KR101494303B1 - Process for producing antibacterial and antiviral glass fiber material - Google Patents

Abstract

The present invention relates to a method for producing an antiviral antiviral glass fiber material which imparts an antimicrobial anti-viral metal ion to a glass fiber.
The present invention relates to a silica-based glass fiber comprising 50% by mass or more of silicon oxide and having an aluminum content of 3% by mass or less and having a fiber diameter of 1 占 퐉 or more and 10 占 퐉 or less, A zeolite layer is formed on the surface by immersing in an alkali aluminum oxide aqueous solution and heating and alkali treatment to bring the zeolite layer into contact with an aqueous solution of a metal compound containing an antibacterial antiviral metal ion to adsorb the metal ion to the zeolite layer, A method for producing a glass fiber material has been proposed.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing an antimicrobial antiviral glass fiber material,

The present invention relates to a method for producing an antiviral antiviral glass fiber material which imparts an antimicrobial anti-viral metal ion to a glass fiber.

Glass fibers are widely used as durable fiber materials. One of its uses is a filter for air purifiers. Conventional air purifiers are intended to remove dust only, but recently, it has been required to further purify air by adding antibacterial and antiviral properties. To this end, fibrous antimicrobial and antiviral materials are required, and it has been studied to adsorb ions such as copper, silver and zinc with antimicrobial antiviral metal ions to glass fibers.

It has been proposed to adsorb metal ions such as silver ions to glass fibers and to coat the glass fibers with zeolite. By forming the zeolite structure by the aluminum oxide addition on the surface of the glass fiber having the basic constitution of silicon oxide (silica), the aluminum oxide portion can accommodate the metal ion.

Examples of the production method include a method in which silica-alumina glass fibers are dipped in an alkaline aqueous solution and subjected to a heating reaction to zeolite the alumina portion of the fiber surface (References 1 and 2) A method in which zeolite is precipitated on the surface of a fiber by immersing it in an aqueous solution in which an aluminum compound (alumina source) and sodium hydroxide (alkaline source) are dissolved in a solvent (silica raw material) have.

(Reference 1) Japanese Laid-Open Patent Publication No. 1999-217241. (Reference 2) Japanese Patent Application Laid-Open No. 2001-39740. (Reference 3) Japanese Patent Application Laid-Open No. 2008-56550.

However, the method of zeolitizing silica-alumina-based glass fibers by dipping them in alkaline aqueous solution has a problem that the glass fibers are not only reduced in weight but also become brittle due to the zeolite formation of the glass fibers themselves.

In addition, in the method of zeolite silica-based glass fiber in an aqueous solution having silicon oxide, aluminum oxide, and sodium hydroxide, it is difficult to weaken the glass fiber itself because the glass fiber itself does not react. However, in comparison with silicon oxide in glass fiber, Because of its high reactivity, zeolite in the stratum that is generated on the glass fiber is produced, and in the form of powder in the form of a powder produced by reaction in the solution, a large amount of zeolite is produced. As in Reference 3, even if the concentration is optimized, it is possible to reduce the amount of powdery zeolite to some extent, but the amount which can not be ignored is by-produced. If there are many such zeolites in powder form, the function of removing dust when used as a filter is deteriorated. Also, when the powdery zeolite is removed, the metal ions added thereto are wasted.

In addition, since metal ions that actually exhibit antibacterial antiviral activity by any method are confined to ions existing on the surface portion of the zeolite, the metal ions present therein are wasted. However, in order to sufficiently secure the density of metal ions on the surface, a certain amount of metal ions must be adsorbed inside the zeolite, and more metal ions must be adsorbed than necessary, resulting in considerable waste.

To solve this problem, zeolite could not be adhered to the silica-based glass fiber by immersing it in an alumina-alkali aqueous solution so that the zeolite can be accumulated only on the surface of the silica-based glass fiber which is hardly weakened.

This is presumably because the silicon oxide constituting the silica-based glass fiber is in a stable bonding state as compared with the silicon oxide existing in a dispersed state in the solution, and thus does not react even in contact with aluminum hydroxide in a strong alkaline environment.

Accordingly, it is an object of the present invention to provide a zeolite for adsorbing an antimicrobial antiviral metal ion in a state in which powdery zeolite is not produced as a by-product in glass fibers used for a filter or the like, and the glass fiber itself is not deactivated.

In the present invention, silica-based glass fiber containing silicon oxide as a main component of glass fiber is used for acid treatment before the alkali treatment to activate the surface, then immersed in an aqueous alkali solution of aluminum oxide, Thereby forming a zeolite layer having a minimum required thickness.

The feature is that silicon oxide, which is one reaction raw material, is placed in a solid state and aluminum oxide which is another reaction starting material is put into a liquid to cause a reaction at the contact surface of the solid and the liquid.

The acid treatment refers to a method in which the upper silica-based glass fiber is immersed in an aqueous acid solution and subjected to a heat treatment, thereby activating silicon atoms on the surface of the silica-based glass fiber.

Therefore, the aluminum atom in the aqueous alkaline solution is easily given to the silicon atom, and a zeolite layer of about one atom of aluminum is formed on the surface of the silica-based glass fiber. This layer is thin enough to have almost no relationship with the shape of the adsorption hole composed of a plurality of atoms of silica-alumina like the crystal structure of zeolite.

The point of adsorbing the generated metal ions thereon can be said to be planar rather than stereoscopic, in the form of a knitting nose.

Although the pore size of the zeolite crystals is in the unit of Å, the fungi and viruses occupy more than a hundred times the size, so that the metal ions adsorbed in the zeolite holes or in the zeolite layer can not be contacted with fungi and viruses, which is wasteful. Almost all the metal ions that do not get up and adsorbed exert the antimicrobial antiviral effect.

The silica-based glass fiber is a glass containing silicon oxide as a main component and a part of an alkali metal or an alkaline earth metal, such as soda glass, and is particularly easy to activate the surface by acid treatment, and the present invention is easy to apply.

On the other hand, when a glass containing a large amount of alumina component is used, it is preferable that the content of alumina component is small in order to embrittle as described above.

According to the present invention, it is possible to obtain a zeolite layer having a minimum thickness required on the surface of the glass fiber, and to reduce the amount of the antibacterial antiviral metal ions adsorbed on the zeolite layer to a minimum amount.

1 is an XRD chart of the material used in Example 1. Fig.
2 is an XRD chart of the material used in Comparative Example 1. Fig.
3 is an XRD chart of the material used in Comparative Example 2. Fig.

Hereinafter, the present invention will be described in detail.

The present invention relates to a method for producing an antimicrobial antiviral glass fiber in which a zeolite layer is formed on the surface of a silica-based glass fiber to adsorb the minimum necessary antimicrobial antiviral metal ion.

The silica-based glass fiber used in the present invention is preferably at least 50 mass% or more of silicon oxide, more preferably 60 mass% or more of silicon oxide, and more preferably 70 mass% or more of silicon oxide. The greater the amount of silicon oxide, the harder it is to be hardened by the acid treatment and the alkali treatment described later, and the strength can be maintained.

It is preferable that the silica-based glass fiber contains an alkali metal, an alkaline earth metal, or both at 20 wt% or more.

Specific examples of the alkali metal include lithium, sodium and potassium, and alkaline earth metals include calcium and magnesium. When the alkali metal and alkaline earth metal are contained in an amount of 20 wt% or more, the surface is easily activated in acid treatment in the future and the metal is likely to react with the acid.

However, if the amount of alkali metal and alkaline earth metal is too much, the possibility of embrittlement in acid treatment and subsequent treatment can not be neglected, so it is preferable that the range is about the same as that of ordinary soda glass (soda lime glass).

The silica-based glass fiber may contain other elements in a range satisfying the content of the above-mentioned silicon oxide, but the smaller the content of aluminum is, the better. When aluminum is contained in a large amount, zeolite progresses not only to the surface of the silica-based glass fiber but also to the inside of the silica-based glass fiber, and embrittlement of the fiber can not be ignored.

Concretely, the aluminum content should be equal to or less than that of general soda lime glass, preferably 3 mass% or less, and more preferably 2 mass% or less.

The shape of the silica-based glass fiber is not particularly limited, but may be a cloth or a yarn. However, if it is a filament, it is necessary to further process after forming a zeolite layer. Since the zeolite layer may be peeled off at this time, it is difficult to form a fiber shape or a linear shape suitable for the purpose of use, It is preferable to apply antibacterial antiviral properties directly to the fibers by applying the manufacturing method of the present invention.

The individual fibers constituting the silica-based glass fiber preferably have a diameter of 1 占 퐉 or more. If it is less than 1 탆, it may be too thin to adsorb zeolite or metal ions on the surface.

On the other hand, it is preferable that the diameter is 10 μm or less. This is because glass wools over 10 μm are not common. Actually, the diameter may be determined according to the property of the filter to be applied in the range of the diameter.

The fiber length of the silica-based glass fiber is not particularly limited.

Next, a description will be given of a processing operation performed on the silica-based glass fiber. The silica-based glass fiber is first subjected to an acid treatment with an acidic aqueous solution to remove impurities to activate the surface, and then an alkali treatment with an aqueous alkali solution containing aluminum oxide is performed to form a zeolite layer on the surface.

Thereafter, it is washed with water to drop an aqueous alkali solution, and then an antimicrobial antiviral treatment liquid having a metal ion of an antimicrobial antivirus is given to adsorb the metal ion.

The acidic aqueous solution needs to be strongly acidic, specifically at least pH 2 or less, more preferably pH 1 or less. and if it exceeds pH 2, the surface of the silica-based glass fiber is less reacted to activate the silicon atoms hardly to be achieved.

As the acidic species to be used, inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid are preferable, and sulfuric acid is preferable because it does not easily evaporate even when heated. However, in the case of sulfuric acid, if the concentration is too high, the reaction may be adversely affected, so 10% by mass (2 specified ()) or more and 20% by mass or less is preferable.

It is preferable that the acidic treatment is performed by immersing the silica-based glass fiber in the acidic aqueous solution and heating. The acid treatment is preferably carried out at 70 ° C or higher, and more preferably at 90 ° C or higher. At low temperatures, the effect of activating the surface of the silica-based glass fibers is insufficient and, if possible, takes too long.

The acid treatment is preferably performed for 1 hour or more. If it is less than 1 hour, the effect of activating the surface may be insufficient even if the temperature of the acidic treatment is 95 ° C. On the other hand, if too much time is spent, the working efficiency is not good, so it is preferable to set it to 8 hours or less. The above-mentioned temperature range is suitable for performing sufficient processing within this time.

After the acid treatment is performed, it is preferable to perform the water washing and the alkali treatment once. If the acidity remains, the alkali is neutralized, which may cause a by-product in the aqueous alkali solution. On the other hand, acid treated surfaces should not be inactive by water wash.

The aqueous alkali solution needs to contain aluminum oxide or at least a component equivalent thereto. A zeolite layer can not be formed on the surface of the silica-based glass fiber unless it has a sufficient amount of aluminum oxide or an equivalent amount of aluminum atoms and oxygen atoms. Concretely, it is preferable to contain aluminum oxide or its equivalent in an amount of 5 mass% or more, more preferably 10 mass% or more. When the concentration is sufficiently high in the soluble range, the treatment effect is improved by that much. However, a compound containing an alkali metal such as sodium aluminate or an alkaline earth metal may be used instead of the aluminum oxide itself. In this case, it is preferable that the amount of aluminum oxide substantially contained is within the above range.

The aqueous alkaline solution needs to be strongly alkaline. Specifically, it needs to be at least pH 12, and pH 13 or more is most preferable. When the pH is less than 12, it is difficult to cause the reaction to cause the zeolite layer to survive even when the silicon atom is activated. The alkali used is preferably an aqueous solution of an alkali metal such as lithium, sodium, potassium, rubidium or cesium or an alkaline earth metal such as magnesium, calcium, strontium or barium, and sodium or potassium is preferable . However, since the silica-based glass fiber may be brittle if the concentration is too high, a concentration of alkali metal or alkaline earth metal of less than 20% by mass is most suitable. Aluminum oxide and an alkali metal or alkaline earth metal need to dissolve both in the alkali aqueous solution, but the weight mixing ratio may be about 3: 1 to 1: 3. If one side is too small, the reaction for producing zeolite does not proceed well.

It is preferable that the alkali aqueous solution does not mix aluminum oxide with components other than alkali metal or alkaline earth metal, and it is particularly preferable not to add a silicon compound.

If silicon is added, there is a possibility of zeolite formation in the solution prior to reacting with the surface of the silica-based glass fiber.

The alkali treatment may be performed by immersing the silica-based glass fiber activated on the surface by the acid treatment in an alkali aqueous solution of aluminum hydroxide. The alkali treatment is most preferably performed at 70 캜 or higher, and more preferably at 75 캜 or higher.

The zeolite does not sufficiently proceed at a low temperature, and the possibility that the amount capable of adsorbing a metal ion to be described later becomes insufficient becomes high. On the other hand, although it is related to the alkali concentration, when the temperature exceeds 90 ° C, the progress of the alkali treatment becomes too fast, and the silica-based glass fiber can be embrittled, so 90 ° C or lower is preferable and 85 ° C or lower is more preferable.

The alkali treatment is preferably performed for 2 hours or more. If the temperature is less than 2 hours, even if the temperature of the alkali treatment is 95 ° C, zeolite formation on the surface is insufficient, and there is a high possibility that an amount capable of adsorbing metal ions to be described later becomes insufficient.

On the other hand, if the time passes too much, the generated zeolite layer does not stay on the surface but becomes thicker than necessary, and even if adsorbed there are many metal ions which are not exposed on the surface, resulting in a lot of waste. Therefore, the alkali treatment is suitable for 10 hours or less, and 6 hours or less is most suitable.

The thickness of the zeolite layer formed on the surface of the silica-based glass fiber by the alkali treatment is preferably as thin as possible, and zeolite is formed only on the contact surface between the solid glass fiber and the aluminum oxide in the alkali aqueous solution, .

Although metal ions which are to be described later are adsorbed on the main aluminum atom, metal ions which are not exposed on the surface are hardly able to exhibit substantially antibacterial antiviral effect, and even if a large amount of aluminum atoms are present therein, they are meaningless and useless to be.

In addition, if the zeolite layer is too thick, the zeolite layer itself may fall off as compared with the original state. Therefore, it is necessary to appropriately adjust the conditions to suit the above-mentioned time, temperature, and concentration range of the acid.

The silica-based glass fiber on the surface of which the zeolite layer has been removed is washed away by the alkali treatment to remove the alkali aqueous solution. And then contains metal ions having antimicrobial antiviral properties and is immersed in an aqueous metal compound solution to adsorb the metal ions to the aluminum atom portion of the zeolite layer.

Silver ions are most preferred as the metal ions having antimicrobial antiviral properties, for example, copper ions, silver ions, and zinc ions are supported to show a strong effect. As the metal compound aqueous solution containing the metal ion, for example, an aqueous silver nitrate solution is received. The amount and the concentration of the metal compound aqueous solution are suitably in an amount and concentration sufficient to adsorb the metal ions to all the sites of the adsorption point on the surface of the zeolite layer. When the difference between the silica-based glass fibers is within the above-mentioned range, an aqueous solution of a metal compound having silver ions in an amount of about 1 to 5% by mass with respect to the weight of the silica-based glass fiber is used, . If it is less than this range, the antiviral property may become insufficient, and if it is too much, the silver ion becomes useless.

The silica-based glass fiber adsorbed on the zeolite layer on the surface of the metal ion thus obtained has antimicrobial antiviral effect by the metal ion. Therefore, the silica-based glass fiber is used as a filter for air conditioning and air cleaner, It exhibits an inhibitory effect against fungi and viruses and maintains sufficient strength.

In addition, since the powdered zeolite does not form a by-product, dust is not easily generated during use.

Hereinafter, the present invention will be described in detail.

(Example 1)

This was immersed in 16 mass% sulfuric acid and treated with acid treatment at 90 占 폚 for 3 hours using a glass wool cloth (Paramount Glass Industries, Ltd., type number: Houseron 430 (insulating glass for home use) . The glass fiber was rinsed in water and immersed in an aqueous alkali solution of sodium aluminate (the Al2O3 concentration was 12 mass%, the NaOH concentration was 16 mass%, the pH was 13 or more), and the alkali treatment was performed at 80 ° C for 5 hours .

Then, the sample was washed with water to remove the alkali, and then a part of the sample was taken and confirmed by X-ray diffraction (using measuring instrument: Miniflexll, manufactured by Rigaku Corporation).

The sampling width is 0.0020 (2? /?), The scan speed is 3.00 (2? / Min), the irradiated X-ray is Cu-K ?, and the irradiation conditions are 30 kV and 15 mA. The results are shown in Fig.

On the other hand, in the remaining samples, silver ions were adsorbed for 120 hours by immersing them in an aqueous solution of silver nitrate having 2 mass% of silver ions based on the mass of the silica-based glass fibers. An aqueous solution of sodium chloride was dropped into the used silver nitrate aqueous solution after the adsorption, but no precipitate of silver chloride was observed. As a result, almost all the silver ions contained in the aqueous solution of Jin - San were adsorbed on the zeolite layer.

Chemical components were segmented by fluorescence X-ray segmentation method using the original glass fiber, glass fiber in an acid treatment step, and glass fiber having a zeolite layer formed on its surface using RIKAKUJO: Primusll.

The results are shown in Table 1.

Chemical composition (%) SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ Na ₂ O CaO K ₂ O TiO ₃ BaO Originally, 63.18 2.01 0.43 14.11 8.73 2.64 0.24 2.45 Acid treatment (acid treatment) 65.58 2.02 0.43 11.35 9.07 2.47 0.21 2.24 Zeolitization (conversion) 61.07 3.78 0.43 11.55 9.42 2.67 0.24 2.25

(Example 2)

Measurement and production were carried out under the same conditions as in Example 1 except that the Al ₂ O ₃ concentration of the alkali aqueous solution was changed to 8 mass%. After the adsorption was carried out in an aqueous solution of silver nitrate, an aqueous solution of sodium chloride was dropped to the used solution, but no silver halide reaction was observed.

Accordingly, if the concentration of aluminum oxide is within this range, it can be inferred that a zeolite layer is sufficiently formed on the entire glass fiber.

(Comparative Example 1)

Production and measurement were carried out under the same conditions as in Example 1 except that acid treatment was not performed. The results of XRD are shown in Fig. Also, after the adsorption test, a large amount of silver precipitated when an aqueous solution of sodium nitrate was dropped into the aqueous solution of silver nitrate. Therefore, it was confirmed that almost no silver ions were adsorbed and almost no zeolite layer remained on the surface of the silica-based glass fiber.

(Comparative Example 2)

Compared with Comparative Example 1, measurements were made under the same conditions except that the concentration of NaOH in the aqueous alkaline solution was 20 mass% and the temperature of the alkali treatment was 90 ° C. The results of XRD are shown in Fig. This silica-based glass fiber was confirmed to be brittle.

After the adsorption test, a large amount of silver precipitated as a result of dropping an aqueous solution of sodium chloride in an aqueous solution of silver nitrate. Therefore, it was confirmed that almost no silver ions were adsorbed and almost no zeolite layer remained on the surface of the silica-based glass fiber.

(Review of XRD)

Compared with Fig. 2 or 3 in which no zeolite layer remained, in Fig. 1, no specific peak of zeolite crystals was observed. It was confirmed that the zeolite layer was so thin that it did not have a thickness enough to detect XRD by zeolite crystals.

<Antibacterial test>

In Example 1, an experiment of antibacterial term was carried out using a silica-based glass cloth impregnated with silver ions. Staphylococcus aureus ATCC 6538P was used as an experimental strain, and the test method was performed by JISL 1902: 2008 quantitative test (bacterium absorption method), and the viable cell count was measured by injection plate culture method.

log a 였기에 시험이 성립된 것을 확인하였다.First, the number of bovine follicles b = 9.6 × 10 ⁶ (ie, log b = 7.0) using a standard cotton is obtained for the number of the bacteria a = 2.70 × 10 ⁴ (ie, log a = 4.4)

log a, it was confirmed that the test was established.

Next, the number of viable cells (o) and the number of viable cells (c) after 18 hours were measured immediately after culturing together with the test solution containing 0.05% of surfactant (Tween 80) added to the silica-based glass fiber surface of Example 1 Above all, the measurement limit was less than 20. Then, the bactericidal activity value L = log a-log b and the bacteriostatic activity value S = (log b-log a) - (log c-log o) were calculated. These values are shown in Table 2. The sterilizing activity value L and the bacteriostatic activity value S also showed good values as a result of showing a sterilizing power behind the contact value without elapsing long time.

sample Viable cell count log number Sterilizing activity value L Bacteriostatic activity S Immediately after (o) <20 <1.3 > 3.1 > 2.6
After 18 hours (c) <20 <1.3

<Antiviral Test>

Inactivation test for influenza virus was carried out by using the antibacterial antiviral fiber material of Experimental Example 1. Specifically, it is as follows.

First, the antimicrobial antiviral fiber material obtained in Example 1 was cut into 2 cm x 2 cm, and 0.05 g of the material was sterilized by autoclaving at 121 ° C for 15 minutes. First, a preliminary test was conducted. Then, the virus suspension was dropped into the sample, and after preservation at room temperature for 24 hours, the virus infection value was measured.

Details of the test method are as follows.

1. Experimental virus: Influenza A (H1N1)

2. Cells used: MDCK (NBL-2) cells ATCC CCL-34 strain (Daikin Pharmaceutical Co., Ltd.)

3. Usage medium: Cell growth medium · Eagle MEM medium [NiSSi] (1) [Japan Pharmaceutical] uses 10% by mass of UTC serum. Cellular fiber medium · A medium having the following composition was used.

Eagle MEM medium "Nissui" (1) 1000 ml

14 ml of 10% NaHCO ₃

9.8 ml of L-clutamine (30 g / l)

100 × Vitamin solution for MEM 30 ml

10% albumin 20 ml

0.25% trypsin 20 ml

The preparation procedure of the virus suspension is as follows. First, the cells were cultured using a cell growth medium, and the used cells were cultured in Frasco for tissue culture. The viral inoculation was performed by inoculating the test cell with the cell growth medium in Prasco after in vitro culture. Next, the cell maintenance medium was added, and the cells were incubated with a carbonic acid gas incubator (CO ₂ concentration: 5%) at 37 ° C ± 1 ° C for 1 to 5 days.

After cultivation, the cell morphology was observed using an introduced phase contrast microscope to confirm that a morphological change (cytopathic effect) was taking place in the cells. Next, the culture was centrifuged (30000 r / min, 10 minutes), and the obtained clear solution was used as a virus suspension.

0.2 ml of the virus suspension was added to the sample and stored at room temperature. After 24 hours, the virus suspension suspended in the sample was rinsed with 2 ml of the cell maintenance medium. The virus infection value was measured on this sample.

Cells were monolayer cultured in a tissue culture microplate (96 wells) using a cell growth medium, the cell growth medium was removed, and 0.1 ml of the cell maintenance medium was added. Next, 0.1 ml of the washed solution or its diluted solution was inoculated into four wells and cultured for 4 to 7 days in a carbon gas incubator (CO ₂ concentration: 5%) at 37 ± 1 ° C. After the incubation, an introduced phase contrast microscope by observing the presence or absence of morphological changes of cells (cytopathic effect), which was converted value infection of liquid 1ml corresponds purged by calculating the 50% tissue culture infected dose (TCID _{5 0)} by the Reed-Muench method. the results are Table 3 shows the results.

Also, the control is a plastic chalet (Schale).

Measure log TCID ₅₀ / ml Immediately after inoculation contrast 5.3 After 24 hours
sample 3.0 contrast 4.7

From this, it was confirmed that the control effect of the virus number close to two digits was demonstrated by comparing the sample with the control.

In addition, the sample was washed by centrifugation (3000 r / min for 10 minutes), and the virus infection value was measured against the clear water obtained therefrom. In the preliminary experiment, the cytopathic effect by the subject was not confirmed Respectively.

Claims (4)

Silica-based glass fibers having a fiber diameter of not less than 3 mu m and not more than 10 mu m having an aluminum content of not more than 3% by mass are immersed in an aqueous acid solution and subjected to acid treatment, An antimicrobial antiviral glass fiber material which adsorbs the metal ion to the zeolite layer by contacting an aqueous solution of a metal compound containing the antibacterial antiviral metal ion after forming a zeolite layer on the surface by immersion in an aqueous solution, &Lt; / RTI &gt;
The method according to claim 1,
Wherein the acid aqueous solution is an inorganic acid having a pH of 2 or less and the acid treatment is performed in an environment of 70 占 폚 or more for 1 hour to 8 hours. The method according to claim 1,
Wherein the alkali aqueous solution is an aqueous solution of an alkali metal or alkaline earth metal having a pH of 13 or more and containing 5 mass% or more of aluminum oxide, and the alkali treatment is performed for 2 to 12 hours in an environment of 70 占 폚 or more &Lt; / RTI &gt; An antimicrobial antiviral glass fiber material to which the metal ion is added to the zeolite layer formed on the surface of a glass fiber material produced by the method according to any one of claims 1 to 3.

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