JP2001026438A - Antibacterial agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin exhibiting an excellent antibacterial property and to enhance discoloring resistance and water resistance of the resin by incorporating ZnO, B2O3 and/or P2O5, or Al2O3 and/or ZrO2 and an alkali metal oxide and SiO2 into the resin. SOLUTION: This antibacterial agent contains 0.5-15m mol% at least one kind of oxides selected from the group consisting of a 50-70 mol% ZnO, 20-50 mol% B2O3 and/or P2O5, Al2O3 and ZrO2, 5-10 mol% alkali metal oxide and 0-20 mol% SiO2. A formulated raw material of glass is melted in a melting bath at 1,000-2,000 deg.C and the melted material is rapidly cooled to prepare glass and then the obtained lumpy glass is pulverized to manufacture the antibacterial agent. The antibacterial agent is usually used in a powdery state and the powder having a <=20 μm average particle size is desirably used for dispersibility in resin processing in general and when the resin is processed into a fiber or film product, the powder having a <=5 μm average particle size and a 20 μm maximum particle size is desirably used not to generate lowering of the property.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antibacterial agent comprising glass containing zinc oxide at a high concentration. The antibacterial agent of the present invention has a high antibacterial effect, and has very little discoloration over time during processing, storage and use, and has fungicidal, algal and antibacterial properties when blended with various polymer compounds. It is an antibacterial resin composition which can be processed and used for textile products, paint products, molded products and the like.

[0002]

2. Description of the Related Art Conventionally, as an inorganic antibacterial agent, an antibacterial metal such as silver or copper supported on apatite, zeolite, glass, zirconium phosphate, silica gel or the like is known. These have higher safety than organic antibacterial agents, and are characterized by long lasting antibacterial effects because they do not volatilize or decompose and have excellent heat resistance. Therefore, these antibacterial agents and various polymer compounds are used as antibacterial processed products processed into fibrous, film-like, or various molded articles using the antibacterial resin composition obtained by mixing them with various polymer compounds. I have.

[0003] Above all, an antibacterial agent made of glass containing an antibacterial metal such as silver, copper or zinc can easily control the particle size, refractive index and dissolution of the antibacterial metal according to the purpose. Utilizing it, it is blended and used in various resin compositions.

For example, Japanese Patent Publication No. Hei 4-74453 has been proposed as an antibacterial agent comprising a glass containing silver, and Japanese Patent Laid-Open No. 7-2579 has been proposed as an antibacterial agent comprising a glass containing zinc.
No. 38 has been proposed. However, antibacterial agents made of conventional silver-containing glass have a high antibacterial effect,
Deterioration and deterioration of the resin itself are promoted due to the effect of heat when kneading into the resin and exposure to ultraviolet light after resin processing,
There is a problem that the original excellent properties of the resin processed product are often impaired, such as discoloration of the resin processed product.

[0005] Further, the antibacterial agent made of copper-containing glass is colored blue, and when kneaded into a resin, the resin-processed product is also colored, so that it is difficult to use it for white / light-colored products. In addition, there is a problem in that the range of use is limited due to troubles in matching colors to various colors. Furthermore, the antibacterial agent made of glass containing copper or zinc has a low antibacterial property as compared with glass containing silver. Has to be increased, and there is a problem that the original resin physical properties are deteriorated.

In order to solve these problems, 40 to 55 mol% of P ₂ O ₅ , 35 to 45 mol% of ZnO, Al ₂
O ₃ 5-15 mol%, the B ₂ O ₃ with respect to 100 parts by weight of glass containing 1 to 10 mol%, the Ag ₂ O 0.01 to 1.0
An antibacterial agent containing 0.1% by weight has been proposed (Japanese Patent Laid-Open No. 8-1).
No. 75843). However, Ag ₂ O has been added to exhibit sufficient antibacterial properties in this antibacterial agent.
Has a limited amount of addition in order to suppress discoloration due to silver ions, and is not substantially satisfactory in antibacterial properties. The glass used here is an antibacterial metal (Zn)
Has a high dissolution rate and high initial antibacterial properties, but does not have sufficient sustained antibacterial effects. Further, since the antibacterial agent made of this glass has low water resistance, an antibacterial resin molded product kneaded with the antibacterial agent may be whitened or deformed by warm water or yellowed by heat during processing.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antibacterial agent made of glass which exhibits excellent antibacterial properties when blended with a resin, and which is also excellent in discoloration resistance and water resistance. It is.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that ZnO is contained at a very high concentration and at least one selected from Al ₂ O ₃ and ZrO _2. The borate and / or phosphate glasses using a combination of at least one species and an alkali metal oxide have high antibacterial properties, and are excellent in discoloration resistance and water resistance, and are excellent in solving all the above-mentioned problems. The inventors have found that the present invention has been completed. That is, the present invention provides ZnO of 50
70 mol%, B ₂ O ₃ and / or P ₂ O ₅ 20 to 50 mole%, at least 1 element selected from Al ₂ O ₃ and ZrO ₂
0.5 to 15 mol% of at least seeds and 5
10 mol%, and SiO ₂ is an antibacterial agent comprising a glass containing 0 to 20 mol%.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. ○ Antibacterial agent The antibacterial agent of the present invention contains ZnO in an amount of 50 to 70 mol%, B ₂ O ₃
And / or 20-50 mol% of P ₂ O ₅ , Al ₂ O ₃ and Z
at least one selected from and rO ₂ 0.5 to 15
Mol%, 5 to 10 mol% of alkali metal oxide, and S
the iO ₂ made of glass from 0 to 20 mol. The preferable content ratio of ZnO which is a component for imparting antibacterial performance to the antibacterial agent of the present invention is 55 to 60 mol%. 70 ZnO
If the amount is more than mol%, there is a problem that a stable glass is hardly obtained. If the amount is less than 50 mol%, the antibacterial property of the glass of the present invention becomes insufficient.

The preferred content of B ₂ O ₃ or P ₂ O ₅ is
It is 20 to 40 mol%, and more preferably 25 to 35 mol%. If B ₂ O ₃ or P ₂ O ₅ is added in an amount of more than 50 mol%, the water solubility of the antibacterial agent comprising the glass of the present invention becomes large, and the excellent antibacterial properties and discoloration resistance of the glass of the present invention are obtained. In addition, there is a problem that the water resistance is impaired, and if it is less than 20 mol%, there is a problem that it is difficult to obtain a stable glass.

The preferable content ratio of Al ₂ O ₃ or ZrO ₂ is 1 to 10 mol%. Al ₂ O ₃ or ZrO ₂
If the amount is more than 15 mol%, it is difficult to obtain a stable glass. If the amount is less than 0.5 mol%, the water resistance and discoloration resistance of the antibacterial agent comprising the glass of the present invention are impaired. is there. Preferred examples of the alkali metal oxide include Li2O, Na2O, and K2O.
Is particularly preferred. A preferable content ratio of the alkali metal oxide is 6 to 8 mol. If the alkali metal oxide is added in an amount of more than 10 mol, the water solubility of the glass of the present invention increases, and the sustained antibacterial property, discoloration resistance and water resistance of the antibacterial agent of the present invention are impaired. If it is less than 5 mol%, the solubility of the glass will be low, and sufficient antibacterial properties will not be exhibited.

The essential glass-forming components in the present invention are:
B ₂ O ₃ or _{P 2 O 5, Al 2 O} 3 or is a ZrO _2, it is possible to add other glass forming ingredients as desired. Preferred examples thereof include SiO ₂ and TiO ₂ , with SiO ₂ being particularly preferred. The preferable content ratio of other glass-forming components is 20 mol% or less, more preferably 15 mol% or less. Also, if desired, Mg
O, CaO, CaF _{2 and the} like can be appropriately contained. These so-called "modifying components" are effective in facilitating melting and moldability of the glass, but when contained in a large amount, the water resistance of the glass may be reduced, so that at most 3 mol% or less. And more preferably 1
Mol% or less.

When the antimicrobial agent of the present invention is blended with a resin, it is usually in the form of a powder, and the one having an average particle diameter of 20 μm or less is preferably used for dispersion processing into a resin, and is processed into a fiber product, paint, film or the like. In this case, it is preferable that the average particle diameter is 5 μm or less and the maximum particle diameter is 20 μm or less in order not to cause deterioration in physical properties.

In producing the antibacterial agent of the present invention, a known production method can be adopted. In general, after melting the raw material mixture of glass in a melting pot at 1000 to 2000 ° C., the melt is quenched, and after preparing the glass, the obtained bulk glass is pulverized to easily form the powdered glass. Obtainable.

The antimicrobial agent of the present invention is made of zinc oxide (melting point: about
It may be considered difficult to vitrify because its concentration is higher than that of the conventional antibacterial agent (2000 ° C), but if it is melted at an appropriate melting temperature and quenching means suitable for the cooling characteristics of the melt is used. The glass having any composition according to the present invention can be easily obtained.

In order to enhance the quenching effect, it is effective to increase the contact area between the molten material and the cooling body. For example, the molten material of glass is sandwiched between two rotating metal rollers cooled by a coolant such as water. Is passed through at a high speed to obtain an extremely large cooling effect. By using this cooling method, vitrification is extremely easy. Further, when cooled by this method, since the glass that has come out between the rollers is formed into a thin plate, it can be very easily crushed into a powder.

When the antibacterial agent of the present invention is kneaded into a resin or a fiber, the antibacterial performance is exhibited by the antibacterial agent present on the surface, but the antibacterial agent falls off due to friction, washing, washing and the like on the surface. There is. When shedding is remarkable, the antibacterial effect decreases, and in some cases, the effect disappears in a very short time. When the antibacterial agent of the present invention is kneaded into a resin or the like, it may be subjected to a surface treatment with a silane coupling agent or the like in order to improve adhesion and adhesion and prevent falling off.

The surface treatment agent used in the present invention may be appropriately selected depending on the use, the kind of resin, the processing method, etc., and is conventionally used as a coupling agent for surface treatment of inorganic powder. Any of them can be used, and there is no particular limitation. Specific examples of the surface treatment agent include vinyl silanes such as vinyl triethoxy silane and vinyl trimethoxy silane, and (meth) acryloxy silanes such as γ- (methacryloxy propyl) trimethoxy silane and γ-glycidoxy propyl trimethoxy silane. Sidoxysilane, tetraethoxysilane, silicone oil, tetraisopropoxytitanium, aluminum ethylate and the like can be mentioned. The surface treatment method is not particularly limited, and may be any method conventionally known as a surface treatment method for inorganic powders. For example, there are a dry method, a wet method, a spray method, a gasification method and the like.

The antibacterial agent of the present invention can be used alone, but when used together with a silver-based inorganic antibacterial agent, its antibacterial properties can be further enhanced. This is because a synergistic effect is obtained by two different antibacterial components of zinc ions in the glass and silver ions in the silver-based inorganic antibacterial agent. Further, the antibacterial agent of the present invention has an extremely excellent anti-discoloration effect,
By using a silver-based inorganic antibacterial agent together, coloring and discoloration of the resin product do not occur.

The silver-based inorganic antibacterial agent used in combination with the antibacterial agent of the present invention is not particularly limited as long as it is an inorganic compound supporting silver. Examples of the inorganic compound supporting silver ions include the following. That is, there are inorganic adsorbents such as activated alumina and silica gel, and inorganic ion exchangers such as zeolite, calcium phosphate, zirconium phosphate, titanium phosphate, potassium titanate, hydrated bismuth, hydrated zirconium, and hydrotalcite.

Among these inorganic compounds, an inorganic ion exchanger is preferred because it can strongly support silver ions.
In particular, a silver-based inorganic antibacterial agent comprising a zirconium phosphate salt in which M is Zr in the following general formula [1] is preferable. _{Ag a A b M 2 (PO} 4) 3 · nH 2 O [1] (A is an alkali metal ion, alkaline earth metal ions,
It is at least one ion selected from an ammonium ion or a hydrogen ion, M is a tetravalent metal, and both a and b are positive numbers. Here, m is a valence of A, and n is a number satisfying 0 ≦ n ≦ 6. )

The antibacterial agent of the present invention may be mixed with various other additives as necessary in order to improve kneadability into a resin and other physical properties. Specific examples include pigments, dyes, antioxidants, light stabilizers, flame retardants, antistatic agents, foaming agents, impact modifiers, glass fibers, metal soaps, moisture inhibitors and extenders, coupling agents, fluidity improvements. Agents, deodorants, wood flour, antifouling agents, rust inhibitors, etc. Also,
By further adding an organic antibacterial and antifungal agent, it is possible to improve the fast-acting effect and the antifungal effect.

Preferred examples of the organic antibacterial fungicide compound to be mixed with the antibacterial agent of the present invention include quaternary ammonium salt compounds, fatty acid ester compounds, biguanide compounds, bronopol, phenol compounds, and anilide compounds. Compounds, iodine compounds, imidazole compounds, thiazole compounds, isothiazolone compounds, triazine compounds, nitrile compounds, fluorine compounds, chitosan, tropolone compounds, and organometallic compounds (zinc pyrithione, OBPA), etc. There is.

An antimicrobial resin composition can be easily obtained by blending the antimicrobial agent of the present invention with a resin. The type of resin that can be used is not limited, and may be any of a natural resin, a synthetic resin, and a semi-synthetic resin, and may be any of a thermoplastic resin and a thermosetting resin. The specific resin may be any of a molding resin, a fiber resin, and a rubber-like resin. Examples thereof include polyethylene, polypropylene, vinyl chloride, ABS resin, AS resin, nylon resin, polyester, polyvinylidene chloride, and polystyrene. , Polyacetal, polycarbonate, PBT, acrylic resin, fluorine resin, polyurethane elastomer, polyester elastomer, melamine, urea resin, tetrafluoroethylene resin, unsaturated polyester resin, polyethylene, polypropylene, rayon, acete -, Acrylic, polyvinyl alcohol, cupra, triacete-
Resin for fibers such as g, vinylidene, etc., natural rubber, silicone rubber, styrene butadiene rubber, ethylene propylene rubber, fluorine rubber, nitrile rubber, chlorosulfonated polyethylene rubber, butadiene rubber, synthetic natural rubber, butyl rubber, urethane rubber and acrylic rubber And the like.

The preferred proportion of the antimicrobial agent in the antimicrobial resin composition is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the antimicrobial resin composition. If the amount is less than 0.01 part, the antibacterial property of the antibacterial resin composition may be insufficient. On the other hand, if the amount is more than 10 parts, the antibacterial effect is hardly improved.

Any known method can be employed for incorporating the antimicrobial agent into the resin. For example, an antibacterial agent powder, using an impregnating agent or a dispersant for improving the dispersibility of the antibacterial agent powder to make the powder and the resin easily adhere to each other, using a pellet resin or powder resin and a mixer. Direct mixing method, mixing as described above, forming into a pellet with an extruder, then blending the molded product with the pellet resin, pelletizing the antibacterial agent at a high concentration using wax After molding, a method of blending the molded product with a pellet resin, a method of blending a paste-like composition obtained by dispersing and mixing an antibacterial agent with a high-viscosity liquid material such as a polyol, and the like are incorporated into the pellet resin. .

For the molding of the above antibacterial resin composition, any known processing techniques and machines can be used in accordance with the characteristics of various resins, and heating and mixing at an appropriate temperature or pressure are performed while applying pressure or reducing pressure. Can be easily prepared by mixing, kneading or kneading methods, and their specific operations may be performed by a conventional method, such as lump, sponge, film, sheet, thread, pipe, or a composite thereof. Can be formed into various forms.

The antibacterial resin molded article thus obtained has excellent antibacterial properties and discoloration resistance, which are the components of the antibacterial resin molded article. It does not deteriorate during storage or use of the antibacterial resin composition thereafter.

The use form of the antibacterial agent of the present invention is not particularly limited, and it can be appropriately mixed with other components or compounded with other materials according to the use. For example, it can be used in various forms such as powder, powder dispersion, granule, paint, fiber, paper, film, and aerosol.

Applications The antibacterial resin composition containing the antibacterial agent of the present invention can be used in various fields requiring antifungal, antialgal and antibacterial properties, such as electrical appliances, kitchen products, textile products, home building materials, It can be used as toiletry products, paper products, toys, leather products, stationery and other products. To illustrate more specific applications, appliances include a dishwasher, a dish dryer, a refrigerator, a washing machine, a pot, a television, a personal computer, and a CD.
Boombox, camera, video camera, water purifier, rice cooker, vegetable cutter, register, futon dryer, FAX, ventilation fan, air conditioner, etc. Kitchen products include tableware, cutting board, push-cut, tray, chopsticks, Old tea set, thermos,
Kitchen knife, ladle handle, fly return, lunch box, rice scoop, bowl, drainer, triangle corner, sardine, garbage basket,
There are drain bags and the like.

Textile products include shower curtains, futon cotton, air conditioner filters, pantyhose, socks, towels, sheets, futon sideways, pillows, gloves, epolons, curtains, diapers, bandages, masks. , Sportswear, etc.
House and building material products include decorative boards, wallpapers, floorboards, window films, handles, carpets, mats, artificial marble, handrails, joints, tiles, waxes, and the like. In addition, toiletry products include toilet seats, bathtubs, tiles, pots, filth bowls, toilet brushes, bath lids, pumice stones, soap containers, bath chairs, clothes baskets, showers, wash basins, and paper products. There are medicine boxes, sketchbooks, charts, origami and the like, and toys include dolls, stuffed animals, paper clay, blocks, puzzles and the like.

Further, leather products include shoes, bags, belts, watch bands, interiors, chairs, gloves, hanging leathers, and the like. Stationery includes ball pens, sharp pens, pencils,
There are eraser, crayon, paper, notebook, floppy disk, ruler, post-it, stapler, etc. Other products include insoles, makeup containers, scrubbers, makeup puffs, hearing aids, musical instruments, cigarette filters, cleaning adhesive paper sheets, hanging leather grips, sponges, kitchen towels, and cards.
, Microphones, barber supplies, vending machines, razors, telephones, thermometers, stethoscopes, slippers, costume cases, toothbrushes, sandbox sand, food packaging films, sprays and the like.

[0033]

The mechanism by which the antibacterial agent of the present invention has excellent antibacterial properties, discoloration resistance and water resistance is presumed as follows.
That is, since the glass in the present invention contains a high concentration of ZnO and at the same time contains an appropriate amount of an alkali metal oxide, it has a suitable glass melting property, thereby having a large antibacterial effect and a long lasting effect. Is also excellent. Alkali metal oxides, to increase the solubility of the glass, while the effect of enhancing the antibacterial effect, it may deteriorate the water resistance and color fastness, combined use Al ₂ O ₃ and / or ZrO ₂ By doing so, the glass solubility is adjusted, and as a result, a glass excellent in water resistance and discoloration resistance can be obtained.

[0034]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Example 1 (Preparation of antibacterial agent) A raw material mixture having the composition shown in Table 1 (sample Nos. 1 to 4) was heated and melted at 1000 to 1400 ° C. to produce glass, and the obtained glass was ball milled. To obtain an antibacterial agent composed of glass particles having an average particle size of about 10 μm. Sample No.
5 kg of the antimicrobial agent of No. 2 was placed in a Hensel mixer, and 200 g of an ethanol solution containing 50 g of γ-aminopropyltrimethoxysilane was sprayed with stirring and taken out.
Surface treatment was performed by heat treatment at 0 ° C. for 12 hours (Sample No. 9).

Comparative Example 1 (Preparation of antibacterial agent) An antibacterial agent made of glass was obtained in the same manner as in Example 1 except that the raw material formulations having the compositions shown in Table 1 (samples Nos. 5 to 8) were used. Was.

[0036]

[Table 1]

Test Example 1 (Discoloration test, antibacterial test and water resistance test) Polystyrene resin manufactured by Sumitomo Chemical Co., Ltd. (trade name ST85)
0), the antimicrobial agent (sample Nos. 1-4, 9) was 0.3
% By weight, injection molding machine M-5 manufactured by Meiki Seisakusho Co., Ltd.
Injection molding was performed at a molding temperature of 220 ° C. using 0AII-DM to produce 11 cm × 11 cm × 2 mm antibacterial plates (prototype Nos. 1 to 3) (however, the antibacterial plates of each prototype number are the same as the prototype number). This is a sample using a sample having a sample number, and the same applies hereinafter.) In addition, a resin composition in which the resin composition was retained in a molten state for 5 minutes in a cylinder at the time of injection molding was also molded, and the color was confirmed to evaluate discoloration.

For comparison, the antibacterial agents of samples Nos. 5 to 8 were 0.3.
Molded only by weight% (prototype Nos. 5 to 8) and molded only polystyrene resin (prototype No. 10)
Was similarly injection molded. In addition, the antibacterial activity of the produced various prototype polystyrene plates was evaluated by the following method.

Staphylococcus aureus was used as a test bacterium, and the antibacterial plate was cut into 5 cm × 5 cm, and 0.5 ml of the bacterial solution was used so that the number of bacteria per plate was 10 ⁵ to 10 ^6. Was dropped onto the surface, and a polyethylene film of 4.5 cm × 4.5 cm was put on the surface, and the polyethylene film was uniformly contacted with the surface, and stored at a temperature of 35 ° C. and a humidity of 95 RH% for 24 hours. After 0 hour from the start of storage (the number of theoretically added bacteria) and after storage for 24 hours, the surviving bacteria on the test piece were washed out with a culture medium for measuring the number of bacteria (SCDLP liquid medium). Medium Pour plate method (37 ° C 2
Days) to determine the number of viable cells
It was converted to the number of viable bacteria per mx 5 cm. Table 3 shows the results of the antibacterial test obtained as described above. The initial number of bacteria was 2.5 × 10 ^5. After 24 hours, the number of bacteria in the control solution obtained by performing the same operation using only the bacteria solution without contacting the sample plate was 8.3 × 10 ⁵ .

Further, the resin was changed from polystyrene to polypropylene resin (trade name J10, manufactured by Grand Polymer Co., Ltd.).
5H), except that the prototype polypropylene plates molded in the same manner as prototypes Nos. 1 to 10 were immersed in warm water at 90 ° C. for one week, and the appearance of the plate after immersion was confirmed. The water resistance was evaluated.

[0041]

[Table 2]

The antibacterial plates (prototypes Nos. 1 to 4 and No. 9) containing the antibacterial agent of the present invention have antibacterial properties, discoloration resistance,
It has excellent performance in water resistance. Among the glass components of the present invention, alkali metal oxides and Al ₂ O ₃ and Z
An antibacterial plate containing an antibacterial agent consisting of glass of a component excluding at least one selected from rO ₂ (prototype No.
5) is excellent in discoloration resistance and water resistance, but insufficient in antibacterial properties. An antibacterial plate (prototype No. 6) containing an antibacterial agent made of glass excluding at least one kind of component selected from Al ₂ O ₃ and ZrO _{2 also} has excellent antibacterial properties, but is resistant to discoloration and water. Poor sex.

Also, an alkali metal oxide of 5 mol%
An antibacterial plate (prototype No. 7) containing an antibacterial agent made of glass not containing the above is excellent in discoloration resistance and water resistance, but insufficient in antibacterial properties. Furthermore, compared to the present invention, ZnO
The antibacterial plate (prototype No. 8) in which an antibacterial agent made of glass having a small molar ratio of (a) was inferior in antibacterial properties.

[0044]

The antibacterial agent of the present invention has excellent antibacterial properties, resistance to discoloration and water resistance, and is extremely useful as an antibacterial agent capable of maintaining the antibacterial effect for a long time. By blending the antibacterial agent of the present invention into a resin, an antibacterial resin composition having excellent antibacterial properties, discoloration resistance and water resistance can be easily obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C03C 3/14 C03C 3/14 3/145 3/145 3/17 3/17 3/19 3/19 3 / 21 3/21 C08K 3/22 C08K 3/22 C09D 5/14 C09D 5/14 // C08J 5/00 C08J 5/00 (72) Inventor Toshifumi Wa 4-5-5 Minatomachi, Handa City, Aichi Prefecture F-term in Rit Co., Ltd. (Reference) 4F071 AA22 AB17 AE08 AE22 AF02 AF34 AF52 AH19 BB05 BB06 BC07 4G062 AA09 AA15 BB08 BB09 CC10 DA01 DA02 DA03 DA04 DB01 DB02 DB03 DB04 DC01 DC02 DC03 DC04 DC05 DD01 DD02 DD03 DD03 DD01 ED01 EE01 EF01 EG01 FA01 FA10 FB01 FC01 FC02 FC03 FC04 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 FL01 GA01 GA10 GB01 GC01 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH11 HH13 HH15 HH07 KK01 JJ01 KK01 JJ01 KK01 JJ01 KK10 MM15 NN40 PP14 4H011 AA02 AA03 BA01 BB18 BC18 DA02 DG02 4J002 BB031 BB121 BC061 BD041 BD101 BN151 CB001 CF001 CF071 CG00 CL001 DE056 DE096 DE106 DE146 DH016 DK006 FD186 GK00 4J038 EA001 HA176

Claims (2)

[Claims] 1. ZnO 50 to 70 mol%, B ₂ O ₃ and / or P ₂ O ₅ 20 to 50 mol%, Al ₂ O ₃ and ZrO
₂ , at least one selected from the group consisting of 0.5 to 15 mol%, an alkali metal oxide of 5 to 10 mol%, and SiO ₂
Is an antibacterial agent made of glass containing 0 to 20 mol%. 2. The antibacterial agent according to claim 1, wherein the alkali metal oxide is Na ₂ O.