JPH09301802A - Antibacterial porous glass fiber - Google Patents

Abstract

(57) [Abstract] [Problem] Conventionally, an antibacterial glass cloth is prepared by dissolving an antibacterial component in a glass fiber or directly applying an antibacterial agent,
Alternatively, a powder containing an antibacterial agent is fixed with a binder. Therefore, there are problems that the price is high, the effect does not last long because the amount of antibacterial agent cannot be increased, and it cannot be washed even if it becomes dirty. SOLUTION: An antibacterial agent is gradually released by putting an antibacterial agent such as silver nitrate into the pores of porous glass fiber obtained by treating glass fiber containing an acid-soluble component with hydrochloric acid or the like,
The effect lasted for a long time, and almost no antibacterial agent flowed out even when immersed in water.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the production of porous glass fibers having antibacterial properties.

[0002]

2. Description of the Related Art Glass fibers having antibacterial properties can be used for air conditioner filters, daily humidifiers for ultrasonic humidifiers, kitchens, bathrooms, etc., and their manufacturing method is disclosed in JP-A-05-92.
As disclosed in Japanese Patent Laid-Open No. 113 and Japanese Patent Application Laid-Open No. 06-80527, there is a method of preventing the growth of microorganisms by adhering and applying antibacterial zeolite, antibacterial paint or the like on the filter surface. Depending on the conditions of use, this method may cause zeolite and paint adhered to the glass fiber surface to peel off due to vibration or shock, and if the amount of adhesion increases to increase the antibacterial effect, the filtration resistance will increase when used in filters, etc. , The pressure loss increases, and the filtration and aeration rates decrease.

[0003] In addition, those which use the porosity of silica gel as a carrier and contain complexed silver as an antibacterial agent, and JP-A-HEI-0.
The glass containing silver ions disclosed in JP-A-4-40469 is made into a fine powder, or is disclosed in JP-A-07-25272.
There are also examples in which soluble glass containing a zinc component, which is disclosed in Japanese Patent Laid-Open No. 0, is pulverized and mixed into a resin to form a fiber, or is attached to the fiber. However, there are problems such as not being able to mix a sufficient amount of powder for fiber formation, and the slow elution rate of antibacterial components on the fiber surface, and the problems described above when used by attaching to fibers. In addition to the above, the surface of the powdered antibacterial agent may be covered with an adhesive or the like used for adhering to the glass fiber, and the effect may be reduced. In order to prevent this situation, it has been considered to use glass fibers themselves in which a silver component having an antibacterial action is dissolved, as disclosed in JP-A-06-285314. However, since silver ions are dissolved in the entire glass fiber as one component, if the silver ions on the surface of the glass fiber are consumed, it takes time for the silver ions to move from the inside, and the antibacterial action becomes weaker. Molten glass having a composition containing an ion-releasing component requires a high degree of glass fiber spinning technology, which is a production problem.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a product having a good antibacterial effect, and the glass fiber itself having an antibacterial effect lasts a long time.

[0005]

Means for Solving the Problems The present inventor exerts an antifungal effect, a bactericidal effect, and a deodorizing effect by supporting a chemical agent having an antibacterial property in the pores of a porous glass fiber. Solved.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The antibacterial glass fiber of the present invention is one in which an antibacterial agent is supported in the pores of a porous glass fiber, and the processed glass fiber product is yarn, cloth, roving, Loving cloth, chopped strands, chopped strand mats, non-woven fabrics, powders and the like having the same appearance as the form of products manufactured from ordinary glass fibers.

The porous glass fiber carrying the antibacterial agent is
It can be obtained by acid-treating known glass fibers having a composition suitable for producing porous glass fibers, E glass fibers, or the like. The larger the specific surface area, the more the antibacterial agent that can be contained in the porous glass fiber and the longer its effect, but there are problems such as fiber strength.
It is desirable that it is 00-500 m ² / gr. The pores in the glass fiber carrying the antibacterial agent have a diameter of 3-5 nm.
It is desirable that a large number of particles having a diameter of about 4 nm or less are distributed in the range of. If the diameter of the pores is about 4 nm, it has the same sustained release property as the microcapsules, and the antibacterial effect can be maintained for a long time.

A glass fiber composition particularly suitable for carrying out the present invention is SiO ₂ 50-60 wt%, Al ₂ O ₃ 10-.
_{20wt%, B 2 O 3 20-30wt} %, CaO
0.5-5 wt%, MgO 0-4 wt%, Li ₂ O +
Na ₂ O + K ₂ O 0-0.5%, TiO ₂ 0.5-
5 wt%. Li ₂ O is added in an amount of 0-0.3 wt%. TiO ₂ is added to lower the melting temperature and improve the strength of the porous glass fiber, and Li ₂ O is added to homogenize the phase-separated state, reduce the pore diameter of the porous glass fiber, and reduce variations. . Na ₂ O + K ₂ O is an unavoidable component contained in the raw material. In addition to the above components, ZrO ₂ , F ₂ and SO ₃ are added to the extent that the characteristics of glass are not impaired.
It is possible to contain up to 3 wt% of such components.
Since the glass fiber composition is very finely diameter of the pores can be by acid treatment because of the SiO ₂ with many parts and SiO ₂ less portions phase separation is very small and 3-5 nm, excellent adsorption, The antibacterial agent can be released little by little for a long period of time.

Further, since the acid-treated glass fiber has little decrease in strength, it can be used as a cloth,
Textile products for hospitals and medical care, such as curtains, wall cloths, bed cores and air conditioner filters, vacuum cleaner exhaust filters, cloth, chopped strands, powder products such as FRP, FRTP, paints, etc. It is also possible to add to. As the type of acid required for the acid treatment, nitric acid, which has a small decrease in tensile strength, is suitable, and then sulfuric acid and hydrochloric acid are suitable. Suitable treatment time varies depending on the composition of glass fiber, kind of acid, concentration, treatment temperature, etc.
When the glass fiber is treated at a temperature of 70 ° C. using wt% nitric acid, 90 wt of the present invention can be obtained in about 10-20 minutes.
A porous glass fiber containing at least SiO ₂ is obtained.
However, if the purpose of using the porous glass fiber is gas adsorption, it is desirable that the acid concentration is low in order to reduce the diameter of the pores and increase the specific surface area. The test is determined repeatedly. Also, the type of acid used is not limited to one type of acid and may be a mixture of two or more types of acids, which can be appropriately selected from those capable of efficiently eluting soluble components from the glass of the present invention.

Soluble in solvent or water used in the present invention
Known antibacterial agents such as silver compounds, boric acid, hinokiti
Allyl, benzoic acid, benzalkonium chloride, dipheni
Among known antibacterial agents such as sodium chloride and potassium sorbate
It is selected according to the purpose of use. Among them, silver-based antibacterial agents
Is the safest and has E. coli, Staphylococcus, Pseudomonas aeruginosa
A wide range of bacteria such as bacteria and molds such as black mold
It exhibits antibacterial properties against the surrounding microorganisms. Silver is in a metallic state
Has a small antibacterial effect and is excellent due to the ionization of silver.
Exerts excellent antibacterial properties. However, chlorine
Ions are everywhere, and chloride makes chloride easy
Changes to silver chloride and returns to the state of silver that is not ionized by light
And the antibacterial property is reduced. In the present invention, the following method
It succeeded in sustaining the ionization of silver. Porous
10 wt% of glass fiber suitable for manufacturing glass fiber
Treated with hydrochloric acid to wash the glass fiber surface with water and
After drying with hydrochloric acid left, it is immersed in an aqueous solution of silver nitrate to form pores.
Silver chloride is formed inside. High concentration of hydrochloric acid exists in the pores
Existing complex ions [Agcl_Two]^-It has become. This
As it is, silver remains ionized, but more stable
Ammonia water, thiosulfate water soluble to generate complex ions
Complex ions [Ag (NH_Three)_Two]
⁺, [Ag (S_TwoO _Three)_Two]^3-It can be.

Furthermore, in order to more stably and effectively release the effect of the antibacterial agent for a long period of time, it is possible to cover the pores of the fiber carrying the antibacterial agent with a silica coating, and tetraethoxysilane (hereinafter referred to as TEOS). It is dipped in a liquid having a concentration of 0.05-0.3 wt% and dried. The fiber becomes brittle when immersed in a solution of 0.3 wt% or more, and the effect is small when it is 0.05 wt% or less.

[0012]

【Example】

<Example 1> SiO ₂ 51.8 wt%, Al ₂ O ₃
13.8 wt%, B ₂ O ₃ 26 wt%, CaO
3.6 wt%, MgO 2.4 wt%, Li ₂ O 0.
15 wt%, Na ₂ O 0.15 wt%, K ₂ O 0.
A glass fiber yarn consisting of 200 glass fibers having a composition of 1 wt% and TiO ₂ 2.0 wt% and an average fiber diameter of 7 μm was used, and 60 warps / 25 mm, weft 58
Weaving a book / 25 mm cloth and cutting it into 10 cm squares, 1 piece in 50 gr of 10 wt% hydrochloric acid at a temperature of 70 ° C.
After soaking for 5 minutes, rinse with water at room temperature for 1 minute and then at 30 ° C for 30 minutes.
Dry for minutes, specific surface area 350 m ² / gr, average pore size 4
A porous glass fiber cloth of nm was obtained. Then, this was immersed in an aqueous solution of silver nitrate (50 wt%) to obtain 3.6 w inside the pores.
t% silver chloride was produced. After that, rinse with water for 1 minute at room temperature and then 8
By drying at 0 ° C. for 30 minutes, the hydrochloric acid remaining in the pores was changed to concentrated hydrochloric acid to dissolve silver chloride and obtain an antibacterial glass fiber cloth. After this cloth was immersed in water for 3 hours and dried, the weight loss was measured and the residual amount was calculated to be 3.4% by weight.

<Example 2> The glass cloth used in Example 1 was treated with hydrochloric acid, immersed in an aqueous solution of silver nitrate, and washed with water. After the same operation as in Example 1 was performed, the glass cloth was not dried. 1 for ammonia water (10 wt%)
After immersing for 5 minutes, the silver chloride in the glass fiber pores is converted to a soluble complex ion [Ag (NH ₃ ) ₂ ] ⁺ , then at 30 ° C. for 30 minutes.
After drying for a minute, an antibacterial glass cloth was obtained.

<Embodiment 3> The glass cloth of Embodiment 1 is T
It was dipped in a 0.3 wt% solution of EOS and dried. The glass cloth was dipped in water for 3 hours, dried, and the elution amount was measured. The weight loss of the entire glass cloth was 0.0
It was 6% by weight.

Example 4 A glass fiber yarn made of 200 glass fibers of E glass fiber having an average fiber diameter of 7 μm was used as the warp, and the average fiber diameter 7 used in Example 2 was used as the weft.
Using a glass fiber yarn consisting of 200 μm glass fibers, 60 warps / 25 mm, 58 wefts / 25 mm
After weaving the above cloth and cutting it into 10 cm squares, soak it in 50 gr of 10 wt% nitric acid at a temperature of 70 ° C for 15 minutes, then wash it sufficiently with normal temperature until there is almost no release of nitric acid, and dry at 80 ° C for 30 minutes. did. Since the E glass fiber yarn of the warp had a short acid treatment time, the tensile strength was reduced by about 10%, and the cloth was suitable for an air filter or the like which requires strength.

Comparative Example 1 A silver nitrate aqueous solution (50 wt%) was used in the same manner as in Example 1 except that E glass fiber cloth of the same standard as that used in Example 1 was used and no acid treatment was performed.
%). After that, wash at room temperature for 1 minute and then at 80 ℃ for 3
0.56% by weight of silver nitrate after drying for 0 minutes
An adherent antibacterial glass fiber cloth was obtained.

Test Method for Antibacterial Property Agar medium is prepared by inoculating the test bacterial solution on a flat plate dish having a diameter of 100 mm. The glass fibers of Examples 1 and 2 and Comparative Example 1 cut into a diameter of 28.6 mm were lightly placed on this agar medium and brought into close contact therewith. Then, it was cultured at 37 ° C. for 24 hours. Then, the number of viable bacteria in the surrounding inhibition zone was measured.

[0017]

[Table 1]

[0018]

According to the present invention, since the antibacterial agent is carried in the pores of the porous glass fiber, it is not necessary to attach the antibacterial agent to the fiber with a sizing agent as in the case of powder-supported materials. deterioration,
Does not come off due to vibration or shock. In addition, since the cloth does not cause clogging due to application, the pressure loss of the fluid is small when used for an air filter or the like. Further, in the method of forming a precipitate of silver chloride in the pores of the porous glass fiber, the loss of silver chloride due to the outflow and diffusion from the pores by the subsequent water washing treatment is small. Therefore, the yield of silver chloride is good, and the amount of silver ions in a stable state increases by the subsequent complex ionization treatment, and thus the effect lasts for a long time. In addition, even if the ordinary antibacterial agent is supported in the pores, since the specific surface area is large, the antibacterial agent can be stored in a large amount in the glass fiber,
When the average diameter of the pores is 4 nm or less, the release is sustained and the effect lasts for a long time. Furthermore, by covering the surface of the porous glass fiber carrying the antibacterial agent with TEOS, it is possible to exhibit a more stable and long-term antibacterial effect.

Claims (4)

[Claims] 1. A processed product of antibacterial porous glass fiber in which an antibacterial agent is supported in pores of porous glass fiber produced by eluting a component easily soluble in acid in glass fiber. 2. The antibacterial porous glass fiber processed article according to claim 1, wherein the antibacterial agent is a complexed silver or a silver compound capable of generating silver ions. 3. Porous glass fibers containing a hydrochloric acid solution in their pores are dried, or are not dried and are immersed in a silver nitrate solution to precipitate silver chloride in the pores of the porous glass fibers, wash with water and then dry. Characteristic antibacterial porous glass fiber manufacturing method 4. An antibacterial porous glass fiber prepared by immersing the antibacterial porous glass fiber according to claim 5 in aqueous ammonia or an aqueous thiosulfate solution to form complex ions in the pores, followed by washing with water and drying. Manufacturing method