JP2001261379A - Product having glass layer and method of judging the product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensively producible product capable of exhibiting an excellent antimicrobial action. SOLUTION: In this product comprising a substrate 15 having a glass layer 12, the glass layer 12 has a rich layer 13 containing Ag in a high concentration on the surface side and the Ag concentration of the rich layer 3 is highest on the surface side and is gradually decreased in the depth direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a product having a glass layer such as a glass product, a ceramic product or a porcelain product exhibiting an antibacterial action, and a method for judging the product.

[0002]

2. Description of the Related Art For example, antibacterial metals such as Ag, Cu, and Zn are known to have antibacterial properties. Therefore, conventionally, for example, when manufacturing glass products, ceramic products, or enamel products exhibiting an antibacterial action, the entire semi-finished product before imparting the antibacterial action is a glass layer, or the semi-finished product is formed on a substrate. In general, an antibacterial agent containing an antibacterial metal is dispersed in a glass layer at the same time as manufacturing a substrate or forming a glaze layer.

In the thus obtained product having a glass layer, the antibacterial agent in the glass layer acts on bacteria, kills the bacteria, or suppresses the propagation thereof.

[0004]

However, in the above-mentioned products having a general glass layer, antibacterial action against bacteria on the surface of the glass layer is originally desired, but the product is dispersed in the glass layer. It became clear that the effect was low unless the concentration of the antibacterial agent was increased. For this reason, it was found that a large amount of an antibacterial agent was consumed in order to exert an excellent antibacterial action, resulting in an increase in manufacturing cost.

The present invention has been made in view of the above-mentioned conventional circumstances, and it is an object of the present invention to provide a product which can be manufactured at low cost and has a glass layer capable of exhibiting an excellent antibacterial action. Make it an issue.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems. First, in a product having the above-mentioned general glass layer, a schematic diagram in FIG. As shown, it was found that the concentration of the antimicrobial metal was lowest at the surface and increased gradually in the depth direction.
And it was also confirmed that a product having such a concentration curve cannot exert an excellent antibacterial action against bacteria on the surface of the glass layer unless the concentration of the antibacterial agent dispersed in the glass layer is increased. On the other hand, the concentration of antibacterial metal is highest on the surface,
For products with a glass layer whose concentration gradually decreases in the depth direction, it was also confirmed that excellent antibacterial action against bacteria on the surface of the glass layer can be exhibited even if the concentration of the antibacterial agent used is not so high. did. Thus, the present invention has been completed.

That is, a product having a glass layer according to the present invention comprises a substrate having a glass layer, the glass layer having a rich layer containing a high concentration of an antibacterial metal on the surface, and a concentration of the antibacterial metal in the rich layer. Is characterized by being highest on the surface side and gradually decreasing in the depth direction.

[0008] The product of the present invention has a rich layer containing a high concentration of antibacterial metal on the surface of the glass layer, so that such antibacterial metal acts on bacteria and kills them or suppresses their proliferation. it can. Here, the concentration of the antimicrobial metal in the rich layer is highest on the surface side and gradually decreases in the depth direction. According to the test results of the present inventors, it is possible to exert an excellent antibacterial action against bacteria on the surface of the glass layer without significantly increasing the concentration of the antibacterial agent to be used. Can be avoided.

Therefore, the product of the present invention can be manufactured at low cost and can exhibit an excellent antibacterial action.

According to the test results of the inventors, the alkali metal ion or the alkaline earth metal ion in the glass layer is ion-exchanged to the antibacterial metal ion only by bringing the antibacterial agent into contact with the glass layer of the substrate, Is taken into the glass layer. The amount of the antibacterial metal ion to be substituted in the glass layer can be determined by adjusting the concentration of the antibacterial agent, the contact temperature, the contact time, and the like. As a result, the antibacterial metal ions do not diffuse evenly throughout the glass layer, and a rich layer containing a high concentration of ion-exchanged antibacterial metal ions is provided on the surface side of the glass layer.

Therefore, it is possible to prevent useless antibacterial metal ions from existing inside the rich layer, and to avoid wasteful consumption of antibacterial metal ions.

Here, as a substrate having a glass layer, a glass product, a ceramic product, or an enamel product can be employed. As ceramic products, tiles and sanitary ware can be used.

As the antibacterial agent, an antibacterial metal by evaporation, an antibacterial metal fine powder, a colloid containing the antibacterial metal, and a solution in which the antibacterial metal is dissolved by ions can be used. Ag, Cu, Zn or the like can be adopted as the antibacterial metal. 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, or the like can be used. These antibacterial metals may be a single substance, an alloy, or a compound. However, in order to reduce the contact temperature and shorten the contact time in order to perform ion exchange by contact, it is preferable to use a colloid or a solution having a smaller size of a highly soluble antibacterial metal. More preferably, a solution of silver nitrate, silver sulfate or the like is used. This is because the size of the antibacterial metal is larger than the atom in the colloid, whereas the size of the antibacterial metal is equal to the atom in these solutions. The solution in which the antibacterial metal is dissolved by the ion can be embodied as a treatment liquid containing the antibacterial metal ion and a solvent. Also,
The colloid preferably contains a large amount of antimicrobial metal fine particles, and the solution preferably has a high concentration of antimicrobial metal ions dissolved therein.

According to a practical manufacturing method, the concentration of the antibacterial metal on the surface exceeds twice the concentration of the antibacterial metal inside at a depth of 10 nm from the surface. According to the test results of the inventors, this provides a sufficient antibacterial effect.

In the product of the present invention, it is also preferable that the glass layer contains an antibacterial metal even inside the rich layer. In this case, the concentration of the antibacterial metal becomes substantially uniform in the depth direction. In this case, an antibacterial metal that can exhibit the action of the initial antibacterial metal by ion exchange performed from the surface side of the glass layer and that can effectively exert the action only by ion exchange performed from the surface side of the glass layer is used. As compared with the case of incorporating in the glass layer, the durability is improved, and the amount of antibacterial metal consumed is reduced, so that the production cost can be reduced.

That is, when the antibacterial metal is taken into the glass layer only by ion exchange performed from the surface side of the glass layer, the above-described rich layer is formed on the surface side of the glass layer. According to the test results of the present inventors, such a 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 abrasion may progress from the surface to some extent after use, unless a large amount of antibacterial metal is ion-exchanged to increase the concentration of the antibacterial metal slightly inside the surface side,
The function cannot be effectively exerted only by the metal of such a rich layer. For this reason, in this case, it is impossible to achieve both improvement in durability and reduction in manufacturing cost.

On the other hand, when the antibacterial metal is contained in the glass layer in advance, according to the test results of the present inventors, the concentration of the antibacterial metal is the lowest on the surface side and goes toward the inner side at the back. And gradually increases, and then tends to saturate. For this reason, in this case, if the glass layer contains a large amount of antibacterial metal and the concentration that saturates the glass layer is not increased to some extent when the abrasion progresses from the surface to a certain extent after use, the action of the antibacterial metal alone is still effective. It cannot be used effectively. For this reason, in this case, it is difficult to exhibit the action of the antibacterial metal initially.

In this regard, if the antibacterial metal is previously contained in the glass layer, and the antibacterial metal is taken in by ion exchange from the surface side of the glass layer, a rich layer is formed on the surface side of the glass layer. Antimicrobial metals that saturate at about the same concentration as the rich layer.
That is, the glass layer of the base contains the antibacterial metal even inside the rich layer. If this is the case, the antimicrobial metal action will be better exhibited by the rich layer before wear from the surface immediately after use, and if the wear progresses from the surface to some extent after use, it will still be better due to the internal antibacterial metal. The action of the antibacterial metal is exerted. For this reason,
The action of the antibacterial metal can be exhibited at an early stage, and both improvement in durability and reduction in manufacturing cost can be achieved.

The product having the glass layer of the present invention can be produced by the above-mentioned ion exchange method as a first method, and can also be produced by the following second and third methods.

That is, in the second method, an antibacterial agent is adhered to the surface of the glass layer of the substrate, and then, the antibacterial agent is irradiated with a laser beam. According to the test results of the inventors, the antibacterial function of the product thus manufactured has a rich layer of antibacterial metal on the surface of the glass layer by the action of the laser beam, and the antibacterial performance is remarkably enhanced.

On the other hand, in the third method, first, 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 antimicrobial metal on the surface of the base are provided. Prepare Then, a first glaze made of the first glaze is formed on the surface of the base.
A first glaze layer and a second glaze layer are formed by melting a first glaze layer and a second glaze layer.
Forming a glass layer and a second glass layer; According to the test results of the inventors, the product having antibacterial function produced in this way does not use much antibacterial agent, a rich layer of antibacterial metal is generated on the surface of the glass layer, and the antibacterial performance is remarkably high. Enhanced.

In the product of the present invention, a water-repellent layer containing a water-repellent component is preferably formed on the surface side of the glass layer. In this case, both the antibacterial function and the water-repellent function will be imparted to the surface of the glass layer, and even if moisture containing a large amount of dirt components is used so that the antibacterial effect alone is insufficient. Due to its water repellent function, dirt does not easily remain, and the antibacterial effect can be sufficiently exhibited.

Here, as a method for forming a water-repellent layer containing a water-repellent component on the surface side of the glass layer, a silicon-containing functional group which is bonded to a hydroxyl group present on the surface of the glass layer by a dehydration reaction or a dehydrogenation reaction is used. It is possible to employ the treatment with the water-repellent treatment liquid. If you do this,
The silicon-containing functional group binds to a hydroxyl group (-OH) present on the surface of the 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 possible and does not bind to those metal ions,
It does not combine 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, in a product that uses water containing a large amount of metal ions such as soluble silica at the same time, dirt such as human waste hardly sticks and cleaning thereof becomes easy.

Further, as the water-repellent treatment liquid, a liquid which is not bonded between silicon-containing functional groups can be used. According to the test results of the inventors, this makes it possible to enhance the antifouling effect with respect to water stain resistance, hair dye stain, abrasion resistance and alkali resistance. This is because if the silicon-containing functional groups of the water-repellent treatment liquid are bonded to each other, silicon is increased and silicic acid having a network structure is precipitated in the coating, and it is considered that dirt is easily taken therein.

Further, as the water-repellent treatment liquid, a liquid having a terminal fluorocarbon group bonded to a silicon-containing functional group may be employed. According to the test results of the inventors, the presence of a fluorocarbon group in this way has a high water-repellent effect due to the small critical surface tension of the fluorocarbon group, and is effective against water-resistant stains, hair dye stains and alkali resistance. This is because the effect is large. Fluorocarbon group is -C _n F _{2n +} 1 _(n is 1 ≦ n ≦
12 (natural number of 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.

Further, as the water-repellent treatment liquid, a liquid having no terminal alkyl group bonded to the silicon-containing functional group can be used. According to the test results of the inventors, this makes it possible to enhance the effect on water stain resistance, hair dye stain resistance and alkali resistance.

On the other hand, a liquid having a terminal alkyl group bonded to a silicon-containing functional group can also be used as the water-repellent treatment liquid. According to the test results of the inventors, the presence of the alkyl group in this manner causes the antifouling effect to appear as lipstick stain resistance and abrasion resistance due to the large critical surface tension of the alkyl group.

From the viewpoint of abrasion resistance, a methyl group can be used as the alkyl group. On the other hand, from the viewpoint of alkali resistance, a propyl group or a hexyl group can be used as the alkyl group. According to the test results of the inventors, when the alkyl group is a propyl group, a hexyl group, or the like, the alkyl group is bulky and excellent in alkali resistance, but inferior in abrasion resistance. On the other hand, when the alkyl group is a methyl group, it is excellent in abrasion resistance but inferior in alkali resistance.

When the water-repellent treatment solution has a terminal fluorocarbon group bonded to the silicon-containing functional group and has a terminal alkyl group bonded to the silicon-containing functional group, the liquid repellent treatment liquid has more alkyl groups than the fluorocarbon group. It is preferable to employ According to the test results of the inventors, the water-repellent treatment liquid is not only perfluoroalkylsilane, but has a high effect on lipstick stain resistance and abrasion resistance.

On the other hand, when the water-repellent treatment solution has a terminal fluorocarbon group bonded to the silicon-containing functional group and has a terminal alkyl group bonded to the silicon-containing functional group, the fluorocarbon group is more substituted than the alkyl group. It is also preferable to employ a large number. According to the test results of the inventors, this increases the perfluoroalkylsilane in the water-repellent treatment liquid,
It is highly effective against water stains, hair dye stains, abrasion resistance and alkali resistance.

It is preferable that the silicon-containing functional group and the alkyl group are bonded by dimethylsiloxane (O—Si (CH ₃ ) ₂ ). According to the test results of the inventors, this has a high effect on water stain resistance, hair dye stain resistance, abrasion resistance and alkali resistance.

This dimethylsiloxane is linearly silicified.
In addition to those linking an element-containing functional group and an alkyl group,
Cyclic silicon-containing functional group and alkyl group
It is preferable to use one. Inventors' test results
According to this, this makes it resistant to water stain, lipstick stain, hair dye
Stable against liquid stain, abrasion resistance and alkali resistance
Demonstrate high effect. Dimethylsiloxane is linear
Ingredients having an i-containing functional group and an alkyl group bonded
As an example of the body, Japanese Patent Application Laid-Open No. 8-209118
It is possible to employ a water-repellent treatment liquid obtained by mixing one agent and a second agent.
it can. Here, the first agent contains a perfluoroalkyl group.
Silicon Compound and Hydrolyzable Group-Containing Methyl Polysiloxane
Is a co-hydrolysate with a hydrophilic compound in a hydrophilic solvent.
The two agents are a mixture of an organopolysiloxane and a strong acid.
You. More specifically, the first agent is C ₈F₁₇CH_TwoCH_TwoS
i (OCH_Three)_ThreeAnd Si (CH_ThreeO)_ThreeCH_TwoCH_Two− (S
i (CH_Three)_TwoO)_Ten-Si (CH_Three)_TwoCH_TwoCH_TwoSi
(OCH_Three)_ThreeAnd 0.1N aqueous hydrochloric acid, t-butanol and
Co-hydrolyzed in a hydrophilic solvent consisting of hexane
Yes, the second agent is HO- (Si (CH (CH_Three)_TwoO)₃₀-Si
(CH_Three)_TwoThere is a mixture of OH and methanesulfonic acid.

The inventors have also completed a method for determining a product according to the present invention. That is, the method for judging a product of the present invention comprises a substrate having a glass layer, and the glass layer is a method for judging a product having a rich layer containing a high concentration of an antibacterial metal on the surface,

By analyzing the concentration of the antibacterial metal in the rich layer by X-ray photoelectron spectroscopy, it is determined that the concentration of the antibacterial metal in the rich layer is highest on the surface side and gradually decreases in the depth direction. Features.

In the method for judging a product according to the present invention, it is necessary to measure the concentration distribution of the antimicrobial metal in the rich layer in the depth direction within several hundreds of nm.
Line photoelectron spectroscopy is used. According to this method, not only the concentration distribution of the antibacterial metal by the depth method but also the state analysis of the antibacterial metal is possible. According to the test results of the inventors, it has been found that the antibacterial function differs depending on whether the antibacterial metal in the glass layer is in an atomic state or as an ion, and therefore, the state analysis by X-ray photoelectron spectroscopy is performed. By doing so, a more accurate judgment on the antimicrobial function of the product of the present invention can be made. Further, the method for determining a product of the present invention can be applied to a product of the present invention in which a water-repellent layer containing a water-repellent component is formed on the surface side of a glass layer.

[0036]

Embodiments of the present invention and tests 1 and 2 will be described below with reference to the drawings.

(Embodiment) As shown in FIG. 1, a base 15 which is a semi-finished product of sanitary ware having a glass layer 12 made of a glaze having the following composition on the surface of a base material 10 is prepared. The glass transition point of the glass layer 12 is 700 ° C.

<Mixing ratio of glaze (% by weight)> Feldspar: 53.7 Silica sand: 9.8 Lime: 12.3 Dolomite: 4.8 Frog eyes: 5.1 Zinc white: 2.0 Zircon: 10.1 Frit: 2.2

The substrate 15 is placed on a 50 ± 2 mm square (thickness: 10 ± 2 mm).
55 mm) of test pieces cut into squares (within mm). Each test piece was subjected to a pretreatment consisting of the following steps.

First step: The surface of the glass layer 12 of the test piece is washed with a sponge impregnated with a neutral detergent.

Second step: The surface of the glass layer 12 of the test piece is rinsed in the order of tap water and distilled water.

Third step: The whole test piece is subjected to ultrasonic cleaning with distilled water for 10 minutes and then rinsed with distilled water. This operation 3
Repeat several times.

Fourth step: The test piece is placed in a glass dish and dried with a desiccator (about 12 hours).

Fifth step: The surface of the glass layer 12 of the test piece is lightly wiped with absorbent cotton or nonwoven cloth impregnated with ethanol.

Sixth step: An aqueous solution of silver nitrate (AgNO ₃ ) having a concentration of 0.30 mol / L is prepared as a treatment liquid as an antibacterial agent, and the test piece is completely immersed in this treatment liquid.

Seventh step: The entire surface of the glass layer 12 of the test piece is washed with distilled water.

Eighth step: After heating the surface of the glass layer 12 of the test piece to 100 ° C., it is rapidly cooled to room temperature.

Ninth step: The whole test piece is subjected to ultrasonic cleaning with distilled water for 10 minutes and then rinsed with distilled water.

Tenth step: The test piece is placed in a glass dish and dried with a desiccator (about 12 hours).

In these first to tenth steps, the condition of the sixth step was set to 10 ° C. × 1 second, and a test piece not subjected to the eighth step was designated as sample A. In addition, the condition of the sixth step is set to 30.
° C x 1 second, and the test piece which was not subjected to the eighth step was designated as Sample B. Further, the condition of the sixth step was set to 60 ° C. × 1 second, and a test piece not subjected to the eighth step was designated as sample C. The condition of the sixth step was 60 ° C. × 1800 seconds,
The test piece which did not perform the process is referred to as Sample D. On the other hand, the sixth
The condition of the process was 60 ° C. × 1800 seconds, and the test piece subjected to the eighth process was designated as Sample E. Eleven samples were prepared for each of these samples A to E.

Of these samples A to E, eight samples each were subjected to an X-ray photoelectron spectroscopy test and an antibacterial test. In addition, for each of the samples A to E, the remaining three pieces were subjected to the following water repellent treatment on the surface of the glass layer 12,
It was subjected to an antibacterial test.

First, a perfluoroalkyl group-containing organic silicon
C as an elemental compound₈F₁₇CH_TwoCH_TwoSi (OCH_Three)_Three And a hydrolyzable group-containing methylpolysiloxane compound.
Si (CH_ThreeO)_ThreeCH_TwoCH_Two− (Si (CH_Three)_TwoO)_Ten
-Si (CH_Three)_TwoCH _TwoCH_TwoSi (OCH_Three)_Three Consisting of 0.1N aqueous hydrochloric acid, t-butanol
Co-hydrolyzed in a hydrophilic solvent consisting of hexane and hexane
Prepare one agent. These are silanols (Si-
(OH) group.

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, mixed, applied to the surface of the sample, and left to dry for about 10 minutes. Thereafter, the surface is washed with ethanol and dried.

Thus, samples A to E were obtained in which the water-repellent layer containing the water-repellent component was formed on the surface side of the glass layer.

The silver concentration (atom%) of each of the samples A to E not subjected to the water-repellent treatment was measured by the XPS method (X-ray photoelectron spectroscopy), and the sample A not subjected to the water-repellent treatment was measured. To E and samples A to E subjected to water repellent treatment
For each of the three samples, an antibacterial test was carried out for each of the three samples by the film adhesion method.

Here, the XPS method involves irradiating the surface of the glass layer 12 of a sample placed in an ultra-vacuum with focused soft X-rays, which are separated by a curved single crystal, and detecting photoelectrons emitted from the surface with an analyzer. Is a method of using the information for element identification and quantification. The element information on the surface can be obtained from the binding energy value of the bound electrons in the substance, and the information on the valence and the bonding state can be obtained from the energy shift of each peak. In addition, it can be quantified using the peak area. Table 1 shows the results of the silver concentration of each of the samples A to E not subjected to the water-repellent treatment. In addition, "#" shows that it is below the detection limit.

Samples A to E not subjected to the water-repellent treatment
The samples A to E subjected to the water repellent treatment were subjected to an antibacterial test by a film adhesion method. Table 2 shows the results.

[0059]

[Table 1]

[0060]

[Table 2]

From Table 1, it is found that Samples A to A which have not been subjected to the water-repellent treatment
It can be seen that the glass layer 12 of E has a rich layer 13 containing Ag at a high concentration on the surface as shown in FIG. In addition, it turns out that Ag ions are larger on the surface side of the glass layers 12 of the samples A to E than inside. this is,
Ion exchange is mainly K ion and A, which are close to each other in ionic radius.
It is presumed to have occurred with g ions. In the sample E, since Ag ions were measured to the inside, K ions in the glass layer 12 of the substrate 15 were ion-exchanged into Ag ions by the contact of the processing liquid, and further absorbed by heating.
It can be seen that g ions penetrate into the glass layer 12.

As shown in Tables 1 and 2, Ag was added to the surface of the glass layer 12 in order to impart an antibacterial effect to the surface of the glass layer 12.
It can be seen that it is sufficient to only exist on the pole surface of No. 2. That is, Ag in the rich layer of the glass layer 12
Can act on bacteria to kill them or suppress their reproduction. Here, from Table 1, the concentration of Ag in the rich layer is highest on the surface side and gradually decreases in the depth direction. For this reason, even if the concentration of the processing solution to be used is not so high, since it is possible to exhibit an excellent antibacterial action against bacteria on the surface of the glass layer 12, it can be understood that large consumption of the processing solution can be avoided. In particular, the glass layers 12 of the samples A to E each have a rich layer whose Ag concentration is 1% from the surface.
The concentration was more than twice the concentration of Ag inside 0 nm deep, and a sufficient antibacterial action was obtained.

Further, from Table 2, it can be seen that even when the surface of the glass layer 12 is subjected to the water-repellent treatment, the antibacterial effect is hardly reduced as compared with the case where the water-repellent treatment is not performed. The reason for this is that even if the water-repellent layer 14 is formed on the glass layer 12 by the water-repellent treatment as shown in FIG. 4, the thickness is very small, and the water-repellent layer 14 is bonded only to the surface hydroxyl groups of the glass layer. Therefore, it is considered that the antibacterial effect permeates this drainage layer. Therefore, when a water repellent treatment is performed on the surface of the glass layer 12, both the antibacterial function and the water repellent function are imparted to the surface of the glass layer 12, and the antibacterial effect alone is insufficient. Even if water containing a large amount of dirt components is used, the dirt hardly remains due to its water repellent function, and the antibacterial effect can be sufficiently exhibited.

Therefore, it can be seen that the product of this embodiment can be manufactured at low cost and can exhibit excellent antibacterial action.

(Test 1) A sample F in which Ag was incorporated into the glass layer 12 was produced only by ion exchange performed from the surface side of the glass layer 12. Glass layer 12 in this sample F
The Ag concentration in the sample was measured by the XPS method, and the depth (nm) from the surface and the concentration index (Intensity (Count)
s)). FIG. 6 shows the results. In the figure, F
Indicates the measurement result of the sample F. Further, 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. 6 shows that in the case of X according to the conventional method, Ag
Is the lowest on the surface of the glass layer 12 and gradually increases in the depth direction. That is, it can be seen that 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 F, Ag ions were taken in, and the Ag ions were
It can be seen that the closer to the surface of No. 2, the higher the concentration. That is, as shown in FIG.
2 has a rich layer 13 containing Ag at a high concentration on the surface. The rich layer 13 has the highest Ag concentration on the surface, and the concentration gradually decreases in the depth direction. More specifically, Ag has a concentration that has a peak on the surface side and attenuates in inverse proportion toward the inner side at the back.

(Test 2) Sample 1 in which Ag was incorporated into glass layer 12 only by ion exchange performed from the surface side of glass layer 12, Sample 2 in which Ag was contained in glass layer 12 in advance, Ag is contained in the glass layer 12 in advance, and a sample 3 in which Ag is taken in by performing ion exchange from the surface side of the glass layer 12 is prepared. The Ag concentration in the glass layer 12 in each of the samples 1 to 3 was measured by XPS
The relationship between the depth from the surface (nm) and the concentration index (Intensity (Counts)) by natural logarithm was determined. FIG. 7 shows a schematic result.

As shown in the sample 1 of FIG. 7, when Ag is taken into the glass layer 12 only by ion exchange performed from the surface side of the glass layer 12, a rich layer 13 is formed on the surface side of the glass layer 12. You can see that In this regard, FIG.
Of sample F.

On the other hand, as shown in Sample 2 in FIG. 7, when Ag is contained in the glass layer 12 in advance, the concentration of those Ag is the lowest on the surface side, and it goes to the inner side at the back. It can be seen that it gradually increases and tends to be saturated. This is the same as the sample X in FIG.

Here, in Sample 1, considering that the wear may progress to some extent from the surface after use, a large amount of Ag is ion-exchanged to remove the A inside the surface slightly behind the surface side.
Unless the concentration of g is increased, it is considered that the action cannot be effectively exerted only with Ag in such a rich layer. 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, in the case of Sample 2, when the wear progresses to some extent from the surface after use, unless the glass layer 12 contains a large amount of Ag and the concentration for saturation is increased to some extent, the effect can be effectively achieved only with these Ags. It is thought that it cannot be demonstrated. For this reason, in this case, it is understood that the function of the metal is hardly exhibited at the initial stage.

For this reason, as shown in the sample 3 of FIG. 7, the glass layer 12 contains Ag in advance,
By performing ion exchange from the surface side of the glass layer 12, Ag
It can be understood that, if the concentration is taken, a rich layer is formed on the surface side of the glass layer 12 and Ag that saturates at a concentration substantially equal to the concentration of the rich layer can be included. That is, sample 3
As shown in FIG. 3, the glass layer 12 has a rich layer 13 containing Ag at a high concentration on the surface, and also contains Ag inside the rich layer 13. The glass layer 12 of the base 15 has a substantially uniform Ag concentration in the depth direction. In this case, the rich layer exhibits excellent antibacterial action before wear from the surface immediately after use, and when the wear progresses from the surface to some extent after use, the excellent antibacterial action is also exhibited by the internal Ag. It is understood that it is exerted. Therefore, it can be seen that if this is the case, the action of Ag can be exhibited at the initial stage, and that both improvement in durability and reduction in manufacturing cost can be achieved.

As shown in FIG. 5, the surface of the glass layer 12 of the sample 3 was subjected to a water-repellent treatment to form the water-repellent layer 14, and the Ag concentration in the glass layer 12 was changed to XPS.
The relationship between the depth from the surface (nm) and the concentration index (Intensity (Counts)) by natural logarithm was determined. In this case, the method of the water-repellent treatment was the same as the case where the samples A to E were subjected to the water-repellent treatment. As a result, like the sample 3 in FIG. 7, it was found that the glass layer 12 had the rich layer 13 containing Ag at a high concentration on the surface, and also contained Ag inside the rich layer 13. Therefore, the same operation and effect as in the case of the sample 3 are produced, and since the surface thereof has the water-repellent layer as shown in FIG. Even if a large amount of water is used, the water repellent function makes it difficult for dirt to remain, and the antibacterial effect can be sufficiently exhibited.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a substrate used in an example of the present invention.

FIG. 2 is a schematic enlarged sectional view of a sample according to a product of an example of the present invention.

FIG. 3 is a schematic enlarged sectional view of a sample according to a product of an example of the present invention.

FIG. 4 is a schematic enlarged sectional view of a sample according to a product of an example of the present invention.

FIG. 5 is a schematic enlarged sectional view of a sample according to a product of an example of the present invention.

FIG. 6 is a graph showing the measurement results of the concentration of Ag in the glass layer in Test 1.

FIG. 7 is a schematic graph showing the measurement results of the concentration of Ag in the glass layer in Test 2.

FIG. 8 is a schematic graph showing a measurement result of a concentration of Ag in a glass layer obtained by a conventional method.

[Explanation of symbols]

 12: glass layer 15: base 13: rich layer 14: water-repellent layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 41/86 C04B 41/86 Z C23C 26/00 C23C 26/00 L C23D 5/00 C23D 5/00 Z G01N 23/227 G01N 23/227 (72) Inventor Takahiro Morita 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Inax Corporation (72) Inventor Yuichiro Aihara 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Co., Ltd. Inside Inax (72) Inventor Tsuru Yamashita 5-1-1 Koie Honcho, Tokoname, Aichi Prefecture Inax Corporation (72) Inventor Haruyuki Mizuno 5-1-1 Koie Honmachi, Tokoname, Aichi Prefecture Inax Corporation (72) Invention Person Hiroaki Kuno 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Shigeo Imai Aichi 5-1-1 Koie Honcho, Tokoname City Inax Corporation (72) Inventor Hiroyuki Miyamoto 5-1-1 Koie Honcho, Tokoname City, Aichi Prefecture Inax Corporation (72) Inventor Noriyuki Sugiyama 5 Koie Honcho, Tokoname City, Aichi Prefecture 1-chome Inax Corporation (72) Inventor Shozo Yamamoto 5-1-1 Koiehoncho, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Akito Suzuki 5-1-1 Koiehoncho, Tokoname-city, Aichi Co., Ltd. Inside Inax (72) Inventor Kazuhiko Hattori 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Inax Corporation (72) Inventor Shungo 5-1-1 Koiehonmachi, Tokoname-shi, Aichi F-Term in Inax Corporation (Reference) 2G001 AA01 BA08 CA03 GA01 GA08 JA12 KA01 LA02 LA06 NA12 NA13 NA17 RA02 RA03 RA05 RA08 RA20 4G059 AA20 AC22 AC30 DA01 DA04 DA09 EA00 EB05 FA05 FA22 FB06 4H011 AA02 BA01 BB18 BC18 DD07 4K044 AA12 CA16

Claims (7)

[Claims] The present invention comprises a substrate having a glass layer, the glass layer having a rich layer containing a high concentration of an antibacterial metal on the surface, wherein the concentration of the antibacterial metal in the rich layer is highest on the surface side and the depth is Product with a glass layer characterized by a gradual decrease in the direction. 2. The concentration of the antibacterial metal on the surface is 10n from the surface.
2. A product having a glass layer according to claim 1, wherein the concentration of the antibacterial metal in the interior of the back is more than twice as high. 3. The product having a glass layer according to claim 1, wherein the glass layer further contains an antibacterial metal inside the rich layer. 4. The product having a glass layer according to claim 3, wherein the concentration of the antibacterial metal is substantially uniform in the depth direction. 5. A water-repellent layer containing a water-repellent component is formed on the front side of the glass layer.
Or a product having a glass layer according to 4. 6. A method for judging a product comprising a substrate having a glass layer, wherein the glass layer has a rich layer containing a high concentration of an antibacterial metal on the surface, wherein the concentration of the antibacterial metal in the rich layer is determined by X-rays. A method for judging a product having a glass layer characterized by analyzing by photoelectron spectroscopy that the concentration of the antibacterial metal in the rich layer is highest on the surface side and gradually decreases in the depth direction. . 7. A method for judging a product having a glass layer according to claim 6, wherein a water-repellent layer containing a water-repellent component is formed on the surface side of the glass layer.