JP2001048595A - Surface treatment of substrate having glass layer and treated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the effective development of an action of a metal such as Ag, Cu and Zn in a surface-treatment of a substrate having a glass layer and provide a product having a glass layer, etc., imparted with excellent surface characteristics and producible with suppressed loss of the metal. SOLUTION: A substrate 15 having a glass layer 12 and a treating agent containing Ag, etc., are prepared beforehand and the glass layer 12 is brought into contact with the treating agent at <100 deg.C to form a treated layer 14. A necessary amount of Ag can be taken into the glass layer 12 by this process by the ion exchange of the alkali metal ion in the layer with anion of Ag, etc. The unnecessary treated layer 14 is optionally removed and the product is heated at a temperature below the glass transition point of the glass layer 12 to effect the impregnation of Ag.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for treating a surface of a substrate having a glass layer, and a product having a glass layer.
This treatment method is suitable for use in imparting an antibacterial function to a treated product comprising a substrate having a glass layer.

[0002]

2. Description of the Related Art For example, metals such as Ag, Cu, and Zn are known to have antibacterial properties. For this reason, conventionally, when manufacturing glass products, ceramic products, or enamel products having an antibacterial function, for example, the entire semi-finished product before imparting the antibacterial function is a glass layer, or the semi-finished product is formed on a substrate. In general, since a glass layer called a glaze layer is provided, an antibacterial agent is generally dispersed in the glass layer at the same time as the production of the base or the formation of the glaze layer.
By dispersing the antibacterial agent in the glass layer in this way, it is possible to impart an antibacterial function to those products at the same time as manufacturing the substrate or forming a glaze layer on the surface of the substrate.

Further, a method has been proposed in which a silver phosphate powder is laminated on the surface of a semi-finished product made of ceramics and then fired (JP-A-6-234585). This method has a feature in that powder is used, and this method can also give a ceramic product an antibacterial function. Furthermore, there has been proposed a method in which a metal layer having antibacterial properties is brought into contact with a glass layer of a semi-finished product made of ceramics, and then heated at a temperature equal to or higher than the glass transition point (Japanese Patent Application Laid-Open No. Hei 8-217492). Gazette). According to this method, the ions in the glass layer and the metal ions can be replaced by ion exchange, whereby the ceramic product can have an antibacterial function.

[0004]

However, when an antibacterial agent is contained in the glass layer by the above-mentioned general method, the antibacterial agent is dispersed evenly over the whole product or has a thickness of about 400 to 500 μm. It will be evenly distributed over the entire thickness of the glaze layer. For example, as shown in FIG. 10, when a glaze layer 202 containing an antibacterial agent 204 is formed on the surface of a ceramic body 200 as a base, the antibacterial agent 204 is dispersed evenly over the entire thickness of the glaze layer 202. Would. In this case, although the antibacterial agent 204 in the glaze layer 202 acts on the bacteria 206 to kill or suppress the growth thereof, the antibacterial agent that truly performs the antibacterial action is the glaze layer 202. Only the antibacterial agent 204 located near the surface. According to the findings of the inventors,
Only the antibacterial agent 204 existing on the very surface layer of about several tens of nm from the surface of the glaze layer 202 actually has an antibacterial effect. For this reason, the antibacterial agent 2 located inside
04 only exists in the glaze layer 202,
No antibacterial effect.

[0005] In other words, for antibacterial purposes, it is sufficient for the antibacterial agent to be present only on the very surface layer of about several tens of nm from the surface of the glass layer, and the antibacterial agent is particularly present in the interior of the glass layer. You don't have to. For this reason, if the antibacterial agent is dispersed throughout the glass layer as in the related art, the antibacterial agent is wasted. Moreover, conventionally,
Since the antibacterial agent was to be dispersed in the glass layer at the same time as the production of the substrate or the formation of the glaze layer, during the melting or firing process for the production of the substrate or the formation of the glaze layer,
Antibacterial agents are likely to evaporate from the surface into the furnace. For this reason, expensive antibacterial agents are wasted, and the concentration of the antibacterial agents is reduced on the most required surface, which makes it difficult to obtain an effective antibacterial effect.

In this respect, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 6-234585 is also the same, since firing is performed after laminating silver phosphate powder. In addition, this method has another disadvantage that energy consumption is large because baking is performed again for antibacterial treatment. Also, Japanese Patent Application Laid-Open No. 8-217
In the case of the method described in Japanese Patent No. 492, since the heat treatment is performed at a temperature higher than the glass transition point, the glass layer is softened when the temperature exceeds the glass transition point. For this reason, when this is cooled and solidified to obtain a product, unreacted metal ions adhere to the surface of the glass layer or are partially incorporated into the glass layer, resulting in waste of metal salts. In addition, there is a disadvantage that the surface properties of the product are deteriorated by unreacted metal ions, and the appearance is impaired. In particular, this is a serious drawback in the case of tiles or the like in which design is important.

[0007] These problems apply not only to the case where a metal having antibacterial properties is incorporated into the glass layer, but also to the case where the metal is incorporated into the glass layer for another purpose. The present invention has been made in view of the above-mentioned conventional circumstances, and relates to a surface treatment method for a substrate having a glass layer and a product having a glass layer, and effectively exerts an action of a metal such as Ag, Cu, and Zn. It is an object of the present invention to make it possible and to make the product have excellent surface properties without causing waste of the metal.

[0008]

The surface treatment method for a substrate having a glass layer according to the present invention comprises preparing a substrate having a glass layer and a treating agent containing a metal, and treating the glass layer at a temperature lower than 100 ° C. The alkali metal ion or the alkaline earth metal ion in the glass layer is ion-exchanged for the metal ion by bringing the treatment agent into contact with the treatment agent.

As the substrate, semi-finished products of glass products, ceramic products or enamel products can be employed.
As ceramic products, tiles, sanitary ware, and the like can be used. Further, the product having a glass layer of the present invention comprises a substrate having a glass layer, and on the surface side of the glass layer, ions of a metal ion-exchanged from alkali metal ions or alkaline earth metal ions in the glass layer. It is characterized by having a metal rich layer containing a high concentration.

According to the test results of the inventors, the alkali metal ion or the alkaline earth metal ion in the glass layer is changed to the metal ion (metal ion) only by bringing the treatment agent into contact with the glass layer of the substrate at a temperature lower than 100 ° C. Hereinafter, it is called a metal ion.)
And the metal ions are taken into the glass layer. The amount of metal ions to be substituted in the glass layer can be determined by adjusting the concentration of the treatment agent, the contact temperature, the contact time, and the like. As a result, the metal ions do not diffuse evenly throughout the glass layer, and a metal-rich layer containing a high concentration of ion-exchanged metal ions is provided on the surface side of the glass layer.

Therefore, there is no useless metal ion inside the metal-rich layer, and the metal ion is not wasted. For this reason, if antibacterial metals such as Ag, Cu, and Zn having antibacterial properties are employed as the metals, the antibacterial metals related to the metal-rich layer on the surface of the glass layer will be contained at a high concentration, and therefore those metals Antimicrobial metals can act on bacteria to kill them or inhibit their proliferation. Further, there is no useless antibacterial metal inside the metal-rich layer, and the antibacterial metal is not wasted.

In the processing method of the present invention, the temperature of 100 ° C.
Contacting the treatment agent with the glass layer at a temperature of less than
The treatment can be performed after the production of the substrate or after the formation of the glaze layer. For this reason, the metal of the treating agent does not volatilize into the furnace from the surface in the course of baking and the like, and
Energy consumption can be suppressed because the treatment is performed at a low temperature of less than 0 ° C.

Further, in the processing method of the present invention, 100 °
Since the treatment is performed at a temperature much lower than the glass transition point of the glass layer of less than C, the glass layer does not soften during the treatment. For this reason, unreacted metal ions do not adhere to the surface of the glass layer on the product after the treatment, and the metal is not wasted, and the surface properties and appearance of the product are maintained.

Therefore, according to the treatment method of the present invention, it is possible to effectively exert the action of the metal, to prevent waste of the metal, and to give the product an excellent surface property. As a treatment agent, metal by vapor deposition,
A metal fine powder, a colloid containing a metal, or a solution in which a metal is dissolved by ions can be used. As the metal, in addition to metals having no antibacterial properties, Ag, Cu,
An antibacterial metal such as Zn can be used. Specifically, organic silver-copper compounds and silver-copper-supported inorganic compounds,
(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, Copper, cuprous oxide, cupric oxide, cupric sulfide, cuprous sulfide, cupric sulfide, copper citrate, copper lactate, and the like can be used. 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, or the like can be used.
These metals may be a simple substance, an alloy, or a compound. However, in the treatment method of the present invention, since ion exchange is performed by contact at a low temperature of less than 100 ° C., in order to shorten the contact time, a colloid having a smaller size of a highly soluble metal and It is preferred to employ a solution. More preferably, a solution of silver nitrate, silver sulfate or the like is used. This is because the size of the metal is larger than the atom in the colloid, whereas the size of the metal is equal to the atom in these solutions. A solution in which such a metal is dissolved by ions can be embodied as a treatment liquid containing metal ions and a solvent. The colloid preferably contains a large amount of metal fine particles, and the solution preferably dissolves metal ions at a high concentration. The treating agent preferably contains a metal or a metal compound at 70% by weight or more. This is because these can shorten the contact time.

In the treatment method of the present invention, when such a solution is employed as a treatment agent, the treatment liquid can be brought into contact with the glass layer at a temperature lower than the boiling point of the solvent. That is, when the solvent is water, the temperature is lower than 100 ° C. If the contact is made at a temperature lower than the boiling point of the solvent, the undried treated layer composed of the treatment liquid is not easily dried, and the excess treated layer can be removed at a high rate. By removing in this manner, unreacted metal ions do not adhere to the surface of the glass layer, etc., on the processed product, so that metal is not wasted, and the surface properties and appearance of the product are maintained. Further, the processing solution after the removal can be reused at a high rate, and the manufacturing cost can be reduced.

If the contact temperature is higher in a range lower than 100 ° C., the contact time can be shortened. For this reason, it is preferable that the treatment agent is brought into contact with the glass layer at a temperature of 15 ° C. or more in consideration of the normal temperature in the factory in winter. Further, it is preferable that the treatment agent is brought into contact with the glass layer at a temperature of 40 ° C. or more in consideration of the residual heat of the firing furnace. Further, it is preferable that the glass layer and / or the treating agent be brought into a temperature equivalent to the treating temperature and the treating agent is brought into contact with the glass layer. If the temperature of the glass layer or the treatment agent is equal to the treatment temperature, there is no heat transfer from one side to the other, and the amount of metal ions substituted in the glass layer determined by the contact time can be kept unchanged. In particular, it is preferable that the glass layer and the treatment agent are brought into a temperature equivalent to the treatment temperature and the treatment agent is brought into contact with the glass layer. When the temperature of the glass layer and the treatment agent is equal to the treatment temperature, heat transfer hardly occurs, and the quality can be stabilized.

After forming an undried processing layer comprising a processing liquid,
It is preferable to remove an excess processing layer. This is because if the processing solution after the removal is reused, the product cost can be reduced. The degree of drying of the treatment layer varies depending on the solvent, the temperature of the glass layer, and the like. In consideration of these points, when the processing layer is difficult to dry, long-term contact is possible, so that a low-concentration processing liquid can be employed. In addition, when the treatment layer is easy to dry, short-time contact is preferable, so that a treatment solution having a high concentration can be employed.

After the contact of the treating agent, it is preferable to heat the glass layer at a temperature lower than the glass transition point of the glass layer so that the metal ions incorporated in the glass layer penetrate into the glass layer. Conventionally, it is considered that the diffusion and permeation of metal ions are integrally performed by heating after contacting fine metal powder or metal salt. For this reason, the total amount of metal ions in the conventional glass layer tends to increase due to the heating time, and the metal ions easily diffuse and penetrate beyond the amount required for antibacterial and the like, resulting in wasteful consumption of metal. Is likely to occur. On the other hand, in the treatment method of the present invention, metal ions taken into the glass layer by ion exchange in an amount required for antibacterial and the like permeate into the glass layer by such heating. Even if heating is performed in this way, if the treatment agent is already removed at that time, the amount of metal ions in the glass layer does not increase as compared to before heating, and the concentration gradient changes. It is thought that it only does. For this reason, it is not necessary to take in and permeate a metal ion more than the amount required for antibacterial and the like, so that wasteful consumption of metal can be prevented. In addition, since the gradient change in the concentration of metal ions occurs slowly in the glass layer, the metal ions do not diffuse evenly throughout the entire glass layer unless the heating is performed for a long time, and the metal ions still remain on the surface side of the glass layer. It is easy to have a metal rich layer. Further, if the treatment agent is removed before heating, blackening due to reduction of the metal contained in the treatment agent during heating and the adhesion of spot-like stains on the glass layer due to the reduction can be prevented.

Since such heating is performed at a relatively low temperature of less than the glass transition point of the glass layer, the metal is less likely to volatilize from the surface, and the presence of the metal-rich layer on the surface can be maintained. Also, energy consumption is small. Furthermore, since the softening of the glass layer does not occur, the surface properties and appearance of the product can be maintained. If the treatment liquid remains on the surface of the glass layer only once after removing the treatment layer, heating the glass layer in that state will stain the surface of the glass layer of the product. Therefore, it is preferable to wash the surface of the glass layer with water or the like before heating.

Preferably, the glass layer is heated at a temperature below 300 ° C., more preferably below 200 ° C., even more preferably below 150 ° C. The reason for this is that if the temperature is lower than 300 ° C., the metal ions easily penetrate sufficiently into the glass layer, and if the temperature is lower than 200 ° C., the metal ions still easily penetrate sufficiently into the glass layer. If the temperature is lower than 150 ° C., the metal ions are still easy to penetrate into the glass layer. This is because no defect is generated.

By heating the glass layer at a temperature lower than the glass transition point of the glass layer after forming the processing layer made of the processing agent, metal ions are taken into and penetrated into the glass layer, and then the processing layer is removed. It is also preferred. This is because if the processing solution after the removal is reused, the product cost can be reduced. It is also preferred that the glass layer of the substrate contains a metal in advance. If this is the case, a metal capable of exhibiting the action of the initial metal by ion exchange performed from the surface side of the glass layer and effectively exerting the action only by ion exchange performed from the surface side of the glass layer can be used. As compared with the case where the metal is taken in, the durability is improved, the amount of metal consumed is reduced, and the manufacturing cost can be reduced.

That is, when the metal is taken into the glass layer only by ion exchange performed from the surface side of the glass layer,
The above-mentioned metal-rich layer will be formed on the surface side of the glass layer. According to the test results of the present inventors, such a metal-rich layer has a concentration that has a peak on the surface side and attenuates inversely to the inner side at the back. For this reason, considering that the wear may progress from the surface to some extent after use, unless a large amount of metal is ion-exchanged to increase the concentration of the metal inside the surface slightly behind the surface side, such a metal-rich layer may be damaged. The effect cannot be effectively exerted only with metal. For this reason, in this case, it is impossible to achieve both improvement in durability and reduction in manufacturing cost.

On the other hand, in the case where metals are contained in the glass layer in advance, according to the test results of the present inventors, the concentrations of those metals are lowest on the surface side and gradually increase toward the inner side at the back. And tends to saturate. For this reason, in this case, even if the wear progresses to some extent from the surface after use, unless the glass layer contains a large amount of metal and the concentration that saturates the glass layer is increased to some extent, the effect is effective only with these metals. Can not be demonstrated. For this reason, in this case, it is difficult to exhibit the action of the metal in the initial stage.

In this regard, if a metal is previously contained in the glass layer and the metal is taken in by ion exchange from the surface side of the glass layer, a metal-rich layer is formed on the surface side of the glass layer, A metal that saturates at approximately the same concentration as that of the metal-rich layer can be included. That is, the glass layer of the base contains metal even inside the metal rich layer. In this case, the metal-rich layer exhibits excellent metal action before wear from the surface immediately after use, and when the wear progresses from the surface to some extent after use, the metal inside is also superior to the metal inside. Will be exerted. For this reason, the action of the metal can be exhibited at the initial stage, and both improvement in durability and reduction in manufacturing cost can be achieved.

In this way, when the metal is previously contained in the glass layer and the metal is taken in by ion exchange from the surface side of the glass layer, it is unavoidable to include the metal in the entire glass layer of the substrate in advance to some extent. Although not
Not only can the entire glass layer be ion-exchanged from the surface side to take in the metal, but also the metal layer can be ion-exchanged from the surface side only at the part of the glass layer where the action of the metal is required more strongly. it can. In the case of using an antibacterial metal, the antibacterial metal is contained in the entire glass layer of the base in advance, and a portion where water flows from a water sealing portion or a rim of a toilet, etc.
The metal can be taken in by ion-exchange from the surface side only at the site that comes into contact with water.

If the antibacterial metal previously added to the glaze constituting the glass layer is adopted as the metal in the glass layer, the antimicrobial action is more excellently exhibited by the metal-rich layer immediately before use and before abrasion from the surface. When the wear progresses from the surface to some extent after use, the excellent antibacterial action is also exhibited by the internal antibacterial metal. For this reason, the action of the antibacterial metal can be exhibited at the initial stage, and both improvement in durability and reduction in manufacturing cost can be achieved.

When an antibacterial metal is contained in the glass layer by the antibacterial agent, the antibacterial agent is contained in the glaze at 0.05 to 10% by weight.
Is preferably contained at a ratio of As a result, the antibacterial agent is placed inside the glass layer deeper than the metal rich layer by 0.05%.
To 10% by weight. According to the test results of the inventors, the antibacterial action is practical within such a range.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention can be implemented as follows. In the embodiment, as shown in FIG. 1, the present invention is embodied in a base material 15 of a semi-finished ceramic product having a glass layer 12 called a glaze layer on the surface of a substrate 10. First, FIG.
As shown in (I), a treatment agent is applied to the surface of the glass layer 12 to form a treatment layer 14.

When a metal powder is used as the treating agent, the metal powder may be present together with a surfactant, and sprayed onto the surface of the glass layer 12 by a nozzle 16 as shown in FIG. Further, as shown in FIG. 2B, a method in which the treatment agent 18 is put into a sieve 20 and the partition plate 24 is retracted to apply the treatment agent 18 from the mesh 22 of the sieve 20 to the surface of the glass layer 12 may be adopted. it can. In this case, as shown in FIGS. 2B and 2I, the treating agent 18 is sprinkled on the surface of the glass layer 12, and as shown in FIGS. When the predetermined amount is reached, the mesh 22 is closed by the partition plate 24, so that the treatment agent 18 does not fall from the mesh 22. Further, it is also possible to use an electrostatic coating (adhesion) method or another method.

On the other hand, when a liquid processing agent is applied, as shown in FIG.
Can be sprayed on the surface. Further, a dipping method (dipping) in which the entire body including the base 15 is immersed in the treatment agent may be employed. Further, it is also possible to employ a curtaining method in which the treatment agent is suspended in a screen shape and the substrate 15 passes through the treatment agent. Further, a method of generating a mist of the treatment agent by ultrasonic waves and attaching the mist to the glass layer 12 can also be adopted.

Thus, the metal ions in the treatment layer 14 are taken into the glass layer 12. As shown in FIG. 1 (I), after forming an undried processing layer 14 made of a processing liquid, or as shown in FIG.
After heating the glass layer 12 at a temperature lower than the glass transition point of the glass layer as shown in (II), the treatment layer 14 can be removed by an appropriate method as shown in FIG. 1 (III).

In order to remove the processing layer 14 on the glass layer 12, for example, as shown in FIG.
Means for wiping or scraping off. In addition, as shown in FIG. 3B, a means for spraying water, air, or the like from the nozzle 26 with vigor and blowing it off may be employed. Further, as shown in FIG. 3C, a means for immersing the entire body including the base 15 in a liquid 28 such as water can be adopted. The removed treatment layer 14 can be collected and reused. In the case of the means shown in FIGS. 3A, 3B and 3C, the removed treatment layer 14 can be easily collected and reused.

When the glass layer is heated at a temperature lower than the glass transition point of the glass layer, as shown in FIG.
Alternatively, it is possible to employ a method in which the substrate 10 and the glass layer 12 are fired in a firing furnace 30 such as a tunnel kiln or a roller hearth kiln, and are then carried into a heating furnace 32 that is continuous with the firing. In addition, after firing in the firing furnace 30, it is also possible to adopt a means for cooling the firing once and then carrying it into the heating furnace 32. That is, heating can be performed in the heating furnace 32 discontinuously from firing in the firing furnace 30.

When the heating is performed in a continuous manner, as shown in FIG. 5, first, the base 15 is baked (for example, baked at 1200 ° C.) while being moved in the sintering furnace 30. And
In the baking furnace 30 or outside the baking furnace 30, for example, 100
After cooling to about ° C, the surface of the glass layer 12 of the substrate 15 is then brought into contact with a treatment agent made of, for example, a silver compound to form a treatment layer 14. Here, the extra processing layer 14
Can be removed. Next, the heating furnace 32 is continuously
This is carried in, moved, and heated at a predetermined heating temperature for a predetermined time. At this time, while spraying,
Alternatively, the silver compound can be brought into contact and heated while moving in the sealed heating furnace 32 in which mist is generated for a predetermined time. If the unnecessary processing layer 14 is not removed after the processing layer 14 is formed, the unnecessary processing layer 14 can be removed when the processing layer 14 is removed from the heating furnace 32. When processing is performed on the substrate 15 that has already been baked, the processing layer 14 is brought into contact with the substrate 15, an unnecessary processing layer 14 is removed if necessary, and the substrate 15 is carried into the heating furnace 32. Then, when the processing layer 14 is not removed after the processing layer 14 is formed, the processing layer 14 is removed when the processing layer 14 is removed from the heating furnace 32.

On the other hand, when the heating is performed in a batch system, FIG.
As shown in (I), first, a fixed amount of the base 15 is collectively inserted into the firing furnace 30, and then, as shown in FIG. 6 (II), the base 15 is fired in a state where the entrance and exit furnace lids are closed ( For example, firing at 1200 ° C.). Then, FIG. 6 (III)
As shown in FIG. 6, when this is cooled to, for example, about 100 ° C., as shown in FIG. 6 (IV), a treatment agent made of, for example, a silver compound is brought into contact with the surface of the glass layer 12 of the base member 15 to form Form. Here, the extra processing layer 14 can be removed. Then, as shown in FIG. 6 (V), the heating furnace 32 is held at a predetermined heating temperature for a predetermined time,
Perform heating. Then, as shown in FIG. 6 (VI), when the heating is completed, the product is taken out. Thereafter, FIG.
As shown in II), when the extra processing layer 14 is not removed after the formation of the processing layer 14, the extra processing layer 14 is removed.

The above is only an example of one processing, and it is of course possible to perform processing by another method.

[0037]

Embodiment 1 Next, Embodiment 1 of the present invention will be described in detail. FIG.
As shown in (A), a substrate 1 made of ceramic having the following composition
Glass layer (glaze layer) consisting of glaze of the following composition on the surface of 0
A substrate 15 having 12 is prepared. The glass transition point of the glass layer 12 is 700 ° C.

On the surface of the glass layer 12 of the substrate 15, Ag ₃ PO ₄ fine powder (average particle size: 0.3 μm) was used as a treating agent.
3 μm) are laminated with a thickness of 0.3 mm to form the treatment layer 14. <Mixing ratio of base 10 (% by weight)> Feldspar: 28.2 Silica sand: 11.8 Sericite: 15.0 Clay: 45.0 <Mixing ratio of glaze (% by weight)> Feldspar: 53.7 Silica sand: 9 8.8 Lime: 12.3 Dolomite: 4.8 Frog: 5.1 Zinc flower: 2.0 Zircon: 10.1 Frit: 2.2 And these were added at 200 ° C. × 2 hours (sample A), 15
Heating is performed under the conditions of 0 ° C. × 2 hours (sample B), 15 ° C. × 2 hours (sample C), or 4 ° C. × 2 hours (sample D).

An aqueous solution containing 3.0% by weight of AgNO ₃ was prepared as a treatment liquid, and this treatment liquid was applied to the surface of the glass layer 12 of the same type of substrate 15 as shown in FIG. 001 g / cm ² is applied to form a treatment layer 14. Then, these were subjected to the conditions of 200 ° C. × 2 hours (sample E), 150 ° C. × 2 hours (sample F), 15 ° C. × 2 hours (sample G) or 4 ° C. × 2 hours (sample H). Heat.

Thereafter, the treated layer 14 on the glass layer 12 was removed, and then subjected to an antibacterial test by a film adhesion method. The antibacterial test and evaluation were performed as follows. <Test method> Culture of test bacteria: (1) Transfer the test bacteria in NA medium (normal agar medium),
Culture at a temperature of 35 to 37 ° C for 16 to 24 hours (pre-culture)
did.

(2) The bacterium pre-cultured in (1) above is subjected to NA
One platinum loop was transplanted to the medium, and the temperature was 35 to 37 ° C and 16 to 2
The cells were cultured for 0 hours (pre-culture). Preparation of bacterial solution for inoculation: NB medium (normal broth medium) was diluted 500-fold with phosphate buffer to adjust the pH to 7.0 ± 0.2.
The 1/500 NB medium prepared above was used, and the pre-cultured bacteria were uniformly dispersed therein to obtain a bacterial solution for inoculation.

Preparation of test pieces: (1) The above test samples A to H were placed in a 50 ± 2 mm square (thickness 10
(within mm), and gently wipe the entire surface 2-3 times with ethanol-soaked gauze or absorbent cotton before drying (pre-treatment). Three samples were prepared for each, and used as antibacterial processed test pieces.

(2) As a comparative sample, a non-processed sample in which the above-mentioned silver compound was not applied and heated was prepared, cut into the same size as the test sample in (1), and processed similarly to the antibacterial processed test piece. Preprocess. Three of these were prepared and used as unprocessed test pieces. Test operation: (1) Antibacterial processed test piece (3 pieces) and non-processed test piece (3
) Were placed in a sterile petri dish, and the test surface was inoculated with 0.4 ml (including 1.0 to 5.0 × 10 ⁵ bacteria) of the inoculum solution, covered with a covering film, and covered. After that, it was stored under conditions of a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more.

(2) Three sterile petri dishes were prepared for the control plot, 0.4 ml of the inoculum was inoculated on the underlaying film placed on each, and a cover film was placed on top of the inoculated bacterial solution and covered. Thereafter, it was stored under the conditions of a temperature of 35 ± 1 ° C. and a relative humidity of 90% or more. Measurement of viable cell count: (1) Prepare three sterile Petri dishes, add the same amount of bacterial liquid for inoculation as inoculated to each test piece, and cover with a coating film. Thereafter, the SCDLP medium (10 m
Immediately in step (1), the bacteria adhering to the coating film are sufficiently washed out into a Petri dish. Agar plate culture method using SA medium (standard agar medium) (temperature: 35 ± 1 ° C)
), The number of viable bacteria in 1 ml of the washed solution was measured, the average value of the three viable cell counts ("control group immediately after inoculation") was determined, and the value obtained by multiplying the average value by A was 10 times. And

The dilution at the time of measuring the number of viable cells was performed using sterile phosphate buffered saline. (2) Sterile Petri dish for control 24 hours after storage (3 pieces)
, The average of three viable cell counts (“control”) measured in the same manner as in the sterilized petri dish described above was determined, and the value obtained by multiplying the average by 10 was designated as B. (3) With respect to the unprocessed test pieces (3 pieces) 24 hours after storage, the bacteria adhering to each of the test piece and the coating film are sufficiently washed out in a sterilized petri dish using the SCDLP medium (10 ml). The number of viable bacteria in 1 ml of the washed liquid was measured by an agar plate culture method using SA medium (cultured at a temperature of 35 ± 1 ° C. for 40 to 48 hours). The average value of “ku” was determined, and a value obtained by multiplying the average value by 10 was designated as C.

(4) The average value of three viable cell counts ("antimicrobial processing test section") of the three antimicrobial processed test pieces 24 hours after storage was measured in the same manner as the non-processed test pieces. Then, a value obtained by multiplying it by 10 was designated as D. <Display of test results>"Difference in increase / decrease value" was calculated by the following equation. The second digit after the decimal point was truncated.

{Log (C / A) -log (D / A)}
= {Log (C / D)} <Test Successful Condition> When all of the following four conditions are satisfied, the test is considered valid. (1) For each of the three viable cell counts in the “control section immediately after inoculation” and the “control section”, calculate using the following formula, and the calculated value is 0.2 or less.

(Highest log value−lowest log value) / (log mean value) ≦ 0.2 (2) B for A (average value of “control group immediately after joining”)
(Average value of “control”) 90% or less. {(AB) / A} × 100 ≦ 90 (3) For each of the three viable cell counts in the “control group immediately after inoculation”,
Their average value is in the range of 1.0 to 5.0 × 10 ⁵ / sheet.

(4) The viable cell count of each of the three non-processed test plots is 1.0 × 10 ³ / sheet or more. <Test strain> (1) Staphylococcus aureus IFO12732 (AT
CC6538P) (2) Escherichia coil IFO3972 (ATCC8
739) <Test preparation> Instruments, equipment and materials: (1) Pipette (milk pipette, 1 ml and 10 ml)
(2) thermostat (model that can be operated with accuracy within ± 1 ° C) (3) desiccator (4) sterile petri dish (inner diameter 80mm-100mm, height 15mm- (5) Coated film (a plastic bag for “Stromacker 400” commercially available for microbial testing (organo: 180
mm x 300 mm x 0.09 mm)
(6) Underlay film (made by cutting a coated film into a size of 50 mm square or more) Medium etc .: (1) Normal puyon medium (NB medium) Meat extract: 0 g Peptone: 10.0 g Sodium chloride: 5.0 g Purified water: 1,000 ml pH: 7.0-7.2 (2) Normal agar medium (NA medium) 1.5% of agar was added to NB medium (1) (3) Standard agar medium (SA medium) Yeast extract: 2.5 g Tryptone: 5.0 g Glucose: 1.0 g Agar: 15.0 g Purified water: 1,000 ml pH: 7.1 ± 0.1 (4 ) SCDLP medium Peptone made of casein: 17.0 g Peptone made of soybean: 3.0 g Sodium chloride: 5.0 g Potassium hydrogen phosphate: 2.5 g Glucose: 2.5 g Lecithin: 1.0 g Polysorbet 80: 7.0 g Purified water: l, 000ml pH: 6.8~7.2 ( 5) ethanol (purity 99%) (7) dissolved in purified water 500ml phosphate buffered saline KH ₂ PO ₄ 34g And 1NN
After the pH was adjusted to 7.2 with aOH, purified water was added to add 1000
ml. 1.25 ml of this solution was added to a physiological saline solution (0.
(800% with 85% NaCl) to make 1000 ml.

<Evaluation> Table 1 shows the results of the antibacterial test of the samples A to D by the film adhesion method. Table 2 shows the results of the difference between the increase and decrease values of the test subjects A to D. Table 3 shows the results of the antibacterial test of the samples E to H by the film adhesion method. Table 4 shows the results of the difference between the increase and decrease values of the samples E to H. An increase / decrease value difference of 2.0 or more was judged to have antibacterial activity. Note that <10 indicates that detection is not possible.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

Tables 1 to 4 show that the samples heated at a temperature of 15 to 200 ° C. (samples A to C and EG) have excellent antibacterial ability. This is because A
The g ions are taken into the glass layer 12 and the Ag ions have penetrated by heating, and the Ag ions are contained in a higher concentration nearer to the surface of the glass layer 12, which is an effect of having an Ag rich layer. .

The Ag concentration in the glass layer 12 of the sample A was measured by secondary ion mass spectrometry, and the depth (nm) from the surface and the concentration index (Intensity (C)
ounts)) and sought a relationship. FIG. 8 shows the results. In the figure, A indicates the measurement result of Sample A. Also, X
Shows the measurement results of a product which was glazed on the substrate 10 with a glaze containing Ag ₃ PO ₄ as an antibacterial agent according to the conventional method, and then fired.

FIG. 8 shows that in the case of X according to the conventional method, the concentration of Ag is lower as the surface is closer to the surface of the glass layer 12. On the other hand, in the case of the sample A according to the first embodiment, the Ag ions are taken in and further penetrated in spite of heating at a low temperature, and the higher the Ag ions are, the closer to the surface of the glass layer 12. Concentration, A
It turns out that it has a g-rich layer.

[0058]

Second Embodiment Next, a second embodiment of the present invention will be described in detail. As in Example 1, an aqueous solution containing 0.01% by weight, 2% by weight, 10% by weight, 70% by weight or 80% by weight and containing AgNO ₃ is prepared as a treatment liquid. And 4 ° C, 10
FIG. 7 under a contact temperature of 30 ° C., 30 ° C. or 50 ° C.
As shown in (B), this treatment liquid is applied at a rate of 0.001 g / cm ² on the surface of the glass layer 12 of the same kind of substrate 15 to form an undried treatment layer 14.

Thereafter, the excess treatment layer 14 is removed under a contact time of 1 second, 10 seconds, 1 minute, 3 minutes, or 10 minutes, and these are heated at 100 ° C. for 30 seconds. . Tables 5 and 6 show the results of the antibacterial test. Table 5 shows the results with E. coli, and Table 6 shows the results with S. aureus.

[0060]

[Table 5]

[0061]

[Table 6]

As shown in Tables 5 and 6, Ag was found to be 70% by weight or more.
If an aqueous solution containing NO ₃ is used as the treatment liquid, for example, 4 ° C.
Ag ions are in contact with the glass layer 12
It turns out that it is taken in. In particular, the longer the contact time, the greater the tendency. Further, it can be seen that the contact time can be shortened if the contact temperature is higher in a range lower than 100 ° C., which is the boiling point of water as a solvent.

Further, according to Tables 5 and 6, after contact, 100
If the heating is performed under the condition of ° C. × 30 seconds, even if the treatment layer 14 is removed after the contact time of 1 second, it is understood that it has excellent antibacterial ability. This is because the required amount of Ag ions is taken into the glass layer 12 by contact with the processing liquid and further penetrated by heating, and the Ag ions are contained in a higher concentration as the surface of the glass layer 12 is closer to the surface. This is the effect of having a rich layer.

When the concentration of AgNO _{3 in} the processing solution is 2% by weight,
The contact temperature is 30 ° C, the contact time is 1 minute, and 1
A sample heated at 00 ° C. for 30 seconds and A in the processing solution
The concentration of gNO ₃ was 70% by weight, the contact temperature was 30 ° C., the contact time was 1 second, and the sample was heated at 100 ° C. for 30 seconds after the contact. The amount (atom%) was measured by X-ray photoelectron spectroscopy (XPS). Here, in the XPS method, the surface of the glass layer 12 of the sample placed in an ultra-vacuum is irradiated with focused soft X-rays that are separated by a curved single crystal, photoelectrons emitted from the surface are detected by an analyzer, and the information is analyzed by element analysis. This method is used for the determination of Table 7 shows the results for the sample having the AgNO ₃ concentration of 2% by weight, and Table 8 shows the results for the sample having the AgNO ₃ concentration of 70% by weight.

[0065]

[Table 7]

[0066]

[Table 8]

From Table 7, it can be seen that the glass layer 12 of the sample has more Ag ions on the surface side as compared to the inside, and conversely the K is extremely smaller than Na ions. For this reason, it can be seen that the ion exchange occurred mainly between K ions and Ag ions having mutually close ionic radii. Therefore,
It can be seen that K ions in the glass layer 12 of the substrate 15 are ion-exchanged into Ag ions by the contact of the treatment agent and are taken in, and further, the Ag ions penetrate into the glass layer 12 by heating.

From Table 8, it can be seen that the concentration of AgNO ₃ was 70%.
When a processing solution having a high concentration of 1% by weight is used, the contact time is 1
It can be seen that even in the case of seconds, substantially the same amount of Ag ions can permeate into the glass layer 12 as compared with the case where the processing solution having a low concentration of AgNO ₃ of 2% by weight is used.

[0069]

[Test 1] First, the glaze of Example 1 and silver powder (99% or more silver, average particle size 10 μm) as an antibacterial agent were prepared, and the antibacterial agent was contained in the glaze at 0.01% by weight and 0.05%. %, 0.1%, 0.5%, 1.0%, 1%
0.05% by weight, which is glazed on the base material 10 and subsequently fired to produce a product. With respect to the glass layer 12 of each of the obtained samples, a difference between increase and decrease values due to Escherichia coli (E. coli) and S. aureus was determined. As in Table 2, etc.
Table 9 shows the results.

[0070]

[Table 9]

The difference between the increase and decrease before polishing was compared with the difference between the increase and decrease after polishing the surface of the glass layer 12 of each sample by 0.1 μm. As in Table 2 and the like, the results are shown in Tables 10 and 11. Table 10 shows the results with E. coli, and Table 11 shows the results with S. aureus.

[0072]

[Table 10]

[0073]

[Table 11]

As can be seen from Tables 9 to 11, when the antibacterial metal is contained in the glass layer 12 in advance, it is difficult to effectively exert the action of the antibacterial metal unless abrasion proceeds from the surface to some extent. . That is, in this case, it is understood that the action of the antibacterial metal is hardly exhibited at the initial stage. This is because, when the antibacterial metal is contained in the glass layer 12 in advance, the concentration of the antibacterial metal is lowest on the surface side, gradually increases toward the inner side at the back, and tends to be saturated. It is.

[0075]

[Test 2] Further, the glaze of Example 1 and silver powder (99% or more of silver, average particle size of 10 μm) as an antibacterial agent were prepared. %, 0.1%, 0.5%, 1.0%, 1%
0.05% by weight, which is glazed on the base material 10 and subsequently fired to produce a product.

The same type of Ag ₃ PO ₄ fine powder as in Example 1 is laminated on the surface of the glass layer 12 of each of the obtained samples at a thickness of 0.3 mm to form a treatment layer 14. And these are 20
0 ° C × 2 hours (heating condition a), 150 ° C × 2 hours (heating condition b), 15 ° C × 2 hours (heating condition c) or 4 ° C × 2 hours (heating condition d) Heat.

Thereafter, the treated layer 14 on the glass layer 12 was removed, and the difference between the increase and decrease before polishing and the difference between after and after polishing the surface by 0.1 μm were compared. As in Table 2, etc., the results are shown in Table 1.
2 to Table 15. Tables 12 and 13 show E. coli (E.
Table 14 and Table 15 show the results with S. aureus. Tables 12 and 14 show results under heating conditions a to c, and Tables 13 and 15 show results under heating conditions d.

[0078]

[Table 12]

[0079]

[Table 13]

[0080]

[Table 14]

[0081]

[Table 15]

[0082]

[Test 3] Further, the glaze of the above-mentioned Example 1 and silver powder (99% or more of silver, average particle size of 10 μm) as an antibacterial agent were prepared, and the antibacterial agent was 0.01% by weight and 0.05% in the glaze. %, 0.1%, 0.5%, 1.0%, 1%
0.05% by weight, which is glazed on the base material 10 and subsequently fired to produce a product.

An aqueous solution (treatment liquid) containing 3.0% by weight of AgNO ₃ of the same kind as in Example 1 was prepared, and the surface of the glass layer 12 of each of the obtained samples was coated with 0.001 g / c of this treatment liquid.
m ² to form a treatment layer 14. Then, these were heated at 200 ° C. × 2 hours (heating condition a), at 150 ° C. × 2
Time (heating condition b), 15 ° C x 2 hours (heating condition c)
Alternatively, heating is performed under the condition of 4 ° C. × 2 hours (heating condition d).

Thereafter, the treated layer 14 on the glass layer 12 was removed, and the difference between before and after the polishing and the difference after the surface was polished by 0.1 μm were compared. As in Table 2, etc., the results are shown in Table 1.
6 to Table 19. Tables 16 and 17 show E. coli (E.col).
Table 18 and Table 19 show the results with S. aureus. Tables 16 and 18 show the results under heating conditions a to c, and Tables 17 and 19 show the results under heating condition d.

[0085]

[Table 16]

[0086]

[Table 17]

[0087]

[Table 18]

[0088]

[Table 19]

From Tables 12 to 19, it can be seen that under the heating conditions a to c, the antibacterial effect appears before polishing, regardless of the amount of the antibacterial agent added in the glaze. This is due to the Ag-rich layer formed on the surface of the glass layer 12. Also,
After the polishing of 0.1 μm, the antibacterial effect appears when the amount of the antibacterial agent in the glaze is 0.05 wt% or more. The only reason that the antibacterial agent had an antibacterial effect even after the polishing of 0.1 μm by adding the antibacterial agent to the glaze was that the amount of the antibacterial agent added was 0.
It is the case of 1 wt% or more. This is because Ag ions are diffused into the glass layer 12 by the process of taking Ag ions into the glass layer 12 under heating conditions.
This is because the internal antibacterial effect has increased.

In the method in which silver powder is only added to the glaze, it is necessary that the addition amount is 0.5 wt or more for a sufficient antibacterial effect. However, when silver powder is added to the glaze and Ag ions are diffused from the surface of the glass layer 12, the amount of silver powder in the glaze is reduced to 0.1.
Even if the content is 05 wt%, the antibacterial effect on the surface is increased, and the high antibacterial effect can be exhibited even after polishing the surface by 100 nm. Therefore, by adding an antibacterial agent to the glaze and diffusing antibacterial metal ions from the surface of the glass layer 12, the amount of the antibacterial agent used for a sufficient antibacterial effect can be suppressed to about 1/10. Understand.

Therefore, when an antibacterial metal is contained in the glass layer 12 by the antibacterial agent, the antibacterial agent is added to the glaze at 0.1%.
If it is contained at a ratio of from 0.05 to 10% by weight, it can be said that a sufficient antibacterial effect is exhibited even in consideration of polishing in actual use.

[0092]

Third Embodiment Next, a third embodiment of the present invention will be described in detail. 0.01% by weight of antibacterial agent in glaze
0.05% by weight, 0.1% by weight, 0.5% by weight, 1.0%
% By weight and 10.0% by weight, which is glazed on the substrate 10 and subsequently fired.

Also, as in Example 2, 0.01% by weight, 2% by weight, 10% by weight, 70% by weight or 80% by weight
, An aqueous solution containing AgNO ₃ is prepared as a treatment liquid. And 4 ° C, 10 ° C, 30 ° C or 50 ° C
The glass layer 1 on the substrate 15 after firing under the contact temperature of
This treatment liquid is applied to the surface of No. ² at a rate of 0.001 g / cm ² to form an undried treatment layer 14.

Thereafter, the excess treatment layer 14 is removed under a contact time of 1 second, and these are heated under conditions of 100 ° C. × 30 seconds. Thereafter, Table 20 and Table 21 show deviations of increase and decrease after polishing the surface by 0.1 μm. Table 20 shows E. coli, and Table 21 shows S. aureus.
The results are shown in FIG.

The antibacterial effects before and after polishing the glaze surface are compared. Tables 5 and 6 for antibacterial effect before polishing
Indicates that no antibacterial agent is contained in the glaze, but before the polishing (unpolished), the antibacterial effect appears when the contact temperature is 10 ° C. or higher. This is due to the Ag-rich layer formed on the surface of the glass layer 12. From this, it can be said that the antibacterial effect appears in an arbitrary amount before the polishing (unpolished), including the antibacterial agent contained in the glaze even if the amount is zero.

Further, after polishing with 0.1 μm, Table 20 was obtained.
According to Table 21 and Table 21, the antibacterial effect in the glaze is 0.05% by weight or more and the contact temperature is 10 ° C or more. 0.1μm just by adding antibacterial agent to glaze
The antibacterial effect after polishing was that the amount of antibacterial agent added was 0.1%.
It is the case of 1% by weight or more. This is because the Ag ions are diffused into the glass layer 12 by the process in which the Ag ions are taken into the glass layer 12 under the heating condition, so that the antibacterial effect inside the glass layer 12 is enhanced.

[0097]

[Table 20]

[0098]

[Table 21]

[0099]

[Test 4] Sample 1 in which Ag was incorporated into glass layer 12 only by ion exchange performed from the surface side of glass layer 12, and Sample 2 in which Ag was previously contained in glass layer 12
And while preliminarily including Ag in the glass layer 12,
By performing ion exchange from the surface side of the glass layer 12, Ag
Ag in the glass layer 12 with respect to the sample 3 in which
The concentration was measured by secondary ion mass spectrometry, and the depth (nm) from the surface and the concentration index (Intensity (Count)
s)). FIG. 9 shows the results.

From the sample 1 in FIG. 9, when Ag is introduced into the glass layer 12 only by ion exchange performed from the surface side of the glass layer 12, an Ag-rich layer may be formed on the surface side of the glass layer 12. Understand. Such an Ag-rich layer is
It has a peak on the surface side and a concentration that attenuates inversely toward the inner side at the back. For this reason, considering that wear may progress from the surface to some extent after use, unless a large amount of Ag is ion-exchanged to increase the concentration of Ag inside the surface slightly behind the surface side, the Ag-rich layer may have a large thickness. The effect cannot be exhibited effectively only with Ag.
Therefore, in this case, it can be seen that it is impossible to achieve both improvement in durability and reduction in manufacturing cost.

On the other hand, from the sample 2 in FIG. 9, when Ag is contained in the glass layer 12 in advance, the concentration of those Ag is the lowest on the surface side and gradually increases toward the inner side at the back. It can be seen that they tend to be saturated. For this reason, in this case, in the case where the wear progresses from the surface to some extent after use, unless the glass layer 12 contains a large amount of Ag and the concentration that saturates the glass layer 12 is increased to some extent, the effect of the Ag alone is effective. Can not be effectively demonstrated. For this reason, in this case, it is understood that the function of the metal is hardly exhibited at the initial stage.

In this regard, from the sample 3 in FIG.
To the glass layer 12 in advance.
It can be understood that if the Ag is taken in by ion exchange from the surface side of the glass layer, an Ag-rich layer is formed on the surface side of the glass layer 12 and Ag that saturates at the same concentration as that of the Ag-rich layer can be included. . That is, the glass layer 12 of the base 15 also contains Ag in the interior deeper than the Ag-rich layer. In this case, the Ag-rich layer exerts an excellent antibacterial action before wear from the surface immediately after use,
It can be seen that when the wear progresses from the surface to some extent after use, excellent antibacterial action is also exhibited by the Ag inside. Therefore, if this is the case, Ag
It can be seen that the effect of (1) can be exerted, and that both improvement in durability and reduction in manufacturing cost can be achieved.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an embodiment of the present invention.

FIG. 2 is a view showing an example of a method for forming a processing layer in the embodiment.

FIG. 3 is an explanatory diagram of a method of removing a processing layer according to the first embodiment.

FIG. 4 is an explanatory diagram of a heating method in the embodiment.

FIG. 5 is a diagram showing an example in which the heating method of FIG. 4 is further embodied.

FIG. 6 is a view showing still another specific example of the heating method of FIG. 4;

FIG. 7 is an explanatory diagram of one embodiment of the present invention.

FIG. 8 is a view showing a measurement result of a concentration of Ag in a glass layer obtained in the same example.

FIG. 9 is a view showing a measurement result of a concentration of Ag in a glass layer obtained in the same example.

FIG. 10 is an explanatory diagram for explaining the background of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Base material 12 ... Glass layer (glaze layer) 14 ... Processing layer 15 ... Substrate 18 ... Processing agent, processing liquid

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Miyamoto 5-1-1 Koie Honcho, Tokoname-shi, Aichi Prefecture Inside Inax Corporation (72) Inventor Shin Shin Matsumoto 5-1-1 Koie Honcho, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Shinji Ito 5-1-1 Koiehoncho, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Takahiro Morita 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Noriyuki Sugiyama 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Shozo Yamamoto 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Akito Suzuki Tokoname Suzuki 5-1-1 Koie Honcho, Ichiichi Inax Co., Ltd. (72) Inventor Kazuhiko Hattori Tokoname, Aichi Prefecture 5-1-1 Emotocho Inax Co., Ltd. (72) Inventor Shungo Tokushima 5-1-1 Koiehoncho, Tokoname-shi, Aichi F-term in Inax Co., Ltd. 4G059 AA01 AC30 HB02 HB12 HB17 HB18 4H011 AA02 BA01 BB18 BC18 DA01 DC10

Claims (19)

[Claims] An alkali metal ion in the glass layer is prepared by preparing a substrate having a glass layer and a treatment agent containing a metal and bringing the treatment agent into contact with the glass layer at a temperature of less than 100 ° C. Alternatively, a surface treatment method for a substrate having a glass layer, wherein the alkaline earth metal ion is ion-exchanged for the metal ion. 2. The method for treating a surface of a substrate having a glass layer according to claim 1, wherein the treatment agent is brought into contact with the glass layer at a temperature of 15 ° C. or higher. 3. The surface treatment method for a substrate having a glass layer according to claim 2, wherein the treatment agent is brought into contact with the glass layer at a temperature of 40 ° C. or higher. 4. The substrate having a glass layer according to claim 1, wherein the glass layer and / or the treating agent are brought into a temperature equivalent to the treating temperature and the treating agent is brought into contact with the glass layer. Surface treatment method. 5. The method for treating a surface of a substrate having a glass layer according to claim 1, wherein the metal has antibacterial properties. 6. The processing agent according to claim 1, wherein the processing agent is a processing solution containing a metal ion and a solvent.
A surface treatment method for a substrate having the glass layer described above. 7. The surface treatment method for a substrate having a glass layer according to claim 6, wherein the treatment liquid is brought into contact with the glass layer at a temperature lower than the boiling point of the solvent. 8. After forming an undried processing layer comprising a processing liquid,
8. The method for treating a surface of a substrate having a glass layer according to claim 7, wherein the excess treatment layer is removed. 9. The method according to claim 1, wherein after the contacting of the treating agent, the glass layer is heated at a temperature lower than the glass transition point of the glass layer, so that the ions of the metal taken in the glass layer penetrate into the glass layer. Claim 1, 2, 3, 4, 5, 6, 7, or 8
A surface treatment method for a substrate having the glass layer described above. 10. After forming a treatment layer comprising a treatment agent, the glass layer is heated at a temperature lower than the glass transition point of the glass layer to take in and permeate the ions of the metal into the glass layer. The surface treatment method for a substrate having a glass layer according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the treatment layer is removed. 11. The method for surface treatment of a substrate having a glass layer according to claim 9, wherein the glass layer is heated at a temperature lower than 300 ° C. 12. The method for treating a surface of a substrate having a glass layer according to claim 11, wherein the glass layer is heated at a temperature lower than 200 ° C. 13. The method for treating a surface of a substrate having a glass layer according to claim 12, wherein the glass layer is heated at a temperature of less than 150 ° C. 14. The substrate according to claim 1, wherein the substrate is a semi-finished product of a glass product, a ceramic product or an enamel product.
14. A surface treatment method for a substrate having a glass layer according to 12 or 13. 15. The glass substrate according to claim 1, wherein the glass layer contains a metal in advance.
A method for treating a surface of a substrate having a glass layer according to 9, 10, 11, 12, 13 or 14. 16. The surface treatment of a substrate having a glass layer according to claim 15, wherein the metal in the glass layer has an antibacterial property previously added to the glaze constituting the glass layer. Method. 17. A metal comprising a substrate having a glass layer, and a metal containing, at a high concentration, ions of a metal ion-exchanged from an alkali metal ion or an alkaline earth metal ion in the glass layer on the surface side of the glass layer. Products with a glass layer characterized by having a rich layer. 18. The product having a glass layer according to claim 18, wherein the glass layer of the substrate further includes a metal inside the metal rich layer. 19. The product having a glass layer according to claim 19, wherein the metal-rich layer and the metal inside have an antibacterial property.