JP2000072483A - Antifungal crystallized glass product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifungal crystallized glass product having antifungal property and decorating property, and to provide its producing method. SOLUTION: An antifungal crystallized glass product is made of a crystallized glass base body on which a surface layer consisting of glass and antifungal metal ion is formed. The glass product is obtd. by applying a suspension containing glass powder and antifungal metal ion on the surface of a glass sheet which has property that it crystallizes by heat treatment, or on the surface of a crystallized glass sheet, and then the glass sheet is heat treated.

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 and a method for producing the same, and more particularly to an antibacterial crystallized glass article used for building materials and a method for producing the same.

[0002]

2. Description of the Related Art Crystallized glass articles soften and flow during crystallization heat treatment and have a smooth, glossy and excellent aesthetic appearance. Further, since it is excellent in chemical durability and mechanical strength, it is widely used for exterior materials, interior materials, floor materials and the like of buildings. In recent years, its use has been widened, and it has been used as a top plate for tables and vanities, a decorative plate around a kitchen, a toilet booth, and the like.

[0003]

With the increasing awareness of health and safety, it has been required to provide building materials with a function (antibacterial property) of suppressing the generation of molds and bacteria. Also, it is required to provide antibacterial properties.

However, the production of crystallized glass requires a heat treatment step at a high temperature of about 1000 ° C. for crystallization. Therefore, even if an antibacterial agent having a heat resistance of 1000 ° C. or less is applied, the crystallized glass is applied to the crystallized glass. It is impossible to impart antibacterial properties. There are also antibacterial agents having a heat-resistant temperature of 1000 ° C. or higher, but since these carriers are mostly ceramics, they hinder the fluidity of the surface of the crystallized glass. For this reason,
It is difficult to obtain a beautiful surface utilizing the softening flow of glass.

An object of the present invention is to provide an antibacterial crystallized glass article having both antibacterial properties and aesthetic properties, and a method for producing the same.

[0006]

As a result of various studies, the present inventor has found that the above object can be achieved by supporting antimicrobial-expressing metal ions on the surface of crystallized glass instead of antimicrobial agents. And propose the present invention.

That is, the antibacterial crystallized glass article of the present invention is characterized in that a surface layer composed of glass and antibacterial metal ions is formed on a substrate made of crystallized glass.

Further, the method for producing an antibacterial crystallized glass article of the present invention comprises the steps of applying a suspension containing glass powder and an antibacterial metal ion to the surface of a glass plate having a property of crystallizing by heat treatment. It is characterized by heat treatment.

Further, another method of manufacturing an antibacterial crystallized glass article according to the present invention comprises applying a suspension containing glass powder and an antibacterial metal ion to the surface of a crystallized glass plate, followed by heat treatment. Features.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the crystallized glass article of the present invention, it is preferable to use a crystallized glass having high mechanical strength and chemical durability as a base material. Crystallized glass on which stellite or garnite is precipitated can be suitably used. More specifically, SiO ₂ 40 to 60% by weight%, Al ₂ O ₃ 10~
25%, MgO 0-12%, ZnO 0-12%, Mg
_{O + ZnO 3~15%, B 2} O 3 2~15%, Na 2 O
_{4~13%, K 2 O 0~5%} , CaO 0~5%, Ba
O 0-5%, TiO ₂ 0-5%, ZrO ₂ 0-5
%, TiO ₂ + ZrO ₂ 0.5 to 8%, As ₂ O _{30 to} 0
It is desirable to use crystallized glass having a composition of 1% and Sb ₂ O ₃ 0 to 1%.

In the present invention, the surface layer comprises glass and metal ions exhibiting antibacterial properties. The thickness of the surface layer is 0.1
It is preferably about 1000 μm.

The glass may be an amorphous glass or a crystallized glass, but is preferably a crystallized glass from the viewpoint of mechanical strength and chemical durability. In particular, when crystallized glass having substantially the same composition as the crystallized glass constituting the base material, warpage due to a difference in expansion can be prevented.

As the antibacterial metal ion, Ag ion, Zn ion, Cu ion and the like can be used, but Ag ion is particularly preferable since it has the highest antibacterial property. When Ag ions are used, it is desirable that trivalent metal ions, particularly Al ions, coexist. The reason for this is that silver has a strong reducing property and becomes a silver colloid, which tends to cause deterioration of antibacterial performance and coloring. However, coexistence of trivalent metal ions can prevent this. . For example, in the case of Al ions, the content of the trivalent metal ions is preferably in the range of 0.1 to 10 in terms of a molar ratio of Al ions / Ag ions. When the molar ratio is less than 0.1, the absolute amount for suppressing the reduction of Ag ions is insufficient, and when the molar ratio is greater than 10, excess Al is present in the surface layer. The displacement may adversely affect the surface smoothness.

The antibacterial crystallized glass article of the present invention having the above constitution can exhibit antibacterial properties by the antibacterial metal ions contained in the surface layer.

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

First, a base material is prepared. As the base material, a glass plate having a property of crystallizing when heat-treated at a temperature higher than the softening point or a crystallized glass plate obtained by crystallizing the glass plate in advance is used. It is preferable to use a glass plate or a crystallized glass plate having high mechanical strength and chemical durability, for example, glass having a property of precipitating forsterite or garnite which has been conventionally used for building materials. It is preferable to use one made of crystallized glass on which forsterite or garnite is precipitated.

A suspension containing a glass powder and an antibacterial metal ion is prepared.

As the solvent, water or a water-soluble alcohol such as ethanol or methanol is used. Normally, water may be used. However, glass having high chemical durability is basically resistant to water, and it may be difficult to uniformly apply glass when water is used as a solvent. In such a case, by using a water-soluble alcohol having a higher wettability to glass than water, it is possible to easily coat the glass surface.

As the glass powder, it is preferable to use glass that can be crystallized from the viewpoint of mechanical strength and chemical durability, and particularly has substantially the same oxide composition as the crystallized glass constituting the base material. It is desirable to use glass. It is desirable to use a glass powder having a small spherical shape with an average particle diameter of 10 μm or less. The amount of the glass powder to be added is preferably 10 to 1000 times the weight of the antibacterial metal by weight. If the glass powder is smaller than 10 times, the absolute amount of the glass powder is too small to be sufficiently applied to the surface of the glass plate, and if it exceeds 1000 times, the glass powder may be sufficiently dispersed in the solvent. It becomes difficult.

Ag ions, Zn ions, Cu ions and the like are preferable as the metal ions exhibiting antibacterial properties. In order to obtain these ions, metal salts such as Ag, Zn, and Cu (silver nitrate, zinc nitrate hexahydrate, cupric chloride dihydrate, etc.) are used. The amount of the metal salt dissolved in the solvent is suitably from 0.01 to 10% by weight. If the amount of dissolution is less than 0.01%, the dispersibility of the metal ions in the solvent will deteriorate when dissolved. Conversely, when the amount of dissolution is more than 10%, the decomposability of metal ions deteriorates. When a metal salt of Ag is used, a trivalent metal salt such as an aluminum salt (aluminum nitrate nonahydrate) is preferably used in combination. The reason is that silver has a strong reducing property, and even if it is taken into glass, it tends to become a silver colloid at high temperatures. In addition, since there is a possibility of being released by evaporation, it is necessary to add a metal salt that becomes a negative charge center when it enters the glass matrix. The concentration is, for example, Al / A
The range of 0.1 to 10 in terms of g mole ratio is desirable.

When water is used as the solvent, a water-soluble thickener is added in accordance with the molar amount of the dissolved metal salt to control the viscosity at the time of coating on a glass plate. 1
It can be adjusted to be ~ 50 cps. Furthermore, an aminosilane-based coupling agent can be added to increase the adhesiveness when applying to the glass plate surface.

To prepare a suspension, first add a metal salt (and further, if necessary, a thickener or a coupling agent) to a solvent, dissolve it completely, and then add glass powder. Can be dispersed.

Next, the suspension is applied to the surface of the glass plate and dried. As a coating method, spray coating, spin coating, dip coating, or the like can be used.

Thereafter, the glass powder is softened and fluidized by heat treatment at a temperature higher than the softening point to fuse and integrate the glass powder with the glass plate and to fix the antimicrobial-expressing metal ions in the surface layer. Thus, a crystallized glass article comprising the base material and the surface layer is obtained. When crystallizable glass is used for a glass powder or a glass plate, a crystal is precipitated by this heat treatment, and a crystallized glass is obtained.

[0025]

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

1. Preparation of Sample [Sample No. 1] First, a glass plate, glass powder, a metal salt for obtaining an antibacterial metal ion, and a trivalent metal salt were prepared.

The glass plate and glass powder contain S by weight.
iO ₂ 50%, Al ₂ O ₃ 15%, MgO 5%, ZnO
5%, B ₂ O ₃ 10%, Na ₂ O 8%, K ₂ O 2%, T
Glass having a composition of 3% of iO _{2 and 2} % of ZrO ₂ and having a property of precipitating forsterite and garnite was used. The glass plate used had a size of 50 × 50 × 10 mm, and the glass powder used was a small sphere having an average particle size of 5 μm.

Silver nitrate was used as a metal salt for obtaining a metal ion exhibiting antibacterial properties.

As the trivalent metal salt, aluminum nitrate nonahydrate was used.

Next, silver nitrate and aluminum nitrate nonahydrate were dissolved in 100 cc of distilled water so that the Al / Ag molar ratio was 1 and the amount of glass powder was 100 times the amount of Ag. The powder was charged and evenly dispersed in the solution.

Subsequently, the suspension thus prepared is
Apply it to the glass plate surface with a spray coater, and dry in a drying oven.
It was dried at 00 ° C. for 30 minutes. Since the glass plate has high water resistance, the surface layer was removed by polishing with SiC to improve the wettability to the suspension.

Thereafter, a heat treatment was performed at 1050 ° C. for 1 hour to obtain a crystallized glass plate having a surface layer of about 1 μm containing Ag ions and having a size of 50 × 50 × 10 mm.

[Sample No. 2] First, a glass plate, glass powder, silver nitrate, and aluminum nitrate nonahydrate were prepared.

The sample No. was placed on the glass plate and the glass powder.
Glass having the same composition as the glass used in 1 was used. The glass plate used had a size of 50 × 50 × 10 mm, and the glass powder used was a small sphere having an average particle size of 3 μm.

Next, silver nitrate and aluminum nitrate nonahydrate were dissolved in 100 cc of distilled water so that the Al / Ag molar ratio was 0.2 and the amount of glass powder was 200 times that of Ag, and was completely dissolved. Thereafter, a glass powder was charged and uniformly dispersed in the solution to prepare a suspension.

Subsequently, the sample No. The suspension was applied to a glass plate in the same manner as in Example 1, dried, and then subjected to a heat treatment to have a surface layer of about 3 μm containing Ag ions.
A crystallized glass plate having a size of 50 × 10 mm was obtained.

[Sample No. 3] First, the sample No. In the same manner as in 1, a glass plate, glass powder, silver nitrate, and aluminum nitrate nonahydrate were prepared.

Next, 100 cc of ethanol (99.5)
%), The Al / Ag molar ratio is 1, and the glass powder is 10% of Ag.
Dissolve silver nitrate and aluminum nitrate nonahydrate so that the volume becomes 0 times, and after completely dissolving, add glass powder,
It was evenly dispersed in the solution.

Subsequently, the suspension thus prepared was
It was applied to the surface of a glass plate with a spray coater and air-dried.

Thereafter, a heat treatment was carried out at 1050 ° C. for 1 hour to obtain a crystallized glass plate having a surface layer of about 1 μm containing Ag ions and having a size of 50 × 50 × 10 mm.

[Sample No. 4] First, the sample No. In the same manner as in 2, a glass plate, glass powder, silver nitrate, and aluminum nitrate nonahydrate were prepared.

Next, 100 cc of ethanol (99.5)
%), A silver powder and an aluminum nitrate nonahydrate were dissolved so that the Al / Ag molar ratio was 0.2 and the glass powder was 200 times the amount of Ag, and after the glass powder was completely dissolved, the glass powder was added. To make a suspension.

Subsequently, the sample No. In the same manner as in Example 3, the suspension was applied to a glass plate, air-dried, and then heat-treated to have a surface layer of about 3 μm containing Ag ions.
A crystallized glass plate having a size of 50 × 10 mm was obtained.

[Sample No. 5] First, a crystallized glass plate,
Glass powder, silver nitrate, and aluminum nitrate nonahydrate were prepared.

On the crystallized glass plate, SiO ₂ 5
0%, Al ₂ O ₃ 15%, MgO 5%, ZnO 5%,
B ₂ O ₃ 10%, Na ₂ O 8%, K ₂ O 2%, TiO ₂
A crystallized glass (50 × 50 × 1) having a composition of 3% and ZrO ₂ 2%, on which forsterite and garnite are deposited.
0 mm). The glass powder includes a small spherical glass having an oxide composition identical to that of the glass plate and having a property of precipitating forsterite and garnite (average particle size of 5 μm).
m) was used.

Next, the sample No. In the same manner as in 1, a suspension was prepared and applied to a glass plate, dried, and then heat-treated to have a surface layer of about 1 μm containing Ag ions.
A crystallized glass plate having a size of 0 × 50 × 10 mm was obtained.

[Comparative Example] The crystallized glass plate prepared in 5 was used as a sample.

2. Test method Next, the test method will be described.

[Preparation of bacterial solution]
The test strain, which had been pre-cultured for 2 hours, was inoculated again into NA medium,
The cells cultured at 7 ± 1 ° C. for 24 hours are uniformly dispersed in 1/500 NB medium, and the number of cells per ml is 1.0 × 10 4
^It was adjusted to be ^{5 to} 1.0 × 10 ⁶ .

[Preparation of Sample] A sample (Sample Nos. 1 to 5 and Comparative Example) was wiped lightly with absorbent cotton impregnated with 99.5% ethanol and air-dried.

[Test operation] Bacterial solution was dropped at a rate of 0.5 ml to the surface of each sample (25 cm ² ), and a polyethylene film was covered thereon and adhered. These are 35
It was stored under conditions of ± 1 ° C. and relative humidity of 90% or more.

[Measurement of viable cell count] After storage for 24 hours, SC
Surviving bacteria were washed out of the sample with a DLP medium, and the viable cell count of the washed liquid was determined by an agar plate culture method using an SA medium (35).
C. for 2 days) and converted to one sample. The initial number of bacteria was 1.5 × 10 ⁵ .

3. Results The results measured using the above method are shown in Table 1.

[0054]

[Table 1]

As is clear from the table, Sample No. 1-5
Each of the samples had a viable cell count of less than 10 and a sterilization rate of 99% or more. On the other hand, in the sample of the comparative example, the number of viable bacteria did not decrease at all.

These facts indicate that the crystallized glass article of the present invention has sufficient antibacterial performance.

[0057]

Industrial Applicability The antibacterial crystallized glass article of the present invention has excellent chemical durability and mechanical strength properties, can obtain aesthetics, and exhibits excellent antibacterial performance over a long period of time. Therefore, generation of mold and bacteria can be prevented. Therefore, it is particularly suitable as a building material used in applications requiring consideration for hygiene, such as table tops, vanity tops, kitchen vanity veneers, toilet booths, and hospital interior materials.

Claims (13)

[Claims] 1. An antibacterial crystallized glass article comprising a substrate made of crystallized glass and a surface layer composed of glass and antibacterial metal ions formed thereon. 2. The antibacterial crystallized glass article according to claim 1, wherein the antibacterial metal ion is an Ag ion. 3. The antibacterial crystallized glass article according to claim 1, wherein the glass of the surface layer is crystallized glass. 4. The antibacterial crystallized glass article according to claim 3, wherein the crystallized glass of the substrate and the crystallized glass of the surface layer have substantially the same composition. 5. The antibacterial crystallized glass article according to claim 1, which is used as a building material. 6. An antibacterial property which comprises applying a suspension containing glass powder and an antibacterial metal ion to a surface of a glass plate having a property of crystallizing while softening and flowing upon heat treatment, followed by heat treatment. A method for producing a crystallized glass article. 7. The method for producing an antibacterial crystallized glass article according to claim 6, wherein Ag ions are used as the antibacterial metal ions. 8. The glass powder according to claim 6, wherein the glass powder has a property of crystallizing upon heat treatment.
A method for producing an antibacterial crystallized glass article. 9. The method for producing an antibacterial crystallized glass article according to claim 8, wherein the glass plate and the glass powder have substantially the same composition. 10. After applying a suspension containing glass powder and antibacterial metal ions to the surface of a crystallized glass plate,
A method for producing an antibacterial crystallized glass article, comprising heat-treating. 11. The method for producing an antibacterial crystallized glass article according to claim 10, wherein Ag ions are used as the antibacterial metal ions. 12. The method for producing an antibacterial crystallized glass article according to claim 10, wherein the glass powder is made of glass having a property of crystallizing when heat-treated. 13. The crystallized glass plate and the glass powder have substantially the same oxide composition.
A method for producing an antibacterial crystallized glass article.