a thickness difference of 20: 1, the second glass layer 5 itself contains the silver compound 6, which makes it unattractive. Nevertheless, the surface is almost the same in appearance as when only the first glass layer 4 is formed, and has a surface with an excellent design.

[0140] Further, the samples of Examples and Comparative Examples have an antibacterial function because the second glass layer 5 or the glass layer 8 contains the silver compound 6 which is an antibacterial metal. Here, in the examples, since the silver compound 6 is contained only in the second glass layer 5 in the glass layer, the concentration of the silver compound 6 on the surface side is high even if a smaller amount of the silver compound 6 than in the comparative example is used. It is possible to realize a higher antibacterial function. In addition, wasteful consumption of the silver compound 6 can be prevented. Further, in the examples, since the second glaze has a higher viscosity at the time of melting than the first glaze, degassing at the time of firing can be performed smoothly, the blistering of the sample can be prevented, and the silver compound 6 at the time of firing can be prevented. Diffuses from the second glass layer 5 into the first glass layer 4 at a slower rate, and a sample can be produced in which the concentration of the silver compound 6 on the surface is kept high.

[0141] Further, in the sample of the example, since the water-repellent layer 7 is formed on the surface of the second glass layer 5, the surface of the second glass layer 5, which is slightly scratched, contains a large amount of dirt components. Even if water is used, its water-repellent function makes it difficult for dirt to remain, and exhibits an excellent antifouling effect. In particular, in the examples, since the phosphoric acid compound was contained in the second glaze, the antibacterial function of the silver compound 6 is more likely to be exhibited. Further, in the embodiment, since the water-repellent layer 7 is formed on the surface of the second glass layer 5, both the antibacterial function and the water-repellent function are imparted, and the antibacterial function alone is insufficient for the antifouling effect. Even if water containing a large amount of stain components is used, the water-repellent function makes it difficult for stains to remain, and the antifouling effect can be sufficiently exhibited. {Third Invention} [0142] Hereinafter, Examples 1 to 7 embodying the third invention will be described together with Comparative Examples 1 to 4. (Example 1) [0143] "Preparation step" First, as shown in FIGS. 12 and 13, a substrate 1 as a base for tiles having the following composition cut into squares of 50 ± 2 mm square (within 10 mm in thickness). Prepare.

[Mixing ratio of base material 1 (mass%)&gt; Feldspar: 28.2 Silica sand: 11.8 Sericite: 15.0 Clay: 45.0 [0145] In addition, prepare the first glaze and the second glaze having the following composition.

&lt;0146] &lt;Mixing ratio of the first glaze (% by mass)&gt; Feldspar: 42.456 Frit: 1.617 Lime: 11.827 Dolomite: 5.054 Zinc oxide: 1.516 Frog eyes: 4.043 Alumina: 1.769 Silica sand: 9.603 Milky white agent: 6.368 Chamotte refractory: 15.163 Pigment: 0.581 Here, the frit has the following composition (% by mass). SiO₂ : 49.3 Al₂O₃ 11.1 CaO: 0.2 Na₂O: 19.1 K₂O: 1.0 B₂O₃ 19.2 [0147] For this first glaze, K₂Contains 2% by mass of O.

&lt;Mixing ratio of second glaze (mass%)&gt; Silica sand: 31.0 Lime: 6.0 Clay: 13.0 Antibacterial agent: 50.0 Here, the antibacterial agent has the following composition (mass%) (hereinafter, the same applies. ). Ag₂O: 25.88 P₂O₅ : 4.98 CaO: 0.01SiO₂ : 56.84 Al₂O₃ : 9.36 Fe₂O₃ : 0.10 K₂O: 0.43 Na₂O: 0.06 SrO: 0.01 Igloss: 2.34 [0149] In the above formulation, 1% by mass of zircon fine particles 3a with an average particle size of 0.81 μm is added as a hard fine particle to make a second glaze. This second glaze contains Na₂Contains 2% by mass of O.

"Glazing Step" As shown in FIG. 12, after the first glaze is applied to the surface of the base material 1 to form the first glaze layer 2, the surface of the first glaze layer 2 is formed as shown in FIG. A second glaze is applied to the side to form the second glaze layer 3.

[Fired step] The base material 1 having the first glaze layer 2 and the second glaze layer 3 is fired at 1210 ° C. As a result, the base material 1 is sintered and the first glaze layer 2 and the second glaze layer 3 are melted, and as shown in FIG. 14, the first glass layer 4 and the second glass layer 5 are placed on the ceramic body 1. Form. Here, on the surface of the second glass layer 5, the zircon fine particles 3a are present in a dispersed state.

[0152] Here, the linear thermal expansion coefficient of the second glass layer 5 linear thermal Rise of the first glass layer 4 less than expansion coefficient, the difference is 3 × 10^-7/ ° C. The coefficient of linear thermal expansion of the first glass layer 4 is smaller than the coefficient of linear thermal expansion of the ceramic body 1, and the difference is 4 × 10.^-7/ ° C. Further, the first glass layer 4 and the second glass layer 5 have a thickness difference of 20: 1. Further, the silver compound 6 as an antibacterial metal is dispersed in the second glass layer 5.

[Water-repellent treatment step] Then, the following water-repellent treatment is applied to the surface of the second glass layer 5.<u style="single">Reason</u>gave.

[0154] First, as a perfluoroalkyl group-containing organosilicon compound [0155] C₈F₁₇CH₂CH₂Si (OCH₃)₃[0156] and [0157] Si (CH) as a hydrolyzable group-containing methylpolysiloxane compound.₃O)₃CH₂CH₂-(Si (CH)₃)₂O)₁₀-Si (CH)₃)₂CH₂CH₂Si (OCH₃)₃[0158] The first agent is prepared by co-hydrolyzing these in a hydrophilic solvent composed of 0.1N hydrochloric acid water, t-butanol and hexane. Each of these is considered to have a silanol (Si-OH) group.

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

[0160] Then, 5 ml of the second agent is added to 5 ml of the first agent and mixed to obtain a water-repellent treatment liquid. After applying this water-repellent treatment liquid to the surface of the ceramic body 1 having the first glass layer 4 and the second glass layer 5, leave it for about 10 minutes to dry it. After this, the surface is washed with ethanol and dried.

[0161] As shown in FIGS. 15 and 16, the ceramic main body 1, the first glass layer 4 composed of the first glaze formed on the ceramic main body 1, and the outer surface side of the first glass layer 4 From the second glass layer 5 which is formed in the glass and contains an antibacterial metal and is composed of a second glaze different from the first glaze, and the water repellent layer 7 which is formed on the surface side of the second glass layer 5 and contains a water repellent component. Then, a sample containing zircon fine particles 3a also present on the surface of the water-repellent layer 7 is obtained from the second glass layer 5. (Example 2) [0162] In the preparation step of Example 1, the second glaze contains 2% by mass of the zircon fine particles 3a of Example 1 as an outer cover. Other conditions are the same as in Example 1. (Example 3) [0163] In the preparation step of Example 1, the second glaze contains 1% by mass of zircon fine particles 3a having an average particle size of 1.55 μm as hard fine particles. Other conditions are the same as in Example 1. (Example 4) [0164] In the preparation step of Example 1, the second glaze contains 2% by mass of the zircon fine particles 3a of Example 3 as an outer cover. Other conditions are the same as in Example 1. (Example 5) [0165] In the preparation step of Example 1, the second glaze contains 1% by mass of zircon fine particles 3a having an average particle size of 20 μm as hard fine particles. Other conditions are the same as in Example 1. (Example 6) [0166] In the preparation step of Example 1, the second glaze contains 2% by mass of the zircon fine particles 3a of Example 5 as an outer cover. Other conditions are the same as in Example 1. (Example 7) [0167] In the preparation step of Example 1, the second glaze contains 4% by mass of the zircon fine particles 3a of Example 5 as an outer cover. Other conditions are the same as in Example 1. (Comparative Example 1) [0168] As shown in FIG. 17, a glaze having the following composition is glazed on a base material 1 of the same type as that of Example 1 to form a glaze layer.

&lt;Mixing ratio of glaze (mass%)&gt; Feldspar: 10.0 Kaolin: 5.0 Frit: 85.0 Here, the frit has the following composition (mass%). SiO₂ : 67.4 Al₂O₃ : 8.6 MgO: 2.7 CaO: 5.7 SrO: 3.2 Na₂O: 2.3 K₂O: 3.2 B₂O₃ : 3.5 ZnO: 2.3 MoO₃ : 1.1 [0170] Bake the substrate 1 with the glaze layer at 1210 ° C. As a result, the glaze layer is melted and the glass layer 8 is formed on the ceramic body 1. In this way, a sample composed of the ceramic body 1 and the glass layer 8 made of glaze formed on the ceramic body 1 is obtained. (Comparative Example 2) [0171] A glaze having the following composition is glazed on a base material 1 of the same type as that of Example 1 to form a glaze layer. Base 1 having a glaze layer is fired at 1210 ° C to obtain a sample similar to the sample of Comparative Example 1 shown in FIG.

[0172] &lt;Glazed compounding ratio (mass%)&gt; Feldspar: 42.456 Frit: 1.617 Lime: 11.827 Dolomite: 5.054 Zinc oxide: 1.516 Frog eyes: 4.043 Alumina: 1.769 Silica sand: 9.603 Milky white agent: 6.368 Chamotte refractory: 15.163 Pigment :: 0.581 Here, the frit is the same as that of Example 1. In the above formulation, 6.3% by mass of zircon fine particles having an average particle size of 1.55 μm are added to the glaze. (Comparative Example 3) [0173] A base material 1 of the same type as that of Example 1, a first glaze composed of the glaze of Comparative Example 2, and a second glaze having the following composition are prepared. The substrate 1 having the first glaze layer and the second glaze layer is calcined at 1210 ° C to obtain a sample. Thus, as shown in FIG. 18, the ceramic body 1, the first glass layer 9 formed on the ceramic body 1 and composed of the first glaze, and the second glass formed on the glass layer 9 and composed of the second glaze. Form layer 10.

&lt;Mixing ratio of the second glaze (mass%)&gt; Silica sand: 31.0 Lime: 2.3 Clay: 12.4 Zinc oxide: 3.9 Frit: 0.5 Antibacterial agent: 50.0 Here, the frit is the same as that of Comparative Example 1. , The antibacterial agent is the same as in Example 1. (Comparative Example 4) [0175] A base material 1 of the same type as that of Example 1, a first glaze composed of the glaze of Comparative Example 2, and a second glaze having the following composition are prepared. The substrate 1 having the first glaze layer and the second glaze layer is fired at 1210 ° C to obtain a sample similar to the sample of Comparative Example 3 shown in FIG.

&lt;Mixing ratio of second glaze (mass%)&gt; Silica sand: 33.0 Lime: 8.5 Alumina: 7.0 Antibacterial agent: 51.2 Here, the antibacterial agent is the same as in Example 1. (Evaluation) [0177] Samples of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared, pinholes on the surface were confirmed with a digital microscope, and smoothness was evaluated. It is shown in Table 3. In Table 3, those having excellent smoothness are marked with , and those lacking smoothness are marked with x.

[0178] [Table 3]<img file="JP4056877B2_D0003.tif" />[0179] From Table 3, it can be seen that the samples of Examples 1 to 7 and Comparative Examples 3 and 4 have almost no pinholes on the surface and exhibit excellent smoothness. On the other hand, it can be seen that the samples of Comparative Examples 1 and 2 have pinholes on the surface, although the amount is slight, and the smoothness is slightly inferior. This is because the glass layers of the samples of Examples 1 to 7 and Comparative Examples 3 and 4 have a first glass layer and a second glass layer, so that pinholes may occur from the influence of the substrate 1 to the first glass layer. Even so, the influence of the base material 1 is unlikely to affect the second glass layer, and pinholes are unlikely to occur on the surface of the second glass layer. Therefore, it can be seen that the samples of Examples 1 to 7 and Comparative Examples 3 and 4 have higher smoothness and can realize excellent antifouling property.

[0180] Further, in the samples of Examples 1 to 7, the diricone fine particles 3a are contained only in an amount that does not affect the coloration of the second glass layer 5, and the surface smoothness of the second glass layer 5 is smooth. Since it exists in a dispersed state so as not to affect the aesthetic appearance, it has an excellent aesthetic appearance.

[0181] Further, since the samples of Examples 1 to 7 have the water-repellent layer 7 on the surface side of the second glass layer 5, water containing a large amount of stain components is contained on the surface that is slightly scratched. Even if it was used, its water-repellent function made it difficult for dirt to remain, and it exhibited an excellent antifouling effect. Further, since the samples of Examples 1 to 7 contain the silver compound 6 which is an antibacterial metal in the second glass layer 5, they have an antibacterial function, which also exerts an excellent antifouling effect. There is.

[0182] Further, the following brushing tests were performed on the samples of Examples 1 to 7 and Comparative Examples 1 to 4.

&lt;Brushing test&gt; A commercially available toothbrush coated with a commercially available abrasive is prepared, and the surface of the sample is slid 20 times under a constant pressing force by this toothbrush. This makes it 4 cm²The total number of scratches (scratches) and the length of the scratches (mm) were calculated. The results are also shown in Table 3.

[0184] From Table 3, it can be seen that the surfaces of the samples of Examples 1 to 7 and Comparative Examples 2 and 4 are not easily scratched. This is because, in the samples of Examples 1 to 7 and Comparative Example 4, the coefficient of linear thermal expansion of the second glass layer is smaller than the coefficient of linear thermal expansion of the first glass layer, so that the second glass layer is the first glass layer. This is because it receives compressive stress due to shrinkage and becomes denser, resulting in higher surface hardness. In particular, in the samples of Examples 1 to 7, the zircon fine particles 3a existing on the water-repellent layer 7 prevent the abrasive from sliding, so that they are not significantly scratched. Therefore, it can be seen that the samples of Examples 1 to 7 are less likely to adhere to stains caused by scratches and cracks, and can exhibit excellent antifouling properties.

Further, as shown in FIG. 19, the X-ray intensity of the Kα ray of potassium in the samples of Examples 1 to 7 is in the low range of 198 cps to 331 cps in the first glass layer 4, whereas the X-ray intensity is as low as 198 cps to 331 cps. It can be seen that the range is as high as 331 cps to 463 cps in the 2 glass layers 5. Therefore, in the samples of Examples 1 to 7, sodium ions having a small ionic radius existing in the second glass layer 5 are ion-exchanged with potassium ions having a large ionic radius in the first glass layer 4 during the firing process. 2 It can be said that potassium ions are diffused in the glass layer 5. Then, the second glass layer 5 itself generates compressive stress, and the second glass layer 5 is strengthened.

&lt;Antibacterial test&gt; Three samples of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared, and an antibacterial performance test was performed by a film method. Table 4 shows the difference in the average increase / decrease of Escherichia coli (IFO3972) at each nutrient concentration. Table 5 shows the difference in the average increase / decrease of Staphylococcus aureus (IFO12732) at each nutrient concentration. In Tables 4 and 5, no antibacterial effect is observed when the average increase / decrease difference is less than 2.0.

[0187] [Table 4]<img file="JP4056877B2_D0004.tif" />[0188] [Table 5]<img file="JP4056877B2_D0005.tif" />[0189] From Tables 4 and 5, regarding the antibacterial function against any of the bacteria, in the samples of Examples 1 to 7, the average increase / decrease difference was maintained at 2.0 or more even if the nutrient concentration was increased. In the samples of Comparative Examples 1 and 2, it can be seen that the average increase / decrease value difference is maintained at 2.0 or more when 1/500 NB or less. Therefore, it can be seen that the samples of Examples 1 to 7 exhibit better antifouling properties than the samples of Comparative Examples 1 and 2. Further, in the samples of Examples 1 to 7, since the silver compound 6 which is an antibacterial metal is contained only in the second glass layer 5 in the glass layer, even if a smaller amount of the antibacterial agent than before is used, the silver on the surface side is used. It can be seen that the concentration of compound 6 can be increased and a higher antibacterial function can be exhibited. It is also found that the samples of Examples 1 to 7 can prevent unnecessary consumption of the antibacterial agent.

[0190] Further, it can be seen that the samples of Examples 1 to 7 show the same degree of average increase / decrease difference as the samples of Comparative Examples 3 and 4. Therefore, as shown in FIG. 15, the samples of Examples 1 to 7 have zircon fine particles 3a existing on the surfaces of the second glass layer 5 to the water-repellent layer 7, but of Comparative Examples 3 and 4. It can be seen that the antifouling property equivalent to that of the sample can be exhibited.

[0191] Therefore, it can be seen that the samples of Examples 1 to 7 have excellent surface smoothness, are less likely to be scratched on the surface, and can reliably exhibit excellent antifouling property. The above examples and application examples are examples, and the first to third inventions can be carried out in a mode in which various modifications are made without departing from the gist thereof.

INDUSTRIAL APPLICABILITY [0192] According to the antifouling treatment method of the first invention, a product having a glass layer capable of exhibiting an excellent antibacterial function as well as being inexpensive to be produced can be produced. .. The reinforced earthenware of the second invention is less likely to scratch the surface of the glass layer. The product having the glass layer of the third invention is hard to be scratched on the surface, and by extension, excellent antifouling property can be surely exhibited.

BRIEF DESCRIPTION OF THE DRAWINGS [0193] FIG. 1 is a cross-sectional view of a substrate and a first glaze layer according to an embodiment of the first invention.

FIG. 2 is a cross-sectional view of a substrate, a first glaze layer, and a second glaze layer according to an embodiment of the first invention.

FIG. 3 is a cross-sectional view of a substrate, a first glass layer, and a second glass layer according to an embodiment of the first invention.

FIG. 4 is a cross-sectional view of a substrate, a first glass layer, a second glass layer, and a water-repellent layer according to an embodiment of the first invention.

FIG. 5 is a cross-sectional view of a substrate and a glass layer according to Comparative Examples 1 and 2 of the first invention.

FIG. 6 is a cross-sectional view of a base material and a first glaze layer according to an embodiment of the second invention.

FIG. 7 is a cross-sectional view of a substrate, a first glaze layer, and a second glaze layer according to an embodiment of the second invention.

FIG. 8 is a cross-sectional view of a ceramic body, a first glass layer, and a second glass layer according to an embodiment of the second invention.

FIG. 9 is a cross-sectional view of a ceramic body, a first glass layer, a second glass layer, and a water-repellent layer according to an embodiment of the second invention.

FIG. 10 is a cross-sectional view of a ceramic body and a glass layer according to a comparative example of the second invention.

FIG. 11 is a surface analysis result of potassium by EPMA of a cross section of a sample of an example of the second invention.

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

FIG. 13 is a cross-sectional view of a substrate, a first glaze layer, and a second glaze layer according to Examples 1 to 7 of the third invention.

FIG. 14 is a cross-sectional view of a ceramic body, a first glass layer, and a second glass layer according to Examples 1 to 7 of the third invention.

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

FIG. 16 is a top view of a sample according to Examples 1 to 7 of the third invention.

FIG. 17 is a cross-sectional view of a sample according to Comparative Examples 1 and 2 of the third invention.

FIG. 18 is a cross-sectional view of a sample according to Comparative Examples 3 and 4 of the third invention.

FIG. 19 shows the results of surface analysis of potassium by EPMA in the cross section of the samples of Examples 1 to 7 of the third invention.

[Explanation of symbols] 1 ... Base (ceramic body, base material) 2 ... 1st glaze layer 3 ... 2nd glaze layer 4 ... 1st glass layer 5 ... 2nd glass layer 6. .. Silver compound (antibacterial metal) 7 ... Water repellent layer 3a ... Hard fine particles (Zircon fine particles)