JP2000072487A - Antibacterial crystallized glass article and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an antibacterial crystallized glass article having a superior antibacterial effect and suitable for use as a building material by forming a coating layer contg. a resin and a powdery antibacterial agent on the surface of a crystallized glass plate and curing the resin. SOLUTION: The surface of a crystallized glass plate is coated with a coating agent prepd. in the form of a slurry, paste or the like by adding a binder, a solvent, etc., to a resin and a powdery antibacterial agent. The resin is then cured by heating or irradiation with light to form a surface layer contg. the antibacterial agent on the glass plate. The crystallized glass plate may be obtd. by piling up many small glass bodies which crystallize while being softened and deformed when heat-treated and carrying out fusion and integration as well as crystallization by heat treatment. A phenolic resin, a polyester resin or a melamine resin may be used as the resin. An antibacterial material from which a metal is leached or an antibacterial material having photocatalytic function may be used as the powdery antibacterial agent.

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 and interior materials, and a method for producing the same.

[0002]

2. Description of the Related Art Crystallized glass articles are widely used as exterior materials and interior materials because of their excellent properties such as chemical durability and mechanical strength, and exhibit a beautiful appearance. It is also being used as a top plate for tables and vanities, a decorative plate around the kitchen, and a toilet booth.

[0003]

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.

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

[0005]

The antibacterial crystallized glass article of the present invention is characterized in that a surface layer made of a resin and an antibacterial agent is formed on a substrate made of crystallized glass.

Further, the method for producing an antibacterial crystallized glass article of the present invention is characterized in that after forming a coating layer containing a resin and an antibacterial agent powder on the surface of a crystallized glass plate, the resin is cured.

[0007]

The antibacterial crystallized glass article of the present invention has a surface layer provided with antibacterial properties by an antibacterial agent. The antibacterial agent powder is present only in the surface layer portion and not in the base material portion, but this is because the article is used as an exterior material or interior material, and if only the surface has antibacterial properties, it functions sufficiently. is there.

In the present invention, the crystallized glass constituting the base material
Use materials with high mechanical strength and chemical durability.
Preferably, for example, SiO 2 in weight percent_Two 40-80
%, Al_TwoO_Three 1-25%, CaO 3-25%, Zn
O 0-15%, BaO 0-20%, B_TwoO_Three 0-1
5%, Na_TwoO + K_TwoO + Li_TwoO 2-25%, MgO
1-20%, TiO_Two 0-5%, ZrO_Two 0-5%, A
s_TwoO_Three 0-1%, Sb_TwoO_Three 0-1% composition, β
-Wollastonite, diopside, debitrite, etc.
Of crystals of SiO 2 or SiO 2 by weight percentage._Two 4
0-70%, Al_TwoO_Three 5-25%, MgO 0-15
%, ZnO 0-15%, MgO + ZnO 3-20
%, B_TwoO_Three 0-15%, Na_TwoO 1-20%, K_TwoO
 0-10%, CaO 0-20%, BaO 0-10
%, TiO_Two0-10%, ZrO _Two 0-10%, TiO
_Two+ ZrO_Two 0-15%, As_TwoO_Three 0-1%, Sb_TwoO_Three
It has a composition of 0-1%, and has
Garnet, zirconolite, diopside, etc.
It is desirable to use those formed by precipitation.

In the present invention, the surface layer comprises a resin and an antibacterial agent.

As the resin, a resin having excellent transparency and high chemical durability can be used, but those which adversely affect the antibacterial function of the antibacterial agent and those which are colored or discolored by reacting with the antibacterial agent are avoided. Should. Specifically, phenolic resin, polyester resin, melamine resin, urea resin, diallyl phthalate resin, epoxy resin, silicone resin, vinyl chloride resin, vinyl acetate resin, polyethylene resin, polystyrene resin Preferred are a polypropylene resin, an acrylic resin, a polyurethane resin, a SAN resin, an ABS resin, a polycarbonate resin, a fluorine resin, a polyimide resin, a polyphenylsulfide resin, and a composite thereof.

As the antibacterial agent, conventionally known antibacterial materials can be used. For example, an antibacterial material that elutes metal ions (ceramic powder such as zeolite supporting a metal such as Ag, Cu, Zn, or Sn, a glass powder that contains Ag, Cu, Zn, or the like in its composition) or an antibacterial material having a photocatalytic function (TiO ₂ powder, TiO ₂ sol, etc.) can be used.

The surface layer preferably has a thickness in the range of 1 to 1000 μm. In order to obtain sufficient antibacterial properties and effective coloring, the surface layer is preferably 1 μm or more. However, if the thickness is more than 1000 μm, peeling due to a difference in expansion from the base material portion is likely to occur. The surface layer is preferably formed so as to cover the entire surface of the base material,
It may be partially formed as long as sufficient antibacterial properties can be obtained. Further, the surface layer may contain an inorganic pigment for coloring and a filler for improving the durability of the surface layer.

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

First, a crystallized glass plate is prepared. A crystallized glass plate is composed of a large number of glass bodies that have the property of crystallizing while being softened and deformed when heat-treated, and then heat-treated for crystallization and fusion-integration. What crystallized by heat-treating the glass plate which has the property to change into a glass can be used.

The former crystallized glass includes, for example, 40 to 80% of SiO ₂ , 1 to 25% of Al ₂ O ₃ ,
aO 3-25%, ZnO 0-15%, BaO 0
_{20%, B 2 O 3 0~15} %, Na 2 O + K 2 O + Li 2 O
2-25%, MgO 1-20%, TiO ₂ 0-5
%, ZrO ₂ 0 to 5%, As ₂ O ₃ 0 to 1%, Sb ₂ O ₃
Those having a composition of 0 to 1% and having precipitated crystals such as β-wollastonite, diopside, and debitrite can be used. In the latter crystallized glass, for example, SiO ₂ 40 to 70% by weight percentage, Al ₂ O ₃ 5 to 25
%, MgO 0-15%, ZnO 0-15%, MgO
_{+ 3~20% ZnO, B 2 O} 3 0~15%, Na 2 O
_{1~20%, K 2 O 0~10%} , CaO 0~20
%, BaO 0-10%, TiO ₂ 0-10%, ZrO
_{2 0~10%, TiO 2 + ZrO} 2 0~15%, As 2 O
₃ 0 to 1%, Sb ₂ O ₃ has 0-1% of the composition, forsterite as a main crystal, it is possible to use gahnite, Jirukonoraito, those obtained by precipitating a diopside and the like.

Next, a binder is added to the resin, the antibacterial agent powder and the like.
A slurry or a paste is prepared by adding a solvent or the like, and is applied to the surface of a glass plate to form a coating layer. For forming the coating layer, methods such as transfer, screen printing, brush coating, and spraying can be used. In particular, the thermal transfer method is suitable for mass production industrially because of its excellent mass productivity. The formed coating layer preferably has a thickness of 1 to 1000 μm.

The resin includes a phenolic resin, a polyester resin, a melamine resin, a urea resin, a diallyl phthalate resin, an epoxy resin, a silicone resin, a vinyl chloride resin, a vinyl acetate resin, a polyethylene resin, Polystyrene resins, polypropylene resins, acrylic resins, polyurethane resins, SAN resins, ABS resins, polycarbonate resins, fluorine resins, polyimide resins, polyphenylsulfide resins, and mixtures thereof can be used.

As the antibacterial agent powder, conventionally known antibacterial materials can be used. For example, an antibacterial material that elutes a metal (ceramic powder such as zeolite carrying metal ions such as Ag, Cu, Zn, and Sn, a glass powder that contains Ag, Cu, Zn, and the like in its composition) and an antibacterial material having a photocatalytic function (Such as TiO ₂ powder) can be used. The average particle size of the antibacterial agent powder is preferably 500 μm or less, and if it is larger than this, the surface gloss is lost or the color tone of the substrate is impaired.

The proportion of the antibacterial agent powder in the coating layer is desirably 0.1 to 50% by weight based on the amount of the resin. When the amount of the antibacterial agent powder is more than 50% by weight, the gloss of the surface layer is lost, and when the amount is less than 0.1% by weight, it is difficult to obtain sufficient antibacterial performance. An inorganic pigment powder for coloring and a filler for improving the durability of the surface layer may be added to the slurry or paste in an amount of 30% by weight or less based on the amount of the resin.

Thereafter, the resin is cured by heating or light irradiation, and an antibacterial crystallized glass article having a surface layer containing an antibacterial agent (or an inorganic pigment, a filler or the like) formed on a crystallized glass substrate. Can be obtained. When the resin is cured by heating, it is desirable not to heat the resin to a temperature higher than the strain point of the crystallized glass plate.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments.

(Example 1) First, SiO ₂ 60 by weight was used.
%, Al ₂ O ₃ 6%, CaO 16%, ZnO 5%,
_{BaO 5%, B 2 O 3} 1%, Na 2 O 4%, K 2 O
A small spherical glass having a composition of ₂ %, 0.5% of Li ₂ O, and 0.5% of Sb ₂ O ₃ and a particle size of 1 to 5 mm was prepared. Subsequently, the small spherical glass was integrated in a mold and heat-treated at 1050 ° C. for 3 hours. In this way, β-wollastonite is precipitated as the main crystal, and a white crystallized glass plate (90) having a smooth, undulating natural marble-like appearance is obtained.
0 × 600 × 15 mm, strain point 600 ° C.).

The resin and the antibacterial agent powder are mixed in a weight ratio of 8: 2.
And kneaded with a butyl acetate solution of polymethacrylate to obtain an ink. Note that a phenolic resin was used as the resin. Antibacterial agent powder contains ZnO by weight
_{40%, B 2 O 3 40} %, Na 2 O 15%, SiO 2
4%, Al ₂ O ₃ 1%, average particle size 100
Glass powder having antimicrobial properties of μm was used.

Next, polyethylene terephthalate (PE)
T) A transfer film was prepared by gravure printing ink on the film.

Further, the produced transfer film was placed on a glass plate, and heated and pressed by a silicon roll to transfer the coating layer (15 μm thick) to the entire surface of the glass plate.

Thereafter, the glass plate was placed in an electric furnace,
By holding at 10 ° C. for 10 minutes, an antibacterial crystallized glass article having a surface layer containing an antibacterial agent was obtained.

The crystallized glass article thus obtained had a thickness of about 15 mm and a thickness of the surface layer of about 10 μm. Appearance, the natural marble pattern of the substrate appears through the transparent surface layer, surface undulation, uneven color, color stripes,
No warpage of the article, no peeling or cracking of the surface layer was observed at all.

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.
Those that were more than one piece were regarded as defective. As a result, E. coli,
The number of viable bacteria was less than 10 for both Staphylococcus aureus, indicating good antibacterial properties.

For comparison, antimicrobial properties were evaluated for samples prepared in the same manner as in Examples except that no antimicrobial agent was contained. As a result, no decrease in the number of E. coli or Staphylococcus aureus was observed.

(Example 2) First, in terms of weight%, SiO ₂ 48
%, Al ₂ O ₃ 21%, Na ₂ O 8.5%, CaO 5
%, TiO ₂ 3.5%, ZrO ₂ 2.5%, B ₂ O ₃
A glass plate having a composition of 9.7%, BaO 1.5%, and Sb ₂ O ₃ 0.3% was heat-treated at 1000 ° C. for 1 hour. In this manner, zirconolite is precipitated as a main crystal, and a white crystallized glass plate (900 × 600 × 8 mm, having a strain point of 550) having a smooth, undulating fire-made surface.
° C).

The resin and the antibacterial agent powder are mixed in a weight ratio of 7:
3 and kneaded with a terpineol solution of ethyl cellulose to form a paste. Note that a polyester resin was used as the resin. As the antibacterial agent powder, a zeolite powder carrying Ag (average particle size: 10 μm) was used.

Next, a paste was screen-printed on the entire surface of the crystallized glass plate to form a coating layer (thickness: 40 μm).

Thereafter, the glass plate was placed in an electric furnace,
By holding at 10 ° C. for 10 minutes, an antibacterial crystallized glass article having a surface layer containing an antibacterial agent was obtained.

The crystallized glass article thus obtained had a thickness of about 8 mm and a surface layer of about 30 μm. The appearance was such that the fired surface of the base material appeared through the transparent surface layer, and no surface undulation, uneven color, stripes, warpage of the article, peeling or cracking of the surface layer were observed at all.

Next, the antibacterial properties were evaluated in the same manner as in Example 1. As a result, it was found that both Escherichia coli and Staphylococcus aureus had less than 10 viable bacteria and had good antibacterial properties.

[0036]

As described above, the antibacterial crystallized glass article of the present invention exhibits excellent antibacterial properties and can 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 and vanity tops, kitchen vanity veneers, toilet booths, and hospital interior materials.

Further, according to the method of the present invention, the above-mentioned antibacterial crystallized glass article can be easily produced without impairing the excellent properties of the crystallized glass.

Claims (2)

[Claims] 1. An antimicrobial crystallized glass article comprising a substrate made of crystallized glass and a surface layer made of a resin and an antimicrobial agent formed on the substrate. 2. A method for producing an antibacterial crystallized glass article, comprising: forming an application layer containing a resin and an antibacterial agent powder on the surface of a crystallized glass plate; and curing the resin.