Antibacterial crystallized glass product

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Industrial application field]

The present invention relates to an antibacterial crystallized glass article used as a building material such as an exterior material and an interior material.

【0002】

[Conventional technology]

Crystallized glass articles are widely used for exterior materials, interior materials, etc. because they have excellent properties such as chemical durability and mechanical strength and exhibit a beautiful appearance. It is also being used for top plates, decorative plates around kitchens, toilet booths, etc.

【0003】

[Problems to be Solved by the Invention]

By the way, due to the growing awareness of safety and health, it is required to give building materials a function to prevent the growth of mold and bacteria (so-called antibacterial properties), and building materials made of crystallized glass are also required to have antibacterial properties. It is required to grant.

【0004】

An object of the present invention is to provide an antibacterial crystallized glass article which has excellent antibacterial properties for a long period of time and is suitable as a building material.

【0005】

[Means for solving problems]

The antibacterial crystallized glass article of the present invention is characterized in that an antibacterial agent adheres to a base material made of crystallized glass.

【0006】

[Action]

The antibacterial crystallized glass article of the present invention exhibits antibacterial properties due to the presence of an antibacterial agent adhering to the surface of the glass article. As the antibacterial agent, a conventionally known inorganic antibacterial agent having a heat resistance of 900 ° C. or higher can be used. For example, an antibacterial powder (Ag, Cu, Zn, Pb, Hg, Sn, etc.) that elutes metal ions can be used. Ceramic powder such as heat-resistant zeolite, glass powder containing Ag, Cu, Zn, etc. in the composition) and antibacterial powder having a photocatalytic function (TiO₂ Powder etc.) can be used. The preferred range for the amount of antibacterial agent attached is 0.01 to 10 g / cm.² , Especially 0.01 ~ 5g / cm² Is. The antibacterial agent is 0.01 g / cm² If it is less, the antibacterial effect will be smaller, 10 g / cm² If it is more than that, the fluidity of the surface becomes poor, and a smooth surface state cannot be obtained.

【0007】

When heat-treated at a temperature higher than the softening point, the base material is softened and deformed, and a large number of glass bodies having the property of precipitating needle-shaped crystals from the surface to the inside are fused and integrated and crystallized. A crystallized glass plate made of glass or a crystallized glass plate obtained by crystallizing a glass plate having the property of growing crystals from crystal nuclei generated inside the glass while being softened and deformed by heat treatment at a temperature higher than the softening point can be used. For the former crystallized glass plate, for example, SiO by weight percentage₂ 40-80%, Al₂ O₃ 1 ~ 25%, CaO 3 ~ 25%, ZnO 0 ~ 15%, BaO 0 ~ 20%, B₂ O₃ 0 ~ 15%, Na₂ O + K₂ O + Li₂ O 2 ~ 25%, MgO 1 ~ 20%, TiO₂ 0 ~ 5%, ZrO₂ A surface crystallized type crystallized glass having a composition of 0 to 5% and having crystals of β-wollastonite, diopside, devitrite, etc. precipitated can be used, and the latter crystallized glass plate can be used. For example, SiO by weight percentage₂ 40-60%, Al₂ O₃ 10 ~ 25%, MgO 0 ~ 12%, ZnO 0 ~ 12%, MgO + ZnO 3 ~ 15%, B₂ O₃ 2 ~ 15%, Na₂ O 4 ~ 13%, K₂ O 0 ~ 5%, CaO 0 ~ 5%, BaO 0 ~ 5%, TiO₂ 0 ~ 5%, ZrO₂ 0-5%, TiO₂ + ZrO₂ 0.5-8%, As₂ O₃ 0 ~ 1%, Sb₂ O₃ Crystallized glass having a composition of 0 to 1% and precipitating forsterite and / or garnate, or SiO by weight percentage₂ 40-70%, Al₂ O₃ 5-25%, Na₂ O 2 ~ 16%, CaO 1 ~ 20%, TiO₂ 0.5 ~ 15%, ZrO₂ 0.1 ~ 10%, CaO + TiO₂ + ZrO₂ 4-25%, B₂ O₃ 0 ~ 15%, P₂ O₅ 0 ~ 5%, K₂ O 0 ~ 5%, BaO 0 ~ 5%, As₂ O₃ 0 ~ 1%, Sb₂O₃ Surface crystallization type crystallized glass such as crystallized glass having a composition of 0 to 1% and having zirconolite precipitated as a main crystal can be used. These crystallized glasses are excellent in chemical durability and mechanical strength, can exhibit a beautiful appearance, and can be suitably used for building material applications.

【0008】

Next, a method for producing the antibacterial crystallized glass of the present invention will be described. The production method of the present invention can be broadly divided into the following four, but is not limited to these.

【0009】

In the first production method, first, a large number of glass bodies having a property of softening and deforming when heat-treated at a temperature higher than the softening point and precipitating crystals from the surface to the inside are prepared. In this glass body, for example, SiO by weight percentage₂ 40-80%, Al₂ O₃ 1 ~ 25%, CaO 3 ~ 25%, ZnO 0 ~ 15%, BaO 0 ~ 20%, B₂ O₃ 0 ~ 15%, Na₂ O + K₂ O + Li₂ O2 ~ 25%, MgO 1 ~ 20%, TiO₂ 0 ~ 5%, ZrO₂ A surface crystallization type crystalline glass having a composition of 0 to 5% and having a property of precipitating crystals such as β-wollastonite, diopside, and diopside can be used. As the glass body, various shapes such as small spherical shape, granular shape, scaly shape, crushed shape, and rod shape can be used.

【0010】

Next, the glass bodies are accumulated in the mold coated with the antibacterial agent powder. Here, it is important to use an inorganic antibacterial agent that can withstand high temperatures in the subsequent firing step as the antibacterial agent powder. As such an antibacterial agent, for example, an antibacterial powder that elutes metal ions (ceramic powder such as heat-resistant zeolite carrying a metal such as Ag, Cu, Zn, Pb, Hg, Sn, etc., Ag, Cu, Zn, etc. is composed. (Glass powder contained in it, etc.) and antibacterial powder having a photocatalytic function (TiO)₂ (Powder, etc.) is preferable. The antibacterial agent powder preferably has an average particle size of 500 μm or less, and the amount of the antibacterial agent powder applied is 0.01 to 10 g / cm with respect to the mold surface.² , Especially 0.01 ~ 5g / cm² It is preferable to adjust so as to be. When accumulating the glass bodies, it is preferable to apply the release material powder in the mold. In this case, the release material powder and the antibacterial agent powder may be applied to the mold separately, or they may be mixed in advance and applied at once. Instead of the method of applying the antibacterial agent powder into the mold, a release sheet containing the antibacterial agent powder may be used.

【0011】

After that, when the heat treatment is performed at a temperature equal to or higher than the softening point of the glass, the glass bodies are fused and integrated while being softened and deformed, and crystals are precipitated from the surface of the glass bodies toward the inside. Further, the antibacterial agent powder applied to the mold is fixed to the surface of the article by the softened glass. In this way, a crystallized glass article in which the antibacterial agent is firmly adhered to the surface of the crystallized glass plate can be obtained. When crystalline glass having the above composition system is used for the glass body, firing is preferably performed in a temperature range of 800 to 1100 ° C.

【0012】

In the second manufacturing method, as in the first manufacturing method, when heat treatment is first performed at a temperature higher than the softening point, a large number of glass bodies having the property of softening and deforming and precipitating crystals from the surface to the inside are produced. prepare.

【0013】

Next, the glass bodies are accumulated in the mold. In accumulating the glass bodies, it is preferable to apply a mold release material powder in the mold or place a mold release sheet on the mold.

【0014】

Subsequently, the antibacterial agent powder is sprayed on the accumulated glass bodies. The antibacterial agent powder may be sprayed directly, or may be kneaded with water, a binder or the like to form a slurry, and sprayed or the like. The amount of antibacterial powder sprayed is 0.01 to 10 g / cm.², Especially 0.01 ~ 5g / cm² The range of is preferable. Instead of the method of spraying the antibacterial agent powder, a mold having the antibacterial agent powder (and a mold release agent) coated on the surface may be placed on the glass body.

【0015】

After that, when the heat treatment is performed at a temperature equal to or higher than the softening point of the glass, the glass bodies are fused and integrated and crystallized, and the sprayed antibacterial agent powder is fixed to the surface of the article by the softened glass. In this way, a crystallized glass article in which the antibacterial agent is firmly adhered to the surface of the crystallized glass plate can be obtained.

【0016】

In the third manufacturing method, first, a glass plate having a property of softening and deforming when heat-treated at a temperature higher than the softening point and having a property of growing crystals from crystal nuclei generated inside the glass is prepared. On this glass plate, for example, SiO by weight percentage₂ 40-60%, Al₂ O₃ 10 ~ 25%, MgO 0 ~ 12%, ZnO 0 ~ 12%, MgO + ZnO 3 ~ 15%, B₂ O₃ 2 ~ 15%, Na₂ O 4 ~ 13%, K₂ O 0 ~ 5%, CaO 0 ~ 5%, BaO 0 ~ 5%, TiO₂ 0 ~ 5%, ZrO₂0-5%, TiO₂ + ZrO₂ 0.5-8%, As₂ O₃ 0 ~ 1%, Sb₂ O₃ Glass with a composition of 0 to 1% and the property of precipitating forsterite and / or garnate, or SiO by weight percentage₂ 40-70%, Al₂ O₃5-25%, Na₂ O 2 ~ 16%, CaO 1 ~ 20%, TiO₂ 0.5 ~ 15%, ZrO₂ 0.1 ~ 10%, CaO + TiO₂ + ZrO₂ 4-25%, B₂ O₃ 0 ~ 15%, P₂ O₅ 0 ~ 5%, K₂ O 0 ~ 5%, BaO 0 ~ 5%, As₂ O₃ 0 ~ 1%, Sb₂ O₃ Volumetric crystallized glass such as glass having a composition of 0 to 1% and having a property of precipitating zirconolite as a main crystal can be used.

【0017】

Next, the glass plate is placed in the mold coated with the antibacterial agent powder. The antibacterial agent powder preferably has an average particle size of 500 μm or less, and the amount of the antibacterial agent powder applied is 0.01 to 10 g / cm with respect to the mold surface.² , Especially 0.01 ~ 5g / cm² It is preferable to adjust so as to be. When placing the glass plate, it is preferable to apply the release material powder in the mold. In this case, the release material powder and the antibacterial agent powder may be applied to the mold separately, or they may be mixed in advance and applied at once. Instead of the method of applying the antibacterial agent powder into the mold, a release sheet containing the antibacterial agent powder may be used.

【0018】

After that, when the heat treatment is performed at a temperature equal to or higher than the softening point of the glass, the glass plate is softened and deformed, crystal nuclei are formed inside the glass, and crystals grow from the crystal nuclei. In addition, the antibacterial agent powder applied to the mold is fixed to the surface of the article by softened glass. In this way, a crystallized glass article in which the antibacterial agent is firmly adhered to the surface of the crystallized glass plate can be obtained. When crystalline glass having the above composition system is used for the glass body, firing is preferably performed in a temperature range of 800 to 1100 ° C.

【0019】

In the fourth manufacturing method, as in the third manufacturing method, a glass plate having a property of first softening and deforming when heat-treated at a temperature higher than the softening point and growing crystals from crystal nuclei generated inside the glass is prepared.

【0020】

Next, the glass plate is placed in the mold. When placing the glass plate, it is preferable to apply the release material powder in the mold.

【0021】

Subsequently, the antibacterial agent powder is sprayed on the surface of the glass plate. The antibacterial agent powder may be sprayed directly, or may be kneaded with water, a binder or the like to form a slurry, and sprayed or the like. The amount of antibacterial powder sprayed is 0.01 to 10 g / cm.² , Especially 0.01 ~ 5g / cm² The range of is preferable.

【0022】

After that, when the heat treatment is performed at a temperature equal to or higher than the softening point of the glass, the glass plate is softened and deformed, and crystals grow from the crystal nuclei generated inside the glass. In addition, the sprayed antibacterial agent powder is fixed to the surface of the article by softened glass. In this way, a crystallized glass article in which the antibacterial agent is firmly adhered to the surface of the crystallized glass plate can be obtained.

【0023】

[Example]

Hereinafter, the present invention will be described based on examples.

【0024】

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

【0025】

As a glass body, SiO by weight%₂ 60%, Al₂ O₃ 6%, CaO 17%, BaO 8%, MgO 2%, Na₂ O 5%, K₂ O 1.5%, Li₂ O Small spherical glass with a composition of 0.5% and a particle size of 1 to 5 mm (softening point 750 ° C) was used.

【0026】

As the antibacterial agent powder, an antibacterial zeolite powder carrying Ag (average particle size 10 μm) was used. The antibacterial agent powder is mixed with the release agent powder (calcium sulfate powder 80% by weight, zinc oxide powder 20% by weight), and the ratio is 10% by weight of the antibacterial agent powder and 90% by weight of the release agent powder. And said.

【0027】

Next, a mixed powder of an antibacterial agent and a mold release agent was applied to the mold. For the formwork, we used a mullite formwork with internal dimensions of 900 x 600 x 30 mm and a stone pattern formed on the bottom surface. The mixed powder was applied to the mold by adding 1000 cc of water to 1.1 kg of the mixed powder to prepare a slurry and using a spray coating machine. The amount of antibacterial agent applied to the surface of the mold is about 0.1 g / cm.² It was adjusted to be.

【0028】

Subsequently, the glass bodies were accumulated in the mold and the surface was smoothed.

【0029】

Then, by heat-treating at 1050 ° C. for 3 hours, a sample having a size of 900 × 600 × 15 mm and having a stone pattern on the surface was obtained.

【0030】

When the precipitated crystals of the obtained sample were confirmed by X-ray diffraction, it was found that β-wollastonite was precipitated as the main crystal. In addition, when the surface with the stone pattern that was in contact with the release agent was observed by EPMA analysis, it was confirmed that Ag, which is an antibacterial component, was present on the surface.

【0031】

Next, the antibacterial property was evaluated. First, a sample was cut out to a size of 50 × 50 mm to obtain a test piece. Next, two types of bacteria, Escherichia coli and Staphylococcus aureus, were prepared, and the concentrations of these bacteria were 2 × 10 respectively.³ /cm² The gelatin adjusted to be the same was processed into a sheet and attached to each test piece after the sterilization treatment. 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 were regarded as poor. As a result, both Escherichia coli and Staphylococcus aureus had less than 10 viable bacteria and had good antibacterial properties.

【0032】

(Example 2) First, a glass body was prepared in the same manner as in Example 1.

【0033】

Also, as an antibacterial agent powder, ZnO 40% by weight, B₂ O₃ 40%, Na₂O 15%, SiO₂ 4%, Al₂ O₃ An antibacterial glass powder (average particle size 50 μm) having a composition of 1% was prepared.

【0034】

Next, the glass bodies were accumulated in the mold and the surface was smoothed. For the mold, a mullite mold having an inner size of 900 × 600 × 30 mm coated with a mold release agent powder (calcium sulfate powder 80% by weight, zinc oxide powder 20% by weight) was used.

【0035】

Subsequently, the antibacterial agent powder was uniformly sprayed on the glass body using a sieve. The amount of spray is about 0.6 g / cm.² It was adjusted to be.

【0036】

Then, by heat-treating at 1050 ° C. for 3 hours, a sample having a size of 900 × 600 × 15 mm and having a glossy natural marble pattern was obtained.

【0037】

When the precipitated crystals of the obtained sample were confirmed by X-ray diffraction, it was found that β-wollastonite was precipitated as the main crystal. Moreover, when the surface on which the antibacterial agent was sprayed was observed by EPMA analysis, it was confirmed that Zn, which is an antibacterial component, was present on the surface. Moreover, when the antibacterial property was evaluated in the same manner as in Example 1, the viable cell count after culturing was less than 10 for both Escherichia coli and Staphylococcus aureus, and had good antibacterial property.

【0038】

(Example 3) First, a glass plate and an antibacterial agent powder were prepared.

【0039】

As a glass plate, SiO by weight%₂ 53.0%, Al₂ O₃ 14.0%, MgO 3.5%, ZnO 4.0%, B₂ O₃ 13.0%, Na₂ O 5.5%, K₂ O 1.3%, CaO 1.0%, TiO₂ 3.0%, ZrO₂1.5%, Sb₂ O₃ A glass plate (softening point 750 ° C) having a composition of 0.2% and a size of 900 × 900 × 5 mm was prepared.

【0040】

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

【0041】

Next, a glass plate was placed on a mullite mold having an inner size of 900 × 900 × 25 mm coated with a mold release agent powder (calcium sulfate powder 80% by weight, zinc oxide powder 20% by weight).

【0042】

Subsequently, the antibacterial agent powder was uniformly sprayed on the glass plate using a sieve. The amount of spray is about 0.1 g / cm.² It was adjusted to be.

【0043】

Then, by heat-treating at 900 ° C. for 1 hour, a sample having a size of 900 × 900 × 5 mm and having a glossy fire-made surface was obtained.

【0044】

When the precipitated crystals of the obtained sample were confirmed by X-ray diffraction, it was found that forsterite and garnite were precipitated. Moreover, when the surface on which the release agent was sprayed was observed by EPMA analysis, it was confirmed that Ag, which is an antibacterial component, was present on the surface. Moreover, when the antibacterial property was evaluated in the same manner as in Example 1, the viable cell count after culturing was less than 10 for both Escherichia coli and Staphylococcus aureus, and had good antibacterial property.

【0045】

[Effect of the invention]

The antibacterial crystallized glass article of the present invention has excellent properties such as chemical durability and mechanical strength, can exhibit a beautiful appearance, and exhibits excellent antibacterial properties over a long period of time. Can be prevented from occurring. Therefore, it is particularly suitable as a building material used for applications requiring hygiene consideration, such as a table or a vanity top plate, a veneer around a kitchen, a toilet booth, or a hospital interior material.

【0046】

The crystallized glass article of the present invention is not limited to the above-mentioned use for building materials, but can also be used as other crystallized glass products such as top plates of smooth-stop cookers and turntables of microwave ovens. Is.