JPH08208357A - Method for antibacterial and antimold processing of ceramic material and its product - Google Patents

Abstract

PURPOSE: To give antibacterial and antimold effects which are sure and continuous to a ceramic product while maintenance for the product is least required, by applying glaze on a ceramic product, spraying a specified antibacterial and antimold soluble glass fine particles thereon, and then baking. CONSTITUTION: After a ceramic product is glazed, antibacterial and antimold soluble glass particles having <=50μm average particle size and <=0.5mg/1g of glass/hr dissolving rate in water at 20 deg.C for 500μm particle size and containing at least one of Ag2 O and ZnO is sprayed on the glaze by 0.001-5mg/cm<2> amt. Then the glass particles are baked with the glaze.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is for maintaining sanitary porcelain products such as tableware, toilet bowls, flooring materials, wall materials, water permeable plates and tiles, bathtubs, washbasins and enamels, etc. The present invention relates to antibacterial and antifungal treatments, and a processing method thereof.

[0002]

BACKGROUND ART Products such as tableware, toilet bowls, flooring materials, wall materials, water-permeable plates, bathtubs and washbasins have a deep connection in daily life, and are often used at the same time as being directly touched by humans. Since there are many opportunities to come into contact with the product, hygiene and aesthetics are especially important. Therefore, in addition to the above-mentioned characteristics, a ceramic product which is a material having durability and warmth in life is preferably used. In particular, the surface is treated with a glaze as a suspension liquid with water added, and the product itself is aesthetically enhanced by baking and vitrifying and fusing it to the product body, while preventing stains, water permeation, and strength. Useful for improving corrosion resistance and electrical properties.

However, in terms of hygiene, at present, it is necessary to clean it manually by a means such as daily or periodical brushing or cleaning with Cl ₂ . It was cumbersome and there was a desire to develop an alternative method. In addition, this method is costly for maintenance, and when Cl ₂ and HCl are used as chemicals to be used, Cl ₂ gas may be generated. There were some problems and I needed to be careful.

Therefore, as a method that has been frequently performed recently, there has been a method in which a commercially available liquid antibacterial or antifungal agent is periodically applied by means such as spraying. Although some annoyance is eliminated compared to the above regular cleaning,
Due to the fact that the drug is easily peeled off by ordinary washing with water and the durability is poor, and the effect of the drug is reduced in a relatively short period of time, frequent spraying work is required.

In addition, Japanese Laid-Open Patent Publication No. 6-127975 discloses a material which is made maintenance-free by mixing and firing a calcium phosphate compound containing silver, copper and zinc with a glaze. However, when copper is used as the metal ion among them, coloring tends to occur, and therefore, the ceramic products often based on white tend to be restricted in use or application. Further, since calcium phosphate is poorly soluble in water, the elution of metal ions is small and the antibacterial and antifungal properties tend to be insufficient. When fluorine is added, the use of silver as a metal ion may cause AgF to be formed, resulting in a decrease in antibacterial and antifungal activity. In the case of containing zinc, if it is contained in an amount of about 10% by weight, the antibacterial and antifungal effects are weak and the properties of the glaze are affected, so it is not possible to add too much, and the range of use Was narrow. Furthermore, since it is mixed and baked with the glaze, metal ions easily enter the inside and do not completely come out to the surface, so a step of acid cleaning is required to activate the surface of the calcium phosphate compound, which is very expensive. It has a drawback that it will end up. This may be because glaze and calcium phosphate do not melt each other. In addition to this, the content of antibacterial and antifungal agents against the glaze is increased, and there is a risk that the characteristics of the glaze are impaired.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional drawbacks and makes it possible to obtain a reliable antibacterial and antifungal effect on ceramic products as maintenance-free as possible.
Further, the color tone is basically white, and there is no limitation on the use, and a method for satisfying the effect persistence, durability, etc. and a ceramic product thereof are provided.

[0007]

According to the present invention, a porcelain is provided with a glaze, and thereafter, an average particle size is 50 μm or less and Ag is used.
₂ O, at least one of ZnO, and the total of alkali components is 0 to 10% by weight with respect to the glass body, and the particle size is 50.
0 μm, dissolution rate in water at 20 ° C. is 0.5 mg /
It is characterized by spraying 0.001 to 5 mg / cm ^{2 of} antibacterial and antifungal soluble glass fine particles having a glass g / Hr or less and baking together with a glaze. It is also characterized in that the glass particles are sprayed and baked on unglazed ceramics using the same soluble glass, and it is characterized by mixing glaze and the glass particles, sprayed on the ceramics, and baked. It is characterized in that the fine glass particles are sprinkled on a ceramic in which a glaze is baked and then baked. The present invention also relates to a product characterized in that a glaze and its glass fine particles are fused on the surface of a ceramic porcelain by mutual fusion.

Here, in the case of zinc-based glass, the glaze used in the present invention may be any combination of alkaline glaze, alkaline lime glaze, lime glaze, feldspar glaze, boric acid glaze, and lead glaze. In this case, lime glaze, feldspar glaze, and boric acid glaze are preferable because of their discoloration.

One or both of silver and zinc can be used as the metal ion having antibacterial and antifungal effects,
Regarding the content of Ag ₂ O and ZnO in the soluble glass, Ag ₂ O is preferably 3% by weight or less from the viewpoint of discoloration,
ZnO is in a range of 10 to 50 mol% more preferable than the effect. If the amount is 10 mol% or less, the effect is weak and, conversely, 5
When it is 0 mol% or more, it is disadvantageous because it adversely affects glass melting, vitrification and glass properties. The alkaline component means the total content of Na ₂ O and K ₂ O components,
These components may be omitted, but it is advantageous to add them in terms of glass melting and vitrification. However, the alkali component should not exceed 10 mol% in the glass. Especially Ag
This is because the glass of the type tends to discolor, and the mutual melting with the glaze deteriorates the durability, causing a problem in the sustainability of the effect. The basic composition of glass is B ₂ O ₃ system, P ₂ O ₅ system, S
Any of iO ₂ may be used, but since it causes deterioration in durability due to mutual melting with the glaze, B ₂ O ₃ 70 mol% or more, P ₂ O ₅ 60 mol% or more, etc. in combination with the glaze,
There are cases that should be avoided.

The particle size is preferably 50 μm or less, more preferably 5 μm or less. Further, those treated with a surface treatment agent or a dispersant with silicone oil or talc are more preferable.
If it is rough, mutual melting and diffusion with the glaze will be insufficient, resulting in crystallization, spots on the appearance, and difficulty in durability. In addition, the soluble glass has an average particle size of 500μ.
It is necessary to use those having a dissolution rate of 0.5 mg / glass g / Hr or less in m at 20 ° C. This is because those having a dissolution rate higher than this have a low durability.

If the amount of spraying is less than 0.001 mg / cm ² , the effect is insufficient, and conversely, if it exceeds 5 mg / cm ² ,
Poor appearance (loss of gloss or discoloration in the case of containing silver) occurs, durability is deteriorated, and antibacterial and antifungal effects are not changed. The method of spraying may be any of spraying, roll coating, powder spraying, etc., but spraying or powder spraying is more preferable. Moreover, you may use a solvent, a binder, etc. In order to apply a thin film uniformly, it is preferable to disperse the powder in the air in the chamber and set it down by sedimentation.

The firing temperature is the firing temperature of the glaze (about 1000).
Up to 1300 ° C). The melting temperature of glass is about 500
This is because, because the temperature is ˜800 ° C., sufficient mutual melting occurs.

When applied to a biscuit plate, the melting rate of the molten glass applied to the water permeable plate is 0.01 mg / g glass /
It must be Hr or less. This is because the meltable glass is sufficiently exposed on the surface, and the sustainability of the effect is poor at a melting rate higher than this.

When the mixture is baked with the glaze, the mixture ratio is preferably 2 to 10% by weight. If less than 2% by weight, antibacterial,
This is because the antifungal effect is low.
This is because it changes the characteristics of the glaze. When spraying and baking on a baked glaze, the dissolution rate is 0.01 mg / glass g / Hr or less, and the spray amount is 0.001 to 0.5 mg.
/ Cm ² . For the same reason as baking with the glaze, if less than 0.001 mg / cm ² , the antibacterial and antifungal effect is low, and if more than 0.5 mg / cm ² , the characteristics of the glaze change.

[0015]

FUNCTION The soluble glass used here is a generic term for glass whose composition has been adjusted in consideration of the physical and chemical properties of the glass so that it has a controlled melting rate, and it is a generic term for specific metal ions. The inclusions are known to be capable of eluting the metal ions at a defined constant rate over an arbitrary period of several hours to several years. The eluted metal ions exert antibacterial and antifungal effects. In the present invention, one is completed by mutually melting this fusible glass with a glaze. Since the baking of the ceramics and the glaze is 1000 to 1300 ° C, the melting temperature of the melting glass exceeds about 500 to 800 ° C, and the glaze and the melting glass are melted with each other.
It will be fused.

[0016] After the glaze is applied to the pottery in advance, the soluble glass is sprinkled and baked in order to cause mutual melting, so that the soluble glass is exposed on the surface, and the pottery itself is exposed to daily water. Upon contact with the soluble glass, the soluble glass is eluted, and along with it, silver or zinc ions having antibacterial and antifungal properties are eluted.

When the fusible glass is fused to the surface of the unglazed glass, the fusible glass also appears on the surface. Therefore, the fusible glass is similarly eluted upon contact with water to exhibit antibacterial and antifungal effects. In addition, a product obtained by mixing soluble glass in advance with a glaze and baking the same has a lower chance of contact between the soluble glass and water as compared with the previous processing method, but similarly exhibits antibacterial and antifungal effects. Furthermore, the same antibacterial and antifungal action as described above can be imparted by melting the soluble glass on the surface of the porcelain product already subjected to the glaze by post-processing and melting it.

[0018]

EXAMPLES First, the following glasses (1) to (4) were prepared. B ₂ O ₃ 50 mol%, MgO 40 mol%, Na
_{2 O5mol%, P 2 O 5} 5mol%, the glass of Ag
Containing 2% by weight of ₂ O, dissolution rate 0.19 mg / g glass
/ Hr, adjusted to an average particle size of 40 μm or less. B ₂ O ₃ 60 mol%, ZnO 30 mol%, Na
The ₂ O10mol% glass dissolution rate 0.04 mg / Glass g / Hr, which was adjusted to less than or equal to the average particle size of 10 [mu] m. B ₂ O ₃ 45 mol%, SiO ₂ 40 mol%, N
a ₂ dissolved O15mol% glass rate 0.6 mg / Glass g / Hr, which was adjusted to less than or equal to the average particle size of 40 [mu] m. Same glass as the above but adjusted to an average particle size of 70 μm.

A porcelain plate (10 × 10 cm) on which glaze (porcelain glaze, 10 mg / cm ² ) was placed was placed in a chamber in which various soluble glasses were suspended in the air for a certain period of time, and placed on the glaze. The amount of spray was determined by increasing the weight. Next, in an electric furnace, the temperature was raised to a predetermined temperature to cause mutual melting and slow cooling. The following evaluation was performed on this sample. Antibacterial effect (apply 1/50 ordinary broth containing E. coli, wrap, and
After washing at 24 ° C. for 24 hours, the cells were washed and the number of viable cells was counted using an SCDA medium. In addition, the external appearance was visually evaluated as × when the whiteness, gloss and smoothness were confirmed to be changed even a little, and as ○ when the state was not changed. After further immersing in water and after 24 hours with a Xe lamp, the presence or absence of light discoloration and peeling was visually examined by the same criteria as above. Table 1 shows the results.

[0020]

[Table 1]

[0021]

As described above, the antibacterial effect of the present invention,
The anti-mildew porcelain processing method and its product should be as maintenance-free as possible, sanitary for a long time, and not impair the appearance by baking antibacterial and antifungal melting glass on the surface of the porcelain product. Can be provided. Therefore, the present invention is extremely large in that it contributes to industrial development as an antibacterial and antifungal ceramics processing method and a product thereof that solves the conventional problems.

Claims (5)

[Claims] 1. An average particle size of 50 after applying a glaze to a ceramic.
μm and below Ag ₂ O, comprising at least one ZnO, antibacterial dissolution rate in 20 ° C. water with a particle size 500μm is equal to or less than 0.5 mg / Glass g / Hr, the antifungal soluble glass particles 0 An antibacterial and antifungal processing method for ceramics, which comprises spraying 0.001 to 5 mg / cm ² and then baking together with glaze. 2. A bismuth porcelain having an average particle size of 50 μm or less and containing at least one of Ag ₂ O and ZnO, and having a particle size of 5
0.01 mg dissolution rate in water at 20 μC at 00 μm
/ An antibacterial and antifungal processing method for ceramics, which comprises spraying antibacterial and antifungal soluble glass particles having a glass g / Hr or less and baking. 3. A glaze and an average particle size of 50 μm or less and Ag
Particle size 500 μm containing at least one of ₂ O and ZnO
And, the antibacterial and antifungal soluble glass particles having a dissolution rate in water at 20 ° C of 0.5 mg / glass g / Hr or less are premixed, sprayed on a ceramic and baked, and then the antibacterial effect of the ceramic is obtained. , Anti-mildew processing method. 4. An average particle size of 50 μm on a ceramic porcelain baked with glaze.
m or less, and contains at least one of Ag ₂ O and ZnO, and has a particle size of 500 μm and a dissolution rate in water at 20 ° C. of 0.01 mg / glass g / Hr or less. An antibacterial and antifungal processing method for ceramics, characterized by baking and baking. 5. A ceramic material containing a glaze and a surface layer further containing at least one of Ag ₂ O and ZnO having an average particle size of 50 μm or less and having a particle size of 500 μm and a dissolution rate of 0.5 mg / glass in water at 20 ° C. An antibacterial and antifungal ceramic product characterized by being fused with antibacterial and antifungal soluble glass fine particles of g / Hr or less.