JPH1160270A - Antimicrobial crystallized glass article and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject glass article having excellent antimicrobial effect over a long period and suitable as a construction material, and to provide a method for producing the above glass article. SOLUTION: First, a number of small glass bodies having such a character that, when subjected to heat treatment at a temperature higher than the softening point, needle crystals are deposited from the surface toward the interior while softening and deforming, are prepared. Next, antimicrobial agent powder is attached to the surface of the glass bodies. Subsequently, the resulting small glass bodies are collected in a mold and heat-treated at a temperature higher than the softening point of the glass, thus obtaining the objective antimicrobial glass article where a number of the small glass bodies are integratedly fused, with needle crystals deposited therein and antimicrobial agent layers formed on the interface among the small glass bodies.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial crystallized glass article used for building materials such as exterior materials, interior materials, flooring materials and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Crystallized glass articles have excellent properties such as chemical durability and mechanical strength and have a beautiful appearance. Therefore, they are widely used as exterior materials, interior materials, floor materials, etc. instead of natural stones. In recent years, its use has been widened, and it has also been used as a tabletop, a vanity top plate, a toilet booth, and the like.

[0003] As a method for producing such a crystallized glass article, a method called an integration method is known. In the integration method, first, when a heat treatment is performed at a temperature higher than the softening point, a large number of glass bodies having a property that needle-like crystals are precipitated from the surface to the inside while softening and deforming are prepared, and then the glass bodies are placed in a mold. And a heat treatment at a temperature equal to or higher than the softening point of the glass, so that a crystallized glass article having a natural marble-like appearance can be obtained.

[0004]

By the way, with the increasing awareness of safety and health, it is required to provide building materials with a function of preventing the generation of mold and bacteria (so-called antibacterial properties). It is also required that antibacterial properties be imparted to building materials.

[0005] As a method of imparting antibacterial properties to building materials,
A method is known in which an antimicrobial agent is mixed with a resin or paint and applied to the product surface.However, the antimicrobial layer formed by this method is not durable, and deteriorates and falls off over a long period of use, resulting in reduced functionality. There is a disadvantage of doing so.

An object of the present invention is to provide an antibacterial crystallized glass article having excellent antibacterial properties over a long period of time and suitable as a building material, and a method for producing the same.

[0007]

SUMMARY OF THE INVENTION The antibacterial crystallized glass article of the present invention is characterized in that, when heat-treated at a temperature higher than the softening point, needle-like crystals precipitate from the surface toward the inside while softening and deforming. A crystallized glass article in which a large number of bodies are fused and integrated and crystals are precipitated,
An antimicrobial layer comprising an antimicrobial agent is formed on the interface of the glass body.

[0008] The method for producing an antibacterial crystallized glass article of the present invention is characterized in that, when heat-treated at a temperature higher than the softening point, a glass body having a property that needle-like crystals precipitate from the surface toward the inside while softening and deforming. A crystal comprising a step of preparing a large number of pieces, a step of accumulating glass bodies in a mold, and a step of fusing and integrating the glass bodies by heat treatment at a temperature equal to or higher than the softening point of the glass and crystallizing the glass bodies. What is claimed is: 1. A method for producing a glass-foamed article, characterized in that an antibacterial agent powder is previously adhered to the surface of a glass body.

[0009]

The antibacterial crystallized glass article of the present invention has an antibacterial property because an antibacterial layer is present at the interface of the glass body. The antibacterial layer is made of a conventionally known antibacterial agent, for example, an antibacterial powder (Ag, Cu, Zn, Pb, H
It is formed of a ceramic powder such as zeolite carrying a metal such as g or Sn, a glass powder containing Ag, Cu, Zn or the like in its composition) or an antibacterial powder having a photocatalytic function (TiO ₂ powder or the like). In addition, it is preferable that content of an antibacterial agent is 0.01-30 weight part with respect to 100 weight part of crystallized glass.

In the glass article of the present invention, the precipitated crystals of the crystallized glass used are β-wollastonite (CaO.SiO ₂ ), diopside (CaO.Mg).
O.2SiO ₂ ), debitrite (Na ₂ O.3CaO)
• Needle-like crystals such as 6SiO ₂ ). These crystals are restricted by the shape of the glass body and precipitate, and the pattern that appears based on the presence and the difference in direction gives the crystallized glass article a natural marble pattern. The composition of the crystallized glass from which the acicular crystals precipitate is, for example, Si by weight percentage.
_{O 2 40~80%, Al 2 O} 3 1~25%, CaO
3-25%, ZnO 0-15%, BaO 0-20
_{%, 0~20% MgO, B 2} O 3 0~15%, Na
₂ O + K ₂ O + Li ₂ O 2 to 25%, TiO ₂ 0
5%, ZrO ₂ 0-5%, and colored oxide 0-5% can be selected.

Next, a method for producing the antibacterial crystallized glass article of the present invention will be described.

First, a glass body and an antibacterial agent powder are prepared.

As the glass body, a glass body having such a property that, when heat-treated at a temperature higher than the softening point, needle-like crystals are precipitated from the surface toward the inside while being softened and deformed.
As the glass particles, those that precipitate various crystals can be used, but those having the property of depositing β-wollastonite, diopside, or devitrite as a main crystal are particularly preferable. As such a glass, for example, SiO ₂ 40 to 80% by weight percentage, Al ₂ O ₃ 1 to 25
%, CaO 3-25%, ZnO 0-15%, BaO
0~20%, 0~20% MgO, B 2 O 3 0~1
5%, Na ₂ O + K ₂ O + Li ₂ O 2 to 25%, Ti
O ₂ 0-5%, ZrO ₂ 0-5%, colored oxide 0
Glass having a composition of 〜5% can be used.
In addition, small glass, small spherical, granular, scale-like, crushed,
What has various shapes, such as a powder form and a stick form, can be used.

As the antibacterial agent powder, a conventionally known antibacterial agent can be used. For example, an antibacterial powder (A
g, Cu, Zn, Pb, Hg, ceramic powder such as zeolite carrying a metal such as Sn, glass powder containing Ag, Cu, Zn, etc. in the composition), and antibacterial powder (TiO ₂ ) having a photocatalytic function Powder). When zeolite is used, it is preferable to select one having excellent heat resistance.

Next, the glass body and the antibacterial agent powder are mixed,
An antibacterial agent powder is attached to the surface of the glass body. As a method of attaching the antibacterial agent powder to the surface of the glass body, first, these are weighed in an appropriate amount and dry-mixed. At this time, an inorganic pigment powder (pigment) may be added together with the antibacterial agent powder. Thereafter, water or a binder may be added in an amount of 0.1 to 5 parts by weight with respect to 100 parts by weight of the glass body, and sufficiently stirred and mixed. The addition amount of the antibacterial agent powder is preferably 0.01 to 30 parts by weight based on 100 parts by weight of the glass body. If the amount of the antibacterial agent powder is less than 0.01 part by weight, it becomes difficult to impart sufficient antibacterial properties to the crystallized glass article, and if it exceeds 30 parts by weight, the softening flow of the glass is reduced in the subsequent heat treatment step. There is a risk.

Subsequently, a large number of small glass bodies having the antibacterial agent powder adhered to the surface are accumulated in a refractory mold. The material and size of the refractory mold are determined in consideration of the heat treatment temperature of the glass, the product size, and the like. As the material of the formwork, metals such as stainless steel and heat-resistant alloy, SiC type, mullite type,
Refractories such as mullite-cordierite and alumina can be used.

Thereafter, when heat treatment is performed at a temperature equal to or higher than the softening point of the glass, each glass body is softened and deformed and fused and integrated with each other, and needle-like crystals such as β-wollastonite are precipitated in each glass body. I do. In addition, an antibacterial layer made of an antibacterial agent is formed at the glass body interface.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 First, a glass body and an antibacterial agent powder were prepared.

As the glass body, SiO ₂ in weight% is used.
60%, Al ₂ O ₃ 5%, CaO 17%, ZnO 6
%, BaO 6%, MgO 1%, Na ₂ O 3%, K
₂ O 1.5%, it was used a small spherical glass having a particle size of 1 to 5 mm (softening point 750 ° C.) having a composition of Li ₂ O 0.5%.

As the antibacterial agent powder, a zeolite powder carrying Ag (average particle size: 10 μm) was used.

Next, 300 g of the antibacterial agent powder was added to 30 kg of the glass body, and the mixture was dry-mixed. Then, 300 g of a 10% PVA aqueous solution was added, and the mixture was stirred and mixed, so that the antibacterial agent powder was adhered to the surface of the glass body.

Subsequently, the mixture was accumulated in a mullite mold and heat-treated at 1100 ° C. for 3 hours to obtain a sample having a size of 900 × 600 × 15 mm.

The surface of the sample thus obtained exhibited a smooth and glossy white natural marble pattern. When the precipitated crystal was confirmed by X-ray diffraction, β-wollastonite was precipitated. When the surface was observed by EPMA analysis, it was confirmed that Ag supported on zeolite was present at the interface of the glass bodies, and that an antibacterial layer was formed.

Next, the antibacterial properties were evaluated. First, a sample was cut out to 50 × 50 mm to obtain a test piece. Next, two types of bacteria, Escherichia coli and Staphylococcus aureus, were prepared, and gelatin adjusted to a concentration of 2 × 10 ³ / cm ² was processed into a sheet, and the test pieces after the sterilization were processed. Respectively. After culturing at 35 ° C. for 48 hours, the number of bacteria was measured, and those with less than 10 viable bacteria were regarded as good, and those with 10 or more viable bacteria were regarded as defective. As a result,
Both Escherichia coli and Staphylococcus aureus had less than 10 viable bacteria, indicating that they had good antibacterial properties.

Further, when the mechanical strength and the lightness (L value) were measured, the mechanical strength was 390 kg / cm ² and the lightness was 93. The mechanical strength is 50 × 250 × 15
It measured using the sample processed to the size of mm by the four-point load method. The lightness was measured with a color difference meter.

For comparison, a sample prepared in the same manner as in the example except that no antibacterial agent was contained had a mechanical strength of 40%.
Although 0 kg / cm ² and lightness were as good as 94, antibacterial properties were evaluated, and no decrease in the number of E. coli and Staphylococcus aureus was observed.

Example 2 First, a glass body, an antibacterial agent powder and an inorganic pigment powder were prepared.

As the glass body, SiO ₂ by weight% is used.
60%, Al ₂ O ₃ 9%, CaO 10%, ZnO 4
%, BaO 4%, MgO 5%, Na ₂ O 4%, K
₂ O 2.5%, a small spherical glass particle size 0.25~1mm having a composition of Li ₂ O 1.5% (softening point 700 ° C.)
It was used.

As an antibacterial agent powder, ZnO 4
_{0%, B 2 O 3 40} %, Na 2 O15%, SiO 2
A glass powder having a composition of 4% and Al ₂ O ₃ 1% (maximum particle size 1000 μm) was used.

As the inorganic pigment powder, a Co-Zn-Al-based spinel (average particle size: 1 μm, blue) was used.

Next, 1 kg of the antibacterial agent powder and 500 g of the inorganic pigment powder were added to 50 kg of the glass body and dry-mixed, and then 500 g of a 10% PVA aqueous solution was added and stirred and mixed. The antibacterial agent powder and the inorganic pigment powder were adhered.

Subsequently, the mixture was accumulated in a mullite mold and heat-treated at 1100 ° C. for 3 hours to obtain a sample having a size of 900 × 900 × 17 mm.

The surface of the sample thus obtained was smooth and glossy, and exhibited a beautiful natural marble-like appearance colored blue by an inorganic pigment present at the interface of the glass bodies. When the precipitated crystals were confirmed by X-ray diffraction, diopside was deposited. The surface is EPM
As a result of the A analysis, it was confirmed that ZnO, which is a main component of the glass powder, was present at the interface of the glass body, and that the antibacterial layer was present. Further, when the antibacterial property was evaluated in the same manner as in Example 1, it was found that the composition had good antibacterial property.

[0035]

The antibacterial crystallized glass article of the present invention has excellent properties such as mechanical strength and chemical durability and exhibits a beautiful appearance. Moreover, since it exhibits excellent antibacterial properties over a long period of time, it is possible to prevent the occurrence of molds and bacteria. Therefore, it is particularly suitable as a building material used in applications requiring consideration for hygiene, such as tabletops, vanity tops, toilet booths, and hospital interior materials.

Further, since the crystallized glass article of the present invention has an antibacterial agent also inside the article, the processed surface has antibacterial properties even if post-processing such as polishing or cutting is performed. No need for antibacterial treatment.

Further, according to the method of the present invention, the above-mentioned antibacterial crystallized glass article can be easily produced at a low cost without deteriorating the excellent properties of the crystallized glass and without greatly changing the conventional process. It is possible to manufacture.

Claims (12)

[Claims] When a heat treatment is performed at a temperature higher than the softening point, a large number of glass bodies having a property that needle-like crystals are precipitated from the surface toward the inside while being softened and deformed are fused and integrated, and crystals are precipitated. An antibacterial crystallized glass article, characterized in that an antibacterial layer made of an antibacterial agent is formed at the interface between the glass bodies. 2. An antimicrobial agent comprising Ag, Cu, Zn, Pb, H
The antibacterial crystallized glass article according to claim 1, wherein the article is made of a ceramic supporting at least one metal selected from g and Sn. 3. The antibacterial crystallized glass article according to claim 1, wherein the antibacterial agent comprises a glass containing at least one selected from Ag, Cu and Zn in the composition. 4. An antibacterial agent having a content of the crystallized glass 100
The antibacterial crystallized glass article according to claim 1, wherein the amount is 0.01 to 30 parts by weight based on part by weight. 5. The antibacterial crystallized glass article according to claim 1, wherein the needle-like crystals are at least one selected from β-wollastonite, diopside, and devitrite. 6. The crystallized glass is composed of SiO ₂ in weight percentage.
_{40~80%, Al 2 O 3 1~25} %, CaO 3
-25%, ZnO 0-15%, BaO 0-20%,
_{0~20% MgO, B 2 O 3} 0~15%, Na 2 O
+ K ₂ O + Li ₂ O 2 to 25%, TiO ₂ 0 to 5
%, The antibacterial crystallized glass article according to claim 5, characterized in that it comprises ZrO ₂ 0-5%, the coloring oxides 0-5% composition. 7. A step of preparing a large number of glass bodies having a property that needle-like crystals are precipitated from the surface toward the inside while being softened and deformed by heat treatment at a temperature higher than the softening point;
A method for producing a crystallized glass article, comprising the steps of: accumulating glass bodies in a mold; and heat-treating the glass bodies by heat treatment at a temperature equal to or higher than the softening point of the glass to fuse and integrate the glass bodies and crystallize the glass bodies. A method for producing an antibacterial crystallized glass article, wherein an antibacterial agent powder is previously adhered to the surface of a glass body. 8. Antibacterial agent powders of Ag, Cu, Zn,
The method for producing an antibacterial crystallized glass article according to claim 7, wherein a ceramic powder supporting at least one metal selected from Pb, Hg, and Sn is used. 9. The method for producing an antibacterial crystallized glass article according to claim 7, wherein a glass powder containing at least one selected from Ag, Cu, and Zn in the composition is used as the antibacterial agent powder. 10. The amount of the antimicrobial agent powder added to the glass body 1
The method for producing an antibacterial crystallized glass article according to claim 7, wherein the amount is 0.01 to 30 parts by weight based on 00 parts by weight. 11. The antibacterial crystal according to claim 7, wherein a glass body having a property of precipitating at least one needle-like crystal selected from β-wollastonite, diopside, and devitrite is used. A method for producing a fossilized glass article. 12. SiO ₂ 40-80 by weight percentage.
_{%, Al 2 O 3 1~25%} , CaO 3~25%, Z
nO 0-15%, BaO 0-20%, MgO 0
_{20%, B 2 O 3 0~15} %, Na 2 O + K 2 O + L
_{i 2 O 2~25%, TiO 2} 0~5%, ZrO 2
The method for producing an antibacterial crystallized glass article according to claim 11, wherein a glass body having a composition of 0 to 5% and a colored oxide of 0 to 5% is used.