JP2002193690A - Stainproof treatment method and product with glass layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a product producible at a low cost and having a glass layer capable of exhibiting an excellent antibacterial function. SOLUTION: In the product, a substrate 1, a first glaze capable of forming a first glass layer 4 on the surface of the substrate 1, and a second glaze capable of forming a second glass layer 5, which contains a silver compound 6, on the surface of the substrate 1, are prepared. A first glaze layer 2 comprising the first glaze is formed on the surface of the substrate 1, and a second glaze layer 3 comprising the second glaze is formed on the upper side of the first glaze layer 2. A first layer 4 and a second glaze layer are formed by melting the first glaze layer 2 and the second glaze layer 3. The second glaze layer 5 has higher viscosity at melting time than the first glaze layer 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antifouling treatment method,
A product having a glass layer.

[0002]

2. Description of the Related Art 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 and an enamel product having an antibacterial function, an antibacterial function is imparted to the surface of a substrate such as a glass molded body, a ceramic molded body, and 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,
A preparation step of preparing a glaze capable of forming a glass layer containing an antimicrobial metal, and a vitrification step of forming a glaze layer made of the glaze on the surface of the substrate and melting the glaze layer to form a glass layer .

[0003] By this antifouling treatment method, a product comprising a substrate having a glass layer and a glass layer comprising the glaze is obtained. In the product having the glass layer thus obtained, the antibacterial metal in the glass layer acts on the bacteria, kills the bacteria, or suppresses the propagation thereof.

[0004]

However, in the above-mentioned general antifouling treatment method, since only a single glass layer is formed on the surface of the substrate, the bacteria on the surface of the glass layer are originally required. However, the antimicrobial function is desired to be exhibited, but the antimicrobial metal is dispersed in the glass layer. And, in the product having the glass layer thus obtained, the effect is low unless the concentration of the antibacterial metal used is increased. For this reason, in this antifouling treatment method, a large amount of antibacterial metal is consumed in order to exhibit an excellent antibacterial function, so that the production cost is increased.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional circumstances, and should solve the problem of manufacturing a product having a glass layer which can be manufactured at a low cost and can exhibit an excellent antibacterial function. Make it an issue.

[0006]

According to the present invention, there is provided an antifouling treatment method comprising an antibacterial treatment step of imparting an antibacterial function to the surface of a substrate.

[0007] The antibacterial treatment step comprises the steps of: forming the base, a first glaze capable of forming a first glass layer on the surface of the base, and a second glaze capable of forming a second glass layer containing an antibacterial metal on the surface of the base.
A preparation process for preparing glaze,

A first glaze comprising the first glaze is formed on the surface of the base.
Forming a glaze layer and a second glaze layer made of the second glaze on the more surface side, and melting the first glaze layer and the second glaze layer to form the first glass layer and the second glass layer; Having a vitrification process to form,

[0009] The second glaze layer is characterized by having a higher viscosity when melted than the first glaze layer.

In the antifouling treatment method of the present invention, first, as a preparation step of the antibacterial treatment step, a base, a first glaze capable of forming a first glass layer on the surface of the base, and a first glaze containing an antibacterial metal on the surface of the base are provided. A second glaze capable of forming two glass layers is prepared.
Then, as a vitrification step of the antibacterial treatment step, a first glaze layer made of a first glaze and a second glaze layer made of a second glaze are formed on the surface of the base, and the first glaze layer and Melting the second glaze layer to form a first glass layer and a second glass layer.

Here, since the second glaze layer has a higher viscosity at the time of melting than the first glaze layer, the antibacterial metal hardly diffuses from the second glass layer on the surface side into the first glass layer, and most of the second antiglare metal is the second glass layer. Stay in the layer. For this reason, in this antifouling treatment method, the antibacterial metal in the second glass layer on the surface side originally desired acts on bacteria and exhibits an excellent antibacterial function without consuming a large amount of antibacterial metal. be able to.

Further, in the antifouling treatment method of the present invention, a first glaze layer made of a first glaze and a second glaze layer made of a second glaze are formed on a more surface side, and the first glaze layer and the second glaze layer are formed. Since the first and second glass layers are formed by melting the glaze layer, in the obtained product, the second glaze impregnates the first glaze layer, and the first and second glass layers are firmly bonded. And the occurrence of cracks at the interface between them can be prevented. In addition, this allows the firing step to be completed at a time, thereby realizing a reduction in manufacturing cost.

Therefore, according to this antifouling treatment method,
It is possible to manufacture a product having a glass layer that can be manufactured at low cost and that can exhibit an excellent antibacterial function.

Thus, a product having the glass layer of the present invention is obtained. A product having a glass layer according to the present invention includes a substrate having a glass layer, the glass layer being formed on a first glass layer made of a first glaze and an outer surface side of the first glass layer,
A second glass layer comprising an antimicrobial metal and a second glaze different from the first glaze.

As a substrate, when a glass product is produced as a product having a glass layer, a glass molded product thereof can be employed. When a ceramic product such as sanitary ware or tile is produced, the ceramic molded product thereof is used. A body can be used, and when manufacturing an enamel product, the metal molded body can be used.

Further, as the antibacterial metal contained in the second glaze, Ag, Cu, Zn or the like can be adopted. 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, Silver sulfate, silver citrate, silver lactate, (3) cuprous phosphate, cupric phosphate, organic copper compounds, cuprous chloride, cupric chloride, cuprous sulfide, cuprous oxide, oxidation Cupric, cupric sulfide, cuprous sulfate, cupric sulfate, copper citrate, copper lactate and the like can be employed. 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 employed.
These antibacterial metals may be a single substance, an alloy, or a compound.

In the product having the glass layer of the present invention, it is preferable that the first glass layer and the second glass layer have a thickness difference of 10: 1 to 30: 1. In this case, even if the second glass layer contains an antimicrobial metal such as Ag, the appearance of the second glass layer is not good, and the appearance is almost the same as the case where only the first glass layer is formed. Since it has no surface, it is possible to obtain a product having a surface with an excellent appearance in design.

According to the test results of the inventors, in the product having the glass layer of the present invention, the second glass layer contains more potassium and less sodium than the first glass layer. I have. Potassium has a larger ionic radius than sodium. For this reason, when forming the glass layer according to the product of the present invention, sodium ions in the second glass layer
It is considered that the ion exchange with the potassium ions in the glass causes a compressive stress in the second glass layer, thereby increasing the strength of the second glass layer.

Further, in the antifouling treatment method of the present invention, the second
It is preferable that the glaze contains a phosphate compound. In the product having the glass layer of the present invention thus obtained, a phosphate compound such as P ₂ O ₅ is present in the second glass layer, and the antibacterial function of the antibacterial metal is more easily exerted. In addition, it is also preferable to include a boric acid compound in the second glaze. In this case, a boric acid compound such as B ₂ O ₃ is present in the second glass layer, and the antibacterial function of the antibacterial metal is more easily exerted.

Further, the antifouling treatment method of the present invention preferably has 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 dirt components is used so that the antifouling effect is insufficient with the antibacterial function alone. Even so, the water-repellent function makes it difficult for dirt to remain, so that the antifouling effect can be sufficiently exhibited.

In this case, the water-repellent treatment step is performed in the second
It can be carried out by forming a coating made of a water-repellent treatment liquid having a silicon-containing functional group that binds to a hydroxyl group present on the surface of the glass layer by a dehydration reaction or a dehydrogenation reaction. When this treatment is performed, the silicon-containing functional group is combined with a hydroxyl group (-OH) present on the surface of the second glass layer by a dehydration reaction or a dehydrogenation reaction to shield the hydroxyl group. For this reason, even if water containing many metal ions such as soluble silica is used, the hydroxyl group is no longer available and does not bind to these metal ions, and does not bind to components such as human waste. In particular, even when water containing soluble silica is used as the metal ion, it does not precipitate or hardly precipitate as silicic acid having a network structure, and it is difficult to take in dirt. Thus, if the water-repellent treatment liquid has this silicon-containing functional group, the product which 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 is easy.

Here, it is preferable that the water-repellent treatment liquid is not bonded between silicon-containing functional groups. According to the test results of the inventors, this results in water-resistant red stains,
It is possible to enhance the antifouling effect on hair dyeing liquid stain, 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 silicon is increased and silicic acid forming a network structure is precipitated in the coating, and dirt is easily taken therein.

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, the presence of the fluorocarbon group in this way makes it easy to exhibit a water repellent function due to the small critical surface tension of the fluorocarbon group, water-resistant stains, hair-dyeing stains, and alkali resistance. Great effect on

Here, the fluorocarbon group is represented by —C _n F _{2n + 1} (n
Is a natural number of 1 ≦ n ≦ 12). According to the test results of the inventors, this has a large number of fluorines and makes the fluorosilane bulky, so that it has a great effect on water stain resistance, hair dye stain resistance, abrasion resistance and alkali resistance.

The water-repellent treatment liquid is a mixture of a first agent and a second agent, and the first agent is a hydrophilic agent between the perfluoroalkyl group-containing organosilicon compound and the hydrolyzable group-containing methylpolysiloxane compound. A co-hydrolysate in a neutral solvent,
The second part can be a mixture of an organopolysiloxane and a strong acid. Here, the perfluoroalkyl group-containing organosilicon compound and the hydrolyzable group-containing methylpolysiloxane compound present in the first agent are combined with a hydroxyl group present 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.

The reason why the perfluoroalkyl group-containing organosilicon compound is used as a constituent component in the first agent is that the large critical surface tension of the fluorocarbon group causes the antifouling effect to appear as a water repellent function, and to prevent water stains and stains. This is because it has a high effect on hair dye stain and alkali resistance. The reason that the hydrolyzable group-containing methylpolysiloxane compound is used as a component in the first agent is that it has a large effect on water stain resistance, hair dye stain resistance and alkali resistance.

The second part is a mixture of an organopolysiloxane and a strong acid. The reason why organopolysiloxane is used as a 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 was used as a component of the second agent is that when the antifouling treatment was performed using the water-repellent treatment liquid prepared by the method according to the present invention, the perfluoroalkyl which is a component in the first agent was used. This is because a strong acid effectively acts as a catalyst for bonding the group-containing organosilicon compound and the hydrolyzable group-containing methylpolysiloxane compound to the hydroxyl group on the surface of the glass layer.

When the first agent and the second agent are mixed, the silanol group of the co-hydrolyzate reacts with the organopolysiloxane and the strong acid to form a siloxane bond (Si--O
-Si), and is considered to be an additional compound in which a plurality of molecules are intricately entangled. For this reason, the water-repellent treatment liquid obtained by mixing the first agent and the second agent contains only one molecule such as a perfluoroalkyl group-containing organosilicon compound, a hydrolyzable group-containing methylpolysiloxane compound, or an organopolysiloxane. It is thought that these molecules are not composed, but are combined as an additional compound or a kind of polymer in which these multiple molecules are intricately entangled, and that the additional compound is strongly bonded to the surface of the substrate. Can be

Thus, a product having the glass layer of the present invention in which the water repellent layer containing the water repellent component is formed on the surface side of the second glass layer is obtained. Since the water-repellent layer is very thin and the water-repellent layer is bonded only to the hydroxyl group on the surface of the second glass layer, it is considered that the antibacterial function permeates the drainage layer.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention and Comparative Examples 1 and 2 will be described below with reference to FIGS.

(Example) "Preparation step" of "antibacterial treatment step" First, a tile base having the following composition was prepared as a ceramic molded body, and the tile base was cut into a 50 ± 2 mm square (within a thickness of 10 mm). 1 and 2
The substrate 1 shown in FIG.

<Mixing ratio (mass%) of tile base material> Feldspar: 28.2 Silica sand: 11.8 Sericite: 15.0 Clay: 45.0

A first glaze and a second glaze having the following composition
Prepare glaze.

<Preparation ratio (mass%) of first glaze> Feldspar: 35.0 Silica sand: 46.9 Lime: 15.9 Clay: 2.2

The first glaze contains 2% by mass of K ₂ O.

<Mixing ratio (% by mass) of second glaze> Silica sand: 31.0 Lime: 6.0 Clay: 13.0 Antibacterial agent: 50.0 Here, the antibacterial agent has the following composition (% by mass): Become. 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 Igloss: 2.34

The second glaze contains 2% by mass of Na ₂ O.

"Vitrification Step" of "Antibacterial Treatment Step" As shown in FIG. 1, a first glaze is applied to the surface of the substrate 1 to form a first glaze layer 2, and as shown in FIG. A second glaze is applied to the surface side of the first glaze layer 2 to form a second glaze layer 3.

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

Here, the second glaze layer 3 is the first glaze layer 2
Since the viscosity at the time of melting is higher than that of the silver compound 6, the silver compound 6 as an antibacterial metal added to the second glaze mostly remains in the second 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] Thereafter, the second glass layer 5
Is subjected to a water-repellent treatment step.

First, as a perfluoroalkyl group-containing organosilicon compound,

C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃

And a hydrolyzable group-containing methylpolysiloxane compound

Si (CH_ThreeO)_ThreeCH_TwoCH_Two− (Si (C
H_Three)_TwoO)_Ten-Si (CH_Three)_TwoCH _TwoCH_TwoSi (OCH
_Three)_Three

Consisting of 0.1 N hydrochloric acid, t
Providing a first agent co-hydrolyzed in a hydrophilic solvent consisting of butanol and hexane; These are considered to have silanol (Si-OH) groups.

Further, the organopolysiloxane (HO-
(Si (CH_Three)_TwoO)₃₀-Si (CH _Three)_TwoOH) and strong
Mixture with methanesulfonic acid as acid as second agent
prepare.

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. Thereafter, it is left to dry for about 10 minutes. Thereafter, the surface is washed with ethanol and dried.

As described above, as shown in FIG.
And a first glass layer 4 formed of a first glaze formed on the substrate 1 and a second glaze formed on the outer surface side of the first glass layer 4 and containing an antibacterial metal and different from the first glaze. A second glass layer 5, formed on the surface side of the second glass layer 5,
A sample comprising the water-repellent layer 7 containing a water-repellent component is obtained.

Here, in the sample of the embodiment, 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. For this reason, the appearance is almost the same as the case where only the first glass layer 4 is formed, even though the appearance is not good.

(Comparative Example 1) As shown in FIG. 5, a glaze having the following composition is glazed on a substrate 1 of the same kind as that of the embodiment to form a glaze layer.

<Mixing ratio (mass%) of glaze> Feldspar: 53.7 Silica sand: 9.8 Lime: 12.3 Dolomite: 4.8 Frog-eyed clay: 5.1 Zinc flower: 2.0 Zircon: 10. 1. Silicic acid frit: 2.2 A mixture of the above-mentioned composition and 0.5% by mass of silver powder (purity: 99% or more, average particle size: 10 μm) is used as a glaze.

The substrate 1 having the glaze layer is fired at 1210 ° C. Thus, the glaze layer is melted, and a glass layer 8 is formed on the base 1 as shown in FIG. In this way, a sample comprising the substrate 1 and the glass layer 8 formed on the substrate 1 and containing an antibacterial metal and made of glaze is obtained.

(Comparative Example 2) A glaze having a silver powder concentration of 5.0% by mass, which is 10 times that of Comparative Example 1, was used. Other antifouling treatment methods and sample configurations are the same as in Comparative Example 1.

(Evaluation) Three samples of each of the above Example and Comparative Examples 1 and 2 were prepared, and an antibacterial performance test was conducted by a film method. Table 1 shows the results.

[0056]

[Table 1]

From Table 1, it can be seen that the antimicrobial function against any of the bacteria has an average increase / decrease value difference of 2.0 or more in the examples even when the nutrient concentration is high, whereas in the comparative example 1, The difference between the average increase and decrease values is maintained at 2.0 or more by 1/50
0 NB or less, and in Comparative Example 2, 1/200 NB
It turns out that it is the following cases. For this reason, it can be seen that the examples are more excellent in the antifouling effect than the comparative examples 1 and 2, even though the amount of the silver powder used in the examples is smaller than that of the comparative examples 1 and 2.

As described above, since the silver compound 6 was present in the second glass layer 5 on the surface side in the examples, the comparative examples 1 and 2
As compared with the case where the antibacterial metal is dispersed throughout the glass layer 8 as described above, the surface concentration is higher with the same amount of the silver compound 6, showing an excellent antibacterial function and wasteful consumption of the antibacterial metal. It can be seen that can be prevented. In particular, in the example, since the phosphate compound was contained in the second glaze, the antibacterial function by the antibacterial metal was more easily 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 provided. Thus, even when water containing a large amount of dirt components is used, dirt hardly remains due to its water repellent function, and the antifouling effect can be sufficiently exhibited.

Therefore, according to the antifouling treatment method of the example, it can be understood that a product having a glass layer capable of exhibiting an excellent antibacterial function can be manufactured at a low cost.

Further, in the antifouling treatment method of the example, degassing during firing was performed smoothly, and blistering of the sample could be prevented.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a base and a first glaze layer according to an example.

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

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

FIG. 4 is a cross-sectional view of a base, a first glass layer, a second glass layer, and a water-repellent layer according to an example.

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... 1st glaze layer 3 ... 2nd glaze layer 4 ... 1st glass layer 5 ... 2nd glass layer 6 ... Antibacterial metal (silver compound) 7 ... Water repellent layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 41/89 C04B 41/89 C C23D 5/00 C23D 5/00 C J13 / 00 13/00 Z ( 72) Inventor Takahiro Morita 5-1-1 Koie Honcho, Tokoname, Aichi Prefecture Inax Corporation (72) Inventor Yuichiro Aihara 5-1-1 Koie Honcho, Tokoname City, Aichi Prefecture Inax Corporation (72) Inventor Ritsu Yamashita 5-1-1 Koiehoncho, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Haruyuki Mizuno 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Shigeo Imai Tokoname Tokoname, Aichi Prefecture 5-1-1 Hommachi Inax Co., Ltd. (72) Inventor Noriyuki Sugiyama 5-1-1 Koiehoncho, Tokoname-shi, Aichi Pref. Kusuuchi (72) Inventor Shungo Tokushima 5-1-1 Koiehonmachi, Tokoname-shi, Aichi F-term in Inax Co., Ltd. (reference) 4G059 AA01 AB01 AB11 AC22 CB09 FA05 FA11 FA22 FB05 GA01 GA04 GA16 4G062 AA01 AA09 BB01 CC08 DA05 DA06 DB03 DC01 DD03 DE01 DF01 EA01 EB02 EC02 ED01 EE02 EF02 EG01 FA01 FA10 FB01 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH04 HH05 HH07 HHH HH HK KK10 MM01 MM40 NN34

Claims (14)

[Claims] 1. An antifouling treatment method having an antibacterial treatment step of imparting an antibacterial function to the surface of a substrate, wherein the antibacterial treatment step comprises the steps of:
A preparation step of preparing a first glaze capable of forming a glass layer and a second glaze capable of forming a second glass layer containing an antimicrobial metal on the surface of the base; Forming a first glaze layer and a second glaze layer composed of the second glaze on the more surface side,
Vitrifying the first glaze layer and the second glaze layer to form the first glass layer and the second glass layer, wherein the second glaze layer is melted from the first glaze layer. An antifouling treatment method characterized by high viscosity at the time. 2. The antifouling treatment method according to claim 1, wherein the second glaze contains a phosphate compound. 3. The antifouling treatment method according to claim 1, further comprising a water repellent treatment step of subjecting the surface of the second glass layer to a water repellent treatment after the antibacterial treatment step. 4. The water-repellent treatment step is performed by forming a film made of a water-repellent treatment liquid having a silicon-containing functional group that binds to a hydroxyl group present on the surface of the second glass layer by a dehydration reaction or a dehydrogenation reaction. The antifouling treatment method according to claim 3, characterized in that: 5. The antifouling treatment method according to claim 4, wherein the water-repellent treatment liquid is not bonded between the silicon-containing functional groups. 6. The antifouling treatment method according to claim 4, wherein the water repellent treatment liquid has a terminal fluorocarbon group bonded to a silicon-containing functional group. 7. The fluorocarbon group is -C _n F _{2n + 1} (where n is 1 ≦ n).
The antifouling treatment method according to claim 6, wherein ≤ 12 (natural number). 8. A water-repellent treatment liquid comprising a mixture of a first agent and a second agent, wherein the first agent comprises a perfluoroalkyl group-containing organosilicon compound and a hydrolyzable group-containing methylpolysiloxane compound. 8. The antifouling treatment method according to claim 7, wherein the second agent is a co-hydrolysate in a hydrophilic solvent, and the second agent is a mixture of an organopolysiloxane and a strong acid. 9. The method according to claim 1, wherein the substrate is a glass molding, a ceramic molding or a metal molding.
The antifouling treatment method according to 2, 3, 4, 5, 6, 7, or 8. 10. A base material having a glass layer, wherein the glass layer is formed on a first glass layer made of a first glaze, and is formed on an outer surface side of the first glass layer and contains an antibacterial metal. A product having a glass layer, comprising a second glass layer made of a second glaze different from the above. 11. A product having a glass layer according to claim 10, wherein the first glass layer and the second glass layer have a thickness difference of 10: 1 to 30: 1. 12. The product having a glass layer according to claim 10, wherein the second glass layer contains a phosphate compound. 13. A product having a glass layer according to claim 10, wherein the second glass layer contains more potassium and less sodium than the first glass layer. . 14. A water repellent layer containing a water repellent component is formed on the surface side of the second glass layer.
A product having the glass layer according to 0, 11, 12 or 13.