JPH08245237A - Composition for antibacterial glass - Google Patents

Abstract

PURPOSE: To obtain an antibacterial glass compsn. advantageous costwise and excellent in quality. CONSTITUTION: This compsn. contains, by weight, 25-60% SiO2 , 18-60% B2 O3 , 0-20% Al2 O3 , 8-30% R2 O (R is Li Na or K) 0-20% R'O (R' is Ca, Mg or Ba), 0-0.1% SO3 , 0-0.2% (expressed in terms of Fe2 O3 ) iron oxide, 0.2-2.0% Ag2 O and 1.5-10% ZnO.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an antibacterial glass composition,
Particularly, a composition for glass and a composition for glass fiber having an excellent antibacterial property, which is suitable for use as a water treatment agent or the like in the form of lump, powder or fiber as it is or by mixing powder or fiber with a resin or the like. Regarding

[0002]

2. Description of the Related Art Monovalent silver ions (Ag ⁺ ) and copper ions (C
It is well known that u ⁺ ) and divalent zinc ion (Zn ^{2 +} ) are toxic to lower animals such as microorganisms. In the present specification, the microorganism is defined to include bacteria, fungi and viruses which are microorganisms in a narrow sense, and protozoa and algae which are microorganisms in a broad sense. In addition, it has a toxic effect (including antibacterial effect) on the above microorganisms,
It is simply antibacterial. Many methods have been proposed for incorporating antibacterial properties by incorporating silver ions into soluble glass. For example, Japanese Patent Laid-Open Nos. 2-302355 and 6-219771 are disclosed.

[0003]

However, in the above-mentioned silver ion-containing glass, the precipitation of silver colloid or metallic silver is observed in JP-A-2-302355, so that the antibacterial property is weakened. In order to solve this, JP-A-6-219771
Then reduce the amount of iron contained in the glass, and add sulfate to the batch to make the glass in the oxidized state,
Precipitation of silver colloid and metallic silver can be prevented, so that the antibacterial property is not impaired. However, the content of Ag2O is usually up to about 2% by weight, and the antibacterial property is not sufficient in that range, and stronger antibacterial property may be required. It is possible to further increase the Ag2O content in order to further improve the antibacterial property, but in that case, the possibility that silver colloid and metallic silver will precipitate will increase, and the brittleness of platinum due to alloying during the use of platinum equipment. It is not economical because it costs a lot of money. In order to improve the antibacterial property, it is considered that copper ions are newly added to the silver ion-containing glass, but since the silver ions are reduced by the redox reaction during melting, in this case, the antibacterial effect is obtained. It is not good because the antibacterial properties of large silver ions are lost.

The present invention solves the above problems and provides an antibacterial glass composition which is cost-effective and excellent in quality.

[0005]

In order to solve the above problems, the following composition is proposed in which conventional Ag2O exhibiting antibacterial properties and ZnO having antibacterial properties, particularly antibacterial properties, are newly added. That is, expressed in weight%, SiO2 25-60 B2O3 18-60 Al2O3 0-20 R2O 8-30 (R = Li, Na, K) RO 0-20 (Ca, Mg, Ba) SO3 0-0.1 The composition for antibacterial glass is characterized by containing iron oxide (converted to Fe2O3) 0-0.2 Ag2O 0.2-2.0 ZnO 1.5-10.

In the present invention, the weight percentage is expressed as: SiO2 35-60 Al2O3 0-20 where SiO2 + Al2O3 40-65 B2O3 18-50 R2O 8-25 (R = Li, Na, K) R'O 0 -20 (R '= Ca, Mg, Ba) However, R2O + R'O8-35 SO3 0.01-0.1 Iron oxide (converted to Fe2O3) 0-0.05 Ag2O 0.2-1.5 ZnO The composition for antibacterial glass fibers is characterized by containing 1.5-10.

In the present invention, the SiO2 component forms the skeleton of glass, and its content is 25 to 60% by weight, preferably 30 to 55% by weight. If it is less than 25% by weight, the amount of silver ions, zinc ions and glass components eluted is too large, and the life (or durability) as an antibacterial glass composition is increased.
Becomes extremely short. On the other hand, if it exceeds 60% by weight, the viscosity increases and it becomes difficult to melt the glass,
The amount of zinc ions eluted is too small to provide sufficient antibacterial properties.
For fibers, the content of SiO2 component is 35-60
%, Preferably 40 to 58% by weight. If it is less than 35% by weight, it becomes difficult to form fibers, and if it exceeds 60% by weight, the antibacterial property becomes weak as described above, and it becomes difficult to melt and fiberize the glass.

The B2O3 component promotes the elution of glass and contributes to the stability of silver ions, and is 18 to 60% by weight, preferably 20 to 55% by weight. If it is less than 18% by weight, the elution amount of silver ions and zinc ions is too small, so that the antibacterial property is weak and metallic silver is likely to be deposited. 60% by weight
If the content exceeds the above range, the glass elution amount becomes too large and the life becomes extremely short, and if more than this amount is contained, it is not very effective in stabilizing silver ions. The amount of B2O3 in glass for fiber is 1
It is 8 to 50% by weight, preferably 20 to 40% by weight.
B2O3 content is less than 18% by weight, or 50% by weight
If it exceeds, it becomes difficult to form fibers.

The Al2O3 component is not an essential component, but it suppresses the elution of glass and contributes to the stabilization of silver ions, and is 0 to 20% by weight, preferably 1 to 10% by weight. If it exceeds 20% by weight, the elution amount of the glass is too small and the antibacterial property is weakened, and the viscosity of the glass is increased to make it difficult to melt. For glass for fibers, it is 0 to 20% by weight, preferably 2 to 15% by weight. If it exceeds 20% by weight,
In addition to the above-mentioned weakening of antibacterial property and difficulty of glass melting, fiberization becomes difficult. For fiberglass, SiO2 and A
The total amount of 12O3 is 40 to 65% by weight, preferably 42 to
It is 63% by weight. If this total amount is less than 40% by weight, the water resistance will be poor and the viscosity will be low, making fiber formation difficult. On the other hand, if it exceeds 65% by weight, the antibacterial property becomes weak and it becomes difficult to melt and fiberize the glass.

R2O (where R = Li, Na, K) promotes melting and elution of glass. Li2O, Na2O,
The total content of K2O and K2O is 8 to 30% by weight, preferably 10 to 20% by weight. If it is less than 8% by weight, the effect of promoting melting is small, and the elution of silver ions and zinc ions is suppressed, and the antibacterial property becomes weak. If it exceeds 30% by weight, the amount of glass eluted is too large, resulting in poor durability. In the glass for fibers, the total content of R2O is 8 to 25% by weight, preferably 10 to 20% by weight. If it exceeds 25% by weight, the viscosity becomes low and it becomes difficult to form fibers.

R'O (where R '= Mg, Ca, Ba) is not an essential component, but like R 2 O, it promotes melting and elution of glass, and MgO, CaO, and BaO.
The total content is 0 to 20% by weight, preferably 0 to 10% by weight. If it exceeds 20% by weight, the amount of glass eluted with R2O becomes too large and the durability becomes poor.
Also, for fibers, it becomes easy to devitrify, and it becomes difficult to make fibers. For fibers, the total R2O component and R'O
The sum of the total of the components (R2O + R'O) is 8 to 35% by weight, preferably 10 to 30% by weight. If it is less than 8% by weight, the effect of accelerating the melting is small, and the water resistance becomes too good and the antibacterial property becomes weak. If it exceeds 35% by weight, the viscosity is lowered, making it difficult to form fibers and the durability is also lowered.

SO3 is a component that stabilizes silver ions, and
~ 0.1% by weight, preferably 0-0.03% by weight,
Particularly for fibers, it is 0.01 to 0.1% by weight, preferably 0.01 to 0.03. SO3 has the effect of preventing the precipitation of silver colloid or metallic silver by keeping the glass in the oxidized state until the temperature rises to a high temperature during melting or remelting. In particular, the effect is remarkable when the glass is remelted to be fiberized. In this composition range, even if a certain amount of sulfate is added to the glass raw material, only a small amount of SO3 remains in the glass, and most of it retains the glass in an oxidized state up to a high temperature as described above. At the same time, they are released as sulfur oxides in the molten atmosphere. Especially for fibers, the effect cannot be expected with the addition amount of sulfate of less than 0.01% by weight, and even if the residual SO3 is contained in excess of 0.1% by weight, the effect is flat. The inclusion of a large amount of 0.1 has problems in the work environment and measures against air pollution.
The upper limit is% by weight.

Fe2O3 is 0-0.2% by weight, preferably 0-0.1% by weight, especially for fibers.
It is 0.05% by weight, preferably 0 to 0.01% by weight.
Fe2O3 is contained in the glass as an impurity in the raw material, but if it is too much, silver colloid or metallic silver tends to precipitate. Especially for fibers, since platinum is used at the time of fiberizing, the Fe2O3 content is 0.05% by weight or less,
It is preferably 0.01% by weight or less. 0.05% by weight
If it is contained in excess of 10%, the adverse effect on the platinum equipment due to the precipitation of the silver colloid or metallic silver cannot be ignored.

The Ag2O component is an essential component that turns into silver ions exhibiting antibacterial properties in glass, and is 0.2 to 2.0% by weight, preferably 0.3 to 1.5% by weight. If it is less than 0.2% by weight, the elution amount of silver ions is too small and the antibacterial property is poor.
If the content is more than 0% by weight, the amount of silver colloid having less antibacterial properties and the precipitation of metallic silver will increase, and since silver is expensive, the upper limit is 2.0% by weight. Ag2O for fibers
The amount is 0.2-1.5% by weight, preferably 0.3-1.0% by weight. If it is contained in an amount of more than 1.5% by weight, it is not economical, and the adverse effect on the platinum equipment due to the above-mentioned precipitation of colloidal or metallic silver (brittleness of platinum due to alloying of silver and platinum) cannot be ignored.

The ZnO component is an essential component that becomes antimony, especially antibacterial zinc ions in glass, and is in the range of 1.5-1.
It is 0% by weight, preferably 2 to 8% by weight. If it is less than 1.5% by weight, the elution amount of zinc ions is too small and the antibacterial property is poor. If it is contained in excess of 10% by weight, the water resistance of the glass itself becomes too good and the glass tends to devitrify. The sex becomes weak. The same applies to the amount of ZnO for fibers, but if the content exceeds 10% by weight, the antibacterial property is weakened because the water resistance is too good, and the glass is devitrified or phase-separated. Fiberizing becomes difficult.

The composition for antibacterial glass fibers of the present invention is required to have a viscosity range that allows easy fiber formation. B
It is desirable that the viscosity corresponding to various short fiber manufacturing methods and long fiber manufacturing methods such as the Tally method, the flame blowing method, and the rotary gas jet method be 10 ³ poises in a predetermined temperature range. That is, the composition for antibacterial glass fibers of the present invention has a temperature of 8 at a viscosity of 10 ³ poise.
It is desirable to have the properties within the range of 0 to 1250 ° C. More preferably, it is 800-1150 degreeC.
If it is less than 800 ° C, the viscosity is too low and it is difficult to fiberize it. At the same time, defects are likely to occur when fiberizing 1250 ° C.
If it is higher than 1, the spinning temperature will be too high and the productivity will be deteriorated. Therefore, the upper limit is 1250 ° C.

In order to exert antibacterial properties in the composition for antibacterial glass fibers according to the present invention, it is necessary to elute silver ions and zinc ions. However, if the water solubility exceeds the limit,
Poor durability should be avoided. As a method for measuring the water solubility of glass, the Japan Optical Glass Industry Association standard (JOGI
S) “Method of measuring chemical durability of optical glass (powder method) 06-1975. The weight loss rate of glass measured by this method is preferably 0.3 to 80% by weight or less. If the content exceeds 0.1%, the antibacterial property is sufficient, but the glass elution rate is too high and the durability is poor, so the upper limit is 80% by weight, and if it is less than 0.3% by weight, the durability is sufficient. Since the elution rate is too small and the antibacterial property is poor, the lower limit is 0.3% by weight, and the preferable fiber diameter of the antibacterial glass fiber produced by the antibacterial glass fiber composition of the present invention is The glass fiber is used in the form of cotton, woven fabric, non-woven fabric or the like.

[0018]

As described above, the composition for antibacterial glass of the present invention is prepared by adjusting the composition of various oxides constituting the glass in an appropriate range, and by using antibacterial silver ion and zinc ion together. This makes it possible to produce antibacterial glass having excellent antibacterial properties.

[0019]

【Example】

(Examples 1 to 8 and Comparative Examples 1 to 6) Silica sand, boric acid, borax, aluminum oxide, lithium carbonate, sodium carbonate, potassium carbonate, so as to have the target compositions shown in Tables 1 and 2.
Basic magnesium carbonate, calcium carbonate, zinc carbonate,
A batch of barium carbonate and silver nitrate was prepared. SO
As the three components, sodium sulphate was added and used when the amount contained in the above raw materials was insufficient. F in normal raw materials
e2O3 was about 50 ppm, and ferric oxide was added when a large amount of Fe2O3 was contained. This batch was placed in an alumina crucible if it was predicted that a large amount of metallic silver was precipitated, otherwise, placed in a platinum crucible and placed in an electric furnace.
It melted by heating at 00 to 1500 ° C. for 2 hours. afterwards,
The molten glass was poured onto a stainless steel plate, shaped into a plate, and then gradually cooled.

With respect to this sample, the deposition of metallic silver, the coloring state of glass, antifungal property, antibacterial property, water solubility and meltability were measured by the following methods. (Situation of deposition of metallic silver) The glass melted and plate-shaped as described above was irradiated with a halogen lamp to obtain a major axis of 10
Metallic silver of μm or more is counted using a magnifying glass with a magnification of 40 times, and is represented by the number per 100 g of glass. When not detected at all (zero number), it is indicated by ◯, and when it is 100 or less, it is indicated by ◯. When the number exceeds 100, it is indicated by x. Since most of the size (major axis) of metallic silver is 100 μm or less, when the number is 100 or less, coloring is not recognized at all and the influence on the quality is small, and it is negligible depending on the product type.

(Glass Coloring State) In the above sample, when there was no brown or yellow colloidal coloring, it was marked with ◯, and when it was colored, it was marked with x.

(Antifungal, Antibacterial) First, by using Sabro-agar medium (for mold) and standard agar (for general bacteria) manufactured by Nissui Pharmaceutical Co., Ltd., molds and bacteria in the air are grown. Each was suspended in water to prepare a fungal and bacterial culture. Next, the glass sample is crushed and classified to 38 μm.
After preparing the following glass powders, using a commercially available press, alumina A-21 (Sumitomo Chemical Co., Ltd.): glass powder = 5
A mixture of 00 mg: 25 mg was molded into one cylindrical pellet (diameter: 1 cm × 0.3 mm), and the pellet was placed almost in the center of the above-mentioned Saburo-agar medium and standard agar medium to prevent mold and bacteria. The culture solution was added dropwise, and the growth of mold and bacteria was observed one week later. When the width of the mold inhibition zone of mold or bacteria is found to exceed 3 mm in the periphery of the pellet, it is indicated by ◎, and the width of the growth inhibition zone is 1 to 3 mm.
When the width of the growth inhibition zone is less than 1 mm, the antifungal and antibacterial properties are poor.

(Water solubility) Japan Optical Glass Industry Association Standard (JO
GIS) "Method for measuring chemical durability of optical glass (powder method) 06-1975", the weight loss rate is measured. If the weight loss rate is 0.3 to 80% by weight or less, the result is ○, and if it exceeds 80% by weight. Was evaluated as poor in durability, and when less than 0.3% by weight, poor in water solubility.

(Melting property) The above-mentioned plate glass sample was melted again, and the temperature at which its viscosity became 10 ² poise was measured by the platinum ball pulling method. When this temperature was 1500 ° C. or less, the melting property was good. It is shown as ◯, and when it exceeds 1500 ° C., it is difficult to melt and shown as x.

[0025]

[Table 1] =================================== Example ---------- −−−−−−−−−−−−−−−−−−−−−−−− No 1 2 3 4 5 6 7 8 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− Composition wt% SiO2 27.8 31.5 26.9 35.5 34.5 40.1 56.2 59.3 Al2O3 16.3 1.5 0.2 0.8 3.3 1.8 6.9 0 B2O3 42.8 37.6 50.7 35.9 34.3 41.0 18.4 23.8 Li2O 0 0 0 2.4 0 0 0 0 Na2O 9.4 10.2 10.8 10.2 21.1 11.5 10.9 13.2 K2O 0 0 0 1.8 3.5 0 1.1 0 MgO 0 12.2 0 4.1 0 0 2.5 0 CaO 0 4.1 0 1.5 0 0 0 0 BaO 0 0 0 0.5 0 0 0 0 SO3 0 0 0.02 0.01 0.01 0.01 0.03 0.05 Fe2O3 0.05 0.15 0.005 0.1 0.03 0.005 0.005 0.005 Ag2O 0.2 0.4 1.8 0.8 0.3 1.2 0.5 0.7 ZnO 3.5 2.5 9.6 6.5 3 4.4 3.5 3 −−−−−−−−−−−−− −−−−−−−−−−−−−−−−−− −−−− Deposition of metallic silver ◎ ○ ○ ○ ○ ◎ ◎ ○ ○ Coloring ○ ○ ○ ○ ○ ○ ○ ○ Antifungal property ○ ○ ◎ ◎ ○ ◎ ○ ○ Antibacterial property ○ ○ ◎ ◎ ○ ◎ ○ ○ Water solubility ○ ○ ○ ○ ○ ○ ○ ○ Meltability ○ ○ ○ ○ ○ ○ ○ ○ ================================== ==

[0026]

[Table 2] ==================================== Comparative Example ---------- −−−−−−−−−−−−−−−−−−−−−−−−−− No 1 2 3 4 5 6 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− Composition wt% SiO2 36.5 40.2 31.1 52.9 17.3 68.2 Al2O3 2.1 0.7 0 0 0 8.5 B2O3 41.2 42.9 49.8 21.3 70.1 10.5 Li2O 0.4 0 0 0 0 0 Na2O 10.2 11.3 14.3 8.5 10.4 9.6 K2O 1.8 0 0 1.2 0 0 MgO 1.5 0 0 0 0 0 CaO 4.1 0 0 0 0 0 BaO 0.6 0 0 0 0 0 SO3 0.03 0 0 0.01 0 0.03 Fe2O3 0.005 0.02 0.4 0.08 0.005 0.1 Ag2O 0.8 0.1 2.8 0.3 0.4 0.6 ZnO 0.8 4.8 2.0 15.8 1.8 2.6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Precipitation of metallic silver ◎ ◎ × ○ ◎ ○ Coloring ○ ○ × ○ ○ ○ Antifungal resistance ◎ × ◎ × ◎ × Antibacterial property × ◎ ○ × ◎ × Water solubility ○ ○ ○ × × × Meltability ○ ○ ○ ○ ○ × ========================== ===========

As is clear from Table 1, all the glasses of Examples have excellent antifungal and antibacterial effects, no glass coloring, and no or negligible precipitation of metallic silver. From the above, it is understood that it is possible to produce antibacterial glass excellent in productivity and quality from the glass composition shown in Table 1. Comparative Example 1 in Table 2 is inferior in antibacterial property, and Comparative Example 2 is inferior in antifungal property. Comparative Example 3 is uneconomical because of the large amount of Ag2O, the precipitation of metallic silver occurs. In Comparative Example 4, since the glass is devitrified, the water solubility is poor and the antifungal and antibacterial properties are poor. Comparative Example 5 is poor in durability because it is too water-soluble. Comparative Example 6 is a glass composition which is inferior in anti-fungal and anti-bacterial properties because it is inferior in meltability and the glass is too little eluted.

(Examples 9 to 16, Comparative Examples 7 to 12) Similar to Examples 1 to 8 and Comparative Examples 1 to 6, the target compositions shown in Examples of Table 3 and Comparative Examples of Table 4 were obtained. Then, after batch preparation, melting, molding and slow cooling were performed. With respect to this plate glass, the deposition of metallic silver, the coloring state of the glass, antifungal, antibacterial, water-soluble, and the quality of fibrosis were measured.

The deposition state of metallic silver, the coloring state of glass, and the water solubility are the same as the measuring methods in Examples 1 to 8 and Comparative Examples 1 to 6 above.

(Antifungal and Antibacterial Properties) First, by using Sabro-agar medium (for mold) and standard agar (for general bacteria) manufactured by Nissui Pharmaceutical Co., Ltd., molds and bacteria in the air are grown. Each was suspended in water to prepare a fungal and bacterial culture. Next, the glass sample is crushed and classified to 38 μm.
After preparing the following glass powder, the glass powder (0.3 g) was made into a cylindrical pellet (diameter 1 cm x
0.3 mm), the pellet was placed in the approximate center of the above-mentioned Saburo-agar medium and standard agar medium, and the mold and bacteria culture solution was added dropwise to observe the growth condition of mold and bacteria after 1 week. . If a mold or bacterial growth-inhibiting zone of more than 3 mm in width is found around the pellet, it is indicated by ◎ because the antifungal and antibacterial properties are very good, and the growth-inhibiting zone is in the range of 1 to 3 mm in width. Antifungal, if
Since the antibacterial property is relatively good, it is indicated by ○, and when the growth inhibition zone is less than 1 mm, the antifungal and antibacterial properties are poor ×
Indicated by.

(Good or bad of fiberization) The plate glass sample was melted again and the temperature at which the viscosity became 10 ³ poise was measured by a platinum ball pulling method, and the temperature was 800 to 115.
When the temperature is in the range of 0 ° C., the fiberization is very good, and therefore is indicated by ⊚. If it exceeds, it is difficult to fiberize,
In addition, since defects are likely to occur, it is indicated by x. However,
Good fiberization, temperature range at 10 ³ poise is 9
Even in the case of 00 to 1250 ° C., when devitrification occurs near the spinning temperature, it is indicated by x.

[0032]

[Table 3] ================================== Example ----- −−−−−−−−−−−−−−−−−−−−−−−− No 9 10 11 12 13 14 15 16 −−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− Composition wt% SiO2 40.8 41.7 54.8 42.1 45.1 50.6 53.4 58.3 Al2O3 5.5 2.7 4.7 2.5 18.6 3.1 6.8 2.1 B2O3 30.6 34.7 27.8 23.6 21.2 20.3 18.5 27.0 Li2O 0 0 0 1.1 0 0 0 1.3 Na2O 10.5 12.2 9.4 9.8 10.5 14.7 17.1 8.6 K2O 0 0 0 2.1 0 8.6 0 0 MgO 5.1 0 0 9.8 0 0 0 0 CaO 2.1 0 0 4.5 0 0 0 0 BaO 0 0 0 2.7 0 0 0 0 SO3 0.02 0.01 0.05 0.02 0.02 0.05 0.03 0.03 Fe2O3 0.005 0.01 0.005 0.03 0.01 0.05 0.02 0.005 Ag2O 0.4 0.9 0.5 0.2 1.2 0.2 0.3 0.6 ZnO 5.0 7.8 2.8 1.6 3.4 2.5 3.9 2.1 −−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−− −−− Precipitation of metallic silver ◎ ○ ◎ ◎ ○ ◎ ○ ○ Coloring ○ ○ ○ ○ ○ ○ ○ ○ Antifungal property ○ ◎ ○ ○ ◎ ○ ○ ○ Antibacterial property ◎ ◎ ○ ○ ○ ○ ○ ○ Water solubility ○ ○ ○ ○ ○ ○ ○ ○ Quality of fiberization ◎ ◎ ◎ ◎ ◎ ○ ○ ◎ ＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝ ==

[0033]

[Table 4] ================================= Comparative Example -------- −−−−−−−−−−−−−−−−−−−−−−− No 7 8 9 10 11 12 −−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−− Composition wt% SiO2 42.1 48.9 52.7 39.9 24.5 71.3 Al2O3 2.5 5.8 7.4 4.2 1.6 2.8 B2O3 23.6 27.5 27.4 29.4 54.3 12.8 Li2O 0 0 0.4 0 6.2 0 Na2O 10.1 7.2 10.6 10.5 9.9 7.1 K2O 2.1 2.7 0 0 0 0 0 MgO 4.5 0 0 0 0 1.3 CaO 9.8 0 0 0 0 0.4 BaO 2.5 0 0 0 0 0 SO3 0.02 0 0.01 0.02 0 0.03 Fe2O3 0.005 0.2 0.005 0.05 0.005 0.1 Ag2O 0.1 1.9 0.5 1.2 0.7 0.5 ZnO 2.7 6.0 1.0 14.8 2.8 3.8 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Precipitation of metallic silver ○ × ◎ ○ ◎ × Coloring ○ × ○ ○ ○ × Mold resistance × ◎ ○ ◎ ◎ × Bacterial ○ ◎ × ◎ ◎ × × Water solubility ○ ○ ○ ○ × × Good or bad fiberization ◎ ◎ ◎ × × × ======================== ========

As is clear from Table 3, all the glasses of Examples have excellent antifungal and antibacterial effects, no coloring of the glass, and no or negligible precipitation of metallic silver. From the above, it is understood that it is possible to produce antibacterial glass fibers excellent in productivity and quality from the glass compositions shown in Table 3. Comparative Example 7 in Table 4 is inferior in antifungal property, and Comparative Example 8 is not economical because precipitation of metallic silver occurs.
Comparative Example 9 is inferior in antibacterial property. In Comparative Example 10, the glass is devitrified and phase-separated, which makes it difficult to form a fiber. Since Comparative Example 11 has too good water solubility, it is inferior in terms of durability and further difficult to be made into fibers. Comparative Example 12 is a glass composition in which the amount of glass eluted is too small, the antifungal and antibacterial properties are inferior, and fiber formation is difficult.

[0035]

As described above, the antibacterial glass composition of the present invention has the following properties: SiO2, B2O3, Al2O3, R2O (R = L
i, Na, K), R'O (R '= Mg, Ca, Ba), A
By adjusting the ratio of g2O and ZnO appropriately,
This makes it possible to manufacture glass with antibacterial properties that is cost-effective and excellent in quality. Further, the composition for antibacterial glass fiber of the present invention, by appropriately adjusting each component,
It enables the production of glass fibers having excellent antibacterial action with excellent productivity and quality.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C03C 3/093 C03C 3/093 14/00 14/00

Claims (5)

[Claims] Claims 1. SiO2 25-60 B2O3 18-60 Al2O3 0-20 R2O 8-30 (R = Li, Na, K) R'O 0-20 (R '= Ca, Mg) , Ba) SO3 0-0.1 iron oxide (converted into Fe2O3) 0-0.2 Ag2O 0.2-2.0 ZnO 1.5-10, composition for antibacterial glass, characterized in that . 2. SiO2 30-55 B2O3 20-55 Al2O3 1-10 R2O 10-20 (R = Li, Na, K) R'O 0-10 (R '= Ca, Mg) , Ba) SO3 0-0.03 iron oxide (converted to Fe2O3) 0-0.1 Ag2O 0.3-1.5 ZnO 2-8, The composition for antibacterial glass according to claim 1. 3. SiO2 35-60 Al2O3 0-20 where SiO2 + Al2O3 40-65 B2O3 18-50 R2O 8-25 (R = Li, Na, K) R'O 0-20 (expressed in% by weight) R ′ = Ca, Mg, Ba) However, R 2 O + R′O 8 to 35 SO 3 0.01 to 0.1 iron oxide (converted to Fe 2 O 3) 0 to 0.05 Ag 2 O 0.2 to 1.5 ZnO 1.5 10. An antibacterial composition for glass fibers, which comprises: 4. SiO2 40 to 58 Al2O3 2 to 15 where SiO2 + Al2O3 42 to 63 B2O3 20 to 40 R2O 10 to 20 (R = Li, Na, K) R'O 0 to 10 (expressed in% by weight) R '= Ca, Mg, Ba) However, R2O + R'O 10-30 SO3 0.01-0.03 iron oxide 0-0.01 Ag2O 0.3-1.0 ZnO 2-8 is contained. The composition for antibacterial glass fiber according to item 3. 5. The antibacterial glass fiber composition according to claim 3, wherein the antibacterial glass fiber composition has a characteristic temperature such that the viscosity at which the viscosity of the antibacterial glass fiber composition becomes 10 ³ poise is 800 to 1250 ° C.