JP3335689B2 - Zeolite-based antibacterial agent, its production method and antibacterial polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver ion-containing zeolite antibacterial agent having excellent discoloration resistance and a process for producing the same.
And an antibacterial polymer composition containing the above-mentioned zedrite antibacterial agent.

[0002]

2. Description of the Related Art Many antibacterial zeolites in which an antibacterial metal ion is adsorbed and supported on a zeolite carrier by ion exchange have been proposed in the past. For example, antibacterial zeolites obtained by replacing ion-exchangeable ions in natural zeolites or synthetic zeolites with metal ions such as silver, copper and zinc (JP-A-60-181002), and ion-exchangeable ions in zeolites These include antimicrobial zeolites (JP-A-63-26580 and JP-A-1-257124) in which ammonium and an antibacterial metal ion or an alkaline earth metal or the like are substituted by an antibacterial metal ion, respectively. These antibacterial zeolites are blended in various resins and paints and are widely used as antibacterial polymer materials or products such as films, fibers or molded articles.

[0003] Of these, white antibacterial zeolite powder carrying silver ions has attracted attention in practical use because it exhibits particularly excellent antibacterial properties and stability. However, this white powder has an inconvenient propensity to exhibit a phenomenon of discoloration when exposed to ultraviolet light, natural light and artificial light, or when exposed to heat. Causes discoloration. The reason that the zeolite-based antibacterial agent is stable and has excellent antibacterial properties but is restricted in industrial use is largely due to the lack of discoloration resistance.

Recently, antibacterial zeolites having improved discoloration resistance formed into a specific composition (Japanese Patent Laid-Open Publication No.
Japanese Patent Application Laid-Open No. 4-134,091) and a non-zeolitic product obtained by calcining an antibacterial zeolite. However, since silver ions are very sensitive to light and heat, it is extremely difficult to improve discoloration resistance without sacrificing antibacterial properties. For example, the antibacterial zeolite obtained by calcining a silver ion-containing zeolite having improved discoloration resistance and calcining ceramics has a high antibacterial property, in which silver ions carried during the ceramicization stage are trapped in pores or converted into silver. It shows a tendency to decline significantly.

[0005]

SUMMARY OF THE INVENTION
Developing a zeolite-based antibacterial agent having improved discoloration resistance while maintaining stable antibacterial properties is a significant challenge for manufacturers and users of silver-based inorganic antibacterial agents. The present inventors have conducted intensive studies to solve this problem, and found that the surface of antibacterial zeolite carrying silver ions was coated with a metal hydroxide or oxide such as Ti, Zr, Ce, or Zn. Then, it was confirmed that the discoloration resistance was significantly improved without impairing the antibacterial ability.

The present invention has been developed on the basis of the above findings, and has as its object to provide a high-performance zeolite-based material which exhibits excellent discoloration resistance to light and heat while maintaining a high level of antibacterial properties. An object of the present invention is to provide an antibacterial agent, a method for producing the same, and an antibacterial polymer composition containing the zeolite-based antibacterial agent.

[0007]

The zeolite-based antibacterial agent according to the present invention for achieving the above-mentioned object comprises a zeolite having at least silver ion as an antibacterial ion on the particle surface of the zeolite antibacterial agent by means of ion exchange. , Ce or Zn is characterized by a property of being covered by one or more metal hydroxides and / or metal oxides.

The zeolite constituting the antibacterial zeolite is not limited to a synthetic product and may be a natural product. However, from the viewpoint of quality, synthetic zeolites of A-type, P-type, X-type or Y-type crystal system, and other sodas Light, analcyme, mordenite, high silica zeolite and the like are preferably used.
In view of cost, zeolite A is most preferred as an industrial raw material. The antibacterial zeolite applicable to the present invention is not limited as long as at least silver ions (including complex ions) as antibacterial metal ions are supported on such a zeolite carrier by ion exchange. The loading amount of silver ion is in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight as Ag, and Zn, Cu, etc. are loaded as other antibacterial metal ions at an arbitrary ratio. Such an antibacterial zeolite is disclosed in
Discoloration-resistant ones described in JP-A-21517 can be preferably used.

The zeolite antibacterial agent according to the present invention comprises Ti, Zr, Ce on the surface of the antibacterial zeolite particles having at least silver ions carried by ion exchange as described above.
Or one or more metal hydroxides and / or oxides selected from Zn (hereinafter, “Ti oxides and the like”)
) Has a characteristic feature. The property that the surface of the antibacterial zeolite is coated with Ti oxide or the like means that Ti, Zr, Ce, Zn
Etc. and an aqueous slurry of an antibacterial zeolite are mixed and neutralized to deposit and coat Ti oxide or the like on the surface of the zeolite particles. In particular, a coating of a composite hydroxide and / or oxide of Ti and Zn is preferred for the purpose of the present invention.

The amount of the coating of Ti oxide or the like is determined by the physical properties of the antibacterial zeolite as the core material, the Ag in the antibacterial zeolite.
In many cases, it is in the range of 5 to 50% by weight, preferably 10 to 30% by weight in terms of oxide (non-hydrate) based on the antibacterial zeolite. If the coating amount is less than 5% by weight, the discoloration resistance of the antibacterial agent is insufficient to improve the resistance to heat and light after compounding the polymer. On the other hand, if it exceeds 50% by weight, it is not possible to expect a higher effect of suppressing discoloration, and it also causes a reduction in antibacterial properties.

The zeolite-based antibacterial agent having such a property is optionally provided with a hydrophobic property in order to improve the dispersibility of the particles, limit the release of silver ions or improve the affinity with the material using the same. It is a preferable embodiment to carry out a chemical treatment. Examples of the hydrophobizing agent in this case include a silane coupling agent, a titanium coupling agent, a metal salt of a higher fatty acid, and an acidic phosphate.

The production method according to the present invention for obtaining a zeolitic antibacterial agent having the above-mentioned properties comprises an antibacterial zeolite carrying at least silver ions by ion exchange, Ti, Zr,
One or more soluble metal salts selected from Ce or Zn and an alkali agent are mixed to form a slurry, and the aqueous zeolite aqueous slurry is subjected to a neutralization reaction in a pH range of 4 to 9 to form a fine water of the metal. The process is characterized by depositing an oxide and depositing and coating the deposited metal hydroxide fine particles on the surface of the zeolite particles.

The antibacterial zeolite carrying silver ions is:
The zeolite serving as a carrier is sufficiently stirred in, for example, an aqueous silver nitrate solution maintained at a constant pH, and A
It is produced by a method of supporting g ⁺ . The same applies to the case where Zn ²⁺ and Cu ²⁺ are supported in addition to Ag ⁺ as an antibacterial metal ion. In the case of Zn ²⁺ , the zinc salt remaining in the mother liquor after the ion exchange reaction is dissolved in an alkaline aqueous solution. If summed, it will precipitate as zinc hydroxide on the zeolite particle surface,
The deposition coating process can be performed continuously. Ti,
As soluble metal salts such as Zr, Ce and Zn, for example, one or more of nitrates, sulfates, organic acid salts or basic salts thereof may be 5 to 50 in terms of oxide with respect to antibacterial zeolite.
It is used within the range of weight%. In addition, sodium hydroxide, potassium hydroxide, ammonium hydroxide, or the like is used as the alkali agent.

The step of mixing these components is not particularly limited. For example, a method in which an aqueous solution of an alkali agent is dropped into a slurry in which an antibacterial zeolite is dispersed in an aqueous solution of a metal salt, a method in which an antibacterial zeolite is dispersed in an aqueous solution of an alkali agent, Either a method of dropping an aqueous solution of a metal salt or a method of simultaneously dropping an aqueous solution of a metal salt and an aqueous solution of an alkali agent into an aqueous slurry of an antibacterial zeolite may be used. However, it is most preferable to employ a method of simultaneously adding an aqueous solution of a metal salt and an aqueous solution of an alkali agent so as to have a constant pH while stirring the aqueous slurry of the antibacterial zeolite. If the concentration of the metal salt aqueous solution is too high, the precipitated hydroxide does not effectively deposit on the surface of the zeolite particles and tends to exist in a free state. . A preferred concentration range is from 0.1 to 1.0 mol / l.

When depositing by the above-described method, it is desirable that the aqueous slurry of the antibacterial zeolite be sufficiently deagglomerated in advance in order to prevent the uncoated surface from being exposed in later use. For this purpose, if necessary, vigorous stirring is carried out with a dispersing agent such as sodium hexametaphosphate, sodium silicate or a surfactant, or a homogenizer, a homogenizer, a method of uniformly dispersing with a strong shearing dispersing machine such as a colloid mill or the like. Is adopted. The slurry concentration is not particularly limited, but is usually 50 to 300 g / l from the viewpoint of productivity and dispersibility.
Is set in the range.

[0016] The neutralization reaction is carried out using p-type aqueous zeolite slurry.
When H is in the range of 4 to 9, preferably 6 to 8, room temperature to
The reaction is performed in a temperature range of 90 ° C, preferably 50 to 70 ° C.
If the pH is less than 4, not only the precipitation of the metal hydroxide becomes insufficient, but also the silver ions in the antibacterial zeolite may be eluted into the mother liquor, and if the pH exceeds 9, depending on the type of metal. In some cases, the precipitated hydroxide may be redissolved.

The neutralization reaction is allowed to proceed under gentle stirring while maintaining the above-mentioned pH range, and further aging results in precipitation of fine metal hydroxides. Is deposited on the surface of the particles and is entirely covered. In this neutralization reaction, two or more kinds of metal hydroxides can be precipitated by a simultaneous precipitation method using a mixed solution of metal salts or a multiple precipitation method using an aqueous solution of a single metal salt and an aqueous solution of an alkali agent sequentially. The method of applying is applied.

By neutralization reaction, Ti, Zr, Ce or Z
The antibacterial zeolite deposited and coated with a metal hydroxide such as n is filtered, washed with water, and then dried by a conventional method, and further dried at 200 to 800 ° C., preferably 300 to 60 ° C. if necessary.
A calcination treatment is carried out in a temperature range of 0 ° C. to remove the zeolite water and to convert a part or all of the metal hydroxide on the surface into an oxide. The dried or dehydrated product thus obtained is subjected to a treatment such as crushing, crushing, and classification to obtain a zeolite antibacterial agent.

The antibacterial polymer composition according to the present invention contains the above zeolite antibacterial agent in 100 parts by weight of the polymer.
1 to 50 parts by weight are blended. Examples of the polymer include polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polystyrene, polyester, ABS resin, polyacetal, polyvinyl alcohol, polycarbonate, acrylic resin, fluorine-containing resin, silicon-containing resin, phenol resin, urea resin, and melamine resin. And unsaturated polyester resin, epoxy resin, polyurethane, rayon, acetate, various thermoplastic elastomers, various natural or synthetic water-soluble resins, natural rubber, synthetic rubber and the like.

The reason why the amount of the zeolite-based antibacterial agent to be added to the polymer is limited to 0.1 to 50 parts by weight per 100 parts by weight of the polymer is that if the amount is less than 0.1 part by weight, the antibacterial property of the polymer composition is sufficient. Can no longer be granted,
If the amount exceeds 50 parts by weight, the physical properties of the polymer are impaired, such as difficulty in molding. In the final form of the polymer composition, it does not exceed at most 10 parts by weight, but a composition with a high content allows the antimicrobial polymer to be handled as a masterbatch.

The antimicrobial polymer composition according to the present invention may contain various types of polymer additives which are commonly used or blended as needed. Such polymer additives include plasticizers, fillers, pigments, UV absorbers,
Examples include antioxidants, stabilizers, antistatic agents, surfactants, and flame retardants. The form of the antibacterial polymer composition is various, such as a pellet, a film, a sheet, a plate, a container, and a fiber, and is formed according to the purpose of use. In addition, if the polymer is used for paints, it is used as an antibacterial paint, and if the polymer is used for adhesives, it is used as an antibacterial adhesive.

[0022]

According to the zeolite-based antibacterial agent of the present invention, antibacterial metal ions including silver ions carried on the core of the antibacterial zeolite are passed through a fine intervening layer such as Ti oxide. Releases antimicrobial action while releasing slowly.
Its antibacterial properties show a broad antibacterial spectrum not only for various bacteria but also for fungal bacteria as well as conventional zeolite-based antibacterial agents. On the other hand, fine Ti oxide or the like deposited and coated on the surface of the antibacterial zeolite particles of the core material functions to effectively increase the discoloration resistance without suppressing the antibacterial action. The details of this mechanism have not yet been elucidated, but probably Ti, Zr, Ce
It is also presumed to be a result of suppression of discoloration due to strong coloring hiding power based on a high refractive index of the coating film formed by the fine particles of the hydroxide or oxide of Zn or ultraviolet absorption.

The high-performance zeolite-based antibacterial agent having both excellent antibacterial properties and discoloration resistance can be industrially produced by the production method of the present invention in which a neutralization reaction is performed in a specific pH range. . Furthermore, the antibacterial polymer composition according to the present invention prevents silver ions from directly acting on heat or light in the polymer and suppresses discoloration and deterioration of the polymer, so that high practicality is imparted in addition to the antibacterial activity. .

[0024]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. In addition, the component content, the ignition loss, and the average particle diameter shown in Table 1 were measured by the following methods. Component content: Quantitative analysis was performed by atomic absorption spectroscopy and ICP. Ignition loss (moisture content): 1 g of a sample was weighed in a porcelain crucible and determined from the weight loss after heating at 800 ° C. for 1 hour. Average particle size: using a Coulter counter (manufactured by Coulter Electronics Co., Ltd.), an aperture tube of 30 μm
Was measured.

Example 1 5 kg of metal-substituted A-type zeolite powder having an average particle size of 3.1 μm and carrying 2.9% by weight and 12.1% by weight, respectively, of Ag ⁺ and Zn ²⁺ as a metal by ion exchange were charged in an amount of 5 l.
Was sufficiently deagglomerated and dispersed and suspended in deionized water. While heating this aqueous zeolite slurry to 60 ° C., a 2.5 mol / l zinc nitrate aqueous solution was added.
l and 2.5 l of aqueous ammonia having a concentration of 1 mol / l were simultaneously added over 1 hour, and neutralized while maintaining the pH at 8. The zinc oxide fine particles precipitated and deposited on the zeolite particles were coated. Subsequently, the mixture was stirred for 2 hours and subjected to an aging treatment. Then, after filtration and washing with a conventional method, 120
C. and dried to obtain a zeolite antibacterial agent of "Sample 1". In this case, the coverage of zinc hydroxide deposited on the surface of the antibacterial zeolite particles was 10.9%. Further, one part of the sample 1 was dehydrated by baking at 500 ° C. for 2 hours to obtain a zeolite antibacterial agent of “sample 2”. The deposition coverage of zinc oxide in this case was 11.0%. Table 1 shows the properties of these zeolite antibacterial agents.

Example 2 1 kg of sodium A-type zeolite powder having an average particle diameter of 2.8 μm was dispersed and suspended in 5 l of ion-exchanged water, and the concentration was 10 g / g.
Then, 5 l of an aqueous solution of silver nitrate and 5 l of an aqueous solution of zinc nitrate having a concentration of 125 g / l were added, and ion exchange was carried out by continuing stirring for 5 hours. Next, aqueous ammonia having a concentration of 1 mol / l was added to raise the pH of the slurry to 9, and excess Zn ²⁺ was precipitated on the surface of the zeolite particles as zinc hydroxide. After filtration and washing according to a conventional method, the filter cake was redispersed in ion-exchanged water, and while heating to 60 ° C., the concentration was 0.5%.
2.5 l of an aqueous solution of titanium sulfate at a concentration of 2 mol / l and 2.5 l of aqueous ammonia at a concentration of 2 mol / l were gradually added at the same time, and neutralized while maintaining the pH at 8. The surface was deposited and coated. Continue 2
The mixture was stirred for a period of time and subjected to an aging treatment. Then, after filtering and washing with a conventional method, drying and pulverization at 120 ° C. were performed to prepare a zeolite antibacterial agent of “Sample 3”. In this case, the coverage of zinc hydroxide deposited on the surface of the antibacterial zeolite particles was 8.3%, and the coverage of titanium hydroxide was 11.0%. Further, a part of the sample 3 was dehydrated by firing at a temperature of 600 ° C. for 2 hours to obtain a zeolite antibacterial agent of “sample 4”. In this case, the deposition coverage of zinc oxide was 7.7%, and the coverage of titanium oxide was 8.5%. Table 1 also shows the properties of these zeolite-based antibacterial agents.

Example 3 In Example 2, an aqueous solution of zirconyl nitrate having a concentration of 0.3 mol / l was used in place of the aqueous solution of titanium sulfate having a concentration of 0.5 mol / l.
mol / l of aqueous ammonia, and the other conditions were the same as in Example 2, and the zeolite-based antibacterial agent of Sample 5 (dry matter) (coverage of zinc hydroxide 8.5%, coverage of zirconium hydroxide) (9.2%) and “Sample 6” (dehydrated product) were prepared as zeolite-based antibacterial agents (coverage of zinc oxide 8.4%, coverage of zirconium oxide 8.6%). The pH in the neutralization reaction at this time was 8.5. Table 1 also shows the properties of these zeolite-based antibacterial agents.

Example 4 In Example 3, a 0.2 mol / l cerium nitrate aqueous solution was used instead of the 0.3 mol / l zirconyl nitrate aqueous solution. (Dry matter) zeolite antibacterial agent (8.7% zinc hydroxide coverage, 7.5% cerium hydroxide coverage) and "Sample 8" (dehydrated) zeolite antibacterial agent (zinc oxide (Cover rate 8.5%, cerium oxide coverage 7.7%). The pH in the neutralization reaction at this time was 7.5. Table 1 also shows the properties of these zeolite-based antibacterial agents.

Example 5 1 kg of the metal-substituted A-type zeolite used in Example 1 was sufficiently deagglomerated in 5 l of ion-exchanged water and dispersed and suspended. While heating the aqueous zeolite slurry at 60 ° C., 2.5 l of a mixture of a 0.25 mol / l concentration of zinc nitrate aqueous solution and a 0.25 mol / l concentration of titanium sulfate aqueous solution
And 2.5 l of aqueous ammonia having a concentration of 1.25 mol / l were simultaneously added, and a neutralization reaction was carried out at pH 7.
Stirring was continued for hours. Then, filtration, washing with water, drying at 120 ° C., and pulverization by a conventional method are performed, and the zeolite-based antibacterial agent of Sample 9 (a zinc oxide coverage of 5.5% and a titanium hydroxide coverage of 6.4) is used. %). In addition, 1 of sample 9
A zeolite-based antibacterial agent (5.5% zinc oxide coverage and 5.4% titanium oxide coverage) of "Sample 10" was prepared by calcining the part at a temperature of 600 ° C and dehydrating. Table 1 also shows the properties of these zeolite-based antibacterial agents.

Example 6 In place of the metal-substituted zeolite A powder of Example 1 (average particle size: 3.1 μm), Ag ⁺ and Zn ²⁺ were ion-exchanged to 2.5% by weight and 11.5% by weight, respectively, as metals. % Of zeolite powder having an average particle diameter of 4.2 μm supported at a ratio of 0.2%, and under the same conditions as in Example 1, the zeolite antibacterial agent (zinc hydroxide) of “Sample 11” (dry product) was used. Of the sample 12 (dehydrated product) and the zeolite-based antibacterial agent (coverage of zinc oxide of 11.2%).
1%). Table 1 shows the properties of these zeolite antibacterial agents.
It was also attached to.

Example 7 Each of Ag ⁺ and Zn ²⁺ was 2.8 by ion exchange.
Wt%, 10.7 wt% supported average particle diameter 0.9μ
1 kg of P-type zeolite powder was dispersed and suspended in 5 l of ion-exchanged water by sufficiently deagglomerating. The aqueous zeolite slurry was heated to 60 ° C. while the concentration was adjusted to 0.
2.5 l of a 5 mol / l aqueous solution of titanium sulfate and 2.5 l of aqueous ammonia having a concentration of 2 mol / l were simultaneously added, a neutralization reaction was carried out at pH 8, and stirring was continued for 2 hours for aging. Then, after filtration and washing with a conventional method, 120
C. and dried to prepare a zeolite-based antibacterial agent of "Sample 13" (titanium hydroxide coverage 12.6%). Further, a zeolite-based antibacterial agent (titanium oxide coverage of 11.1%) of "Sample 14" was obtained in which one part of Sample 13 was fired at a temperature of 500 ° C. and dehydrated. Table 1 also shows the properties of these zeolite-based antibacterial agents.

Comparative Example 1 A ion-exchanged with silver and zinc used in Example 1
Type 15 zeolite powder (antibacterial zeolite)
This was calcined and dehydrated at 600 ° C. to obtain “Sample 16”. The properties of these antibacterial zeolite powders are shown in Table 1.

[0033]

[Table 1]

Next, the antibacterial property of each of the above samples was evaluated by the following method. Bacterial contaminated water (prepared by diluting a sample of 0.5 g of sample with sterile water to reduce the number of bacteria to 1)
0 ⁵ and the ones; for total bacteria test) or molds dilution water (those that have been diluted black mold growth plaster 1g in sterile water 100 ml; added to 50ml of fungal inspection), was gently stirred for 10 min magnetic stirrer. This solution was then used with a simple microorganism measuring instrument, Easy Cult TTC (for testing aerobic bacteria, fungi, and yeasts (manufactured by Sanai Petroleum)) and Easy Cult M (for testing fungi and yeasts (manufactured by Sanai Petroleum)). Culture test. Cultures were for 2 days (total bacteria) or 4 days (fungi) in an incubator at 27-30 ° C.

The evaluation results of the obtained antibacterial properties are shown in Table 2 in comparison with Sample No. In Table 2, "Sample 17" is a comparative example (blank) when no antibacterial zeolite was added. The total number of bacteria was evaluated based on the relationship between the number of colonies and the number of bacteria roughly determined in advance.
Indicates that no colonies were generated. The degree of fungal contamination was evaluated by the following four steps. No pollution:-Light pollution: + Medium pollution: ++ Strong pollution: +++

[0036]

[Table 2]

From the results in Table 2, it can be seen that the present invention (Sample Nos. 1 to 1)
4) showed a high level of antibacterial activity, and it was recognized that the decline in antibacterial activity due to the deposition coating of metal hydroxide or oxide was slight.

Examples 8 to 21 and Comparative Examples 2 to 4 Sample Nos. 1 to 17 were added and mixed at a ratio of 1% by weight to the various polymers shown in Table 3, and the test pieces (length: 180 mm, width: width) were formed by injection molding. 50 mm and a thickness of 1 mm). The discoloration status of these test pieces immediately after molding and after exposure to sunlight for 30 days is determined by using a digital colorimetric color difference calculator [AUD-CH-1 manufactured by Suga Test Instruments Co., Ltd.] to determine the color difference (ΔE) from the white standard plate. It was evaluated by: Table 4 shows the results.
It was shown to.

[0039]

[Table 3] Table Notes: (1) Nippon Unicar Co., Ltd., GS-360 (2) Tonen Chemical Co., Ltd., J-209 (3) Ube Industries, Ltd., 1013B (4) Nippon Zeon Co., Ltd. Zeon 103EP

[0040]

[Table 4]

From the results shown in Table 4, it was confirmed that the antibacterial polymer compositions according to the examples had significantly improved discoloration resistance, particularly the degree of discoloration after 30 days, as compared with the comparative examples.

[0042]

As described above, at least Ti, Zr and Ce are formed on the surface of the antibacterial zeolite particles carrying silver ions.
Alternatively, the zeolite-based antibacterial agent of the present invention in which at least one metal hydroxide selected from Zn and / or metal oxide is interposed between the coating and the fine metal hydroxide or oxidized coating interposed without impairing the antibacterial performance. It has extremely stable properties against light, heat, etc. due to the concealing action of the object and the ultraviolet absorbing ability. For this reason, when it is blended with various polymers, it becomes possible to obtain an antibacterial polymer composition having excellent antibacterial properties and discoloration resistance, which have been impossible so far. Therefore, the range of application for polymers has expanded even more than before, and it has a good appearance as a coating, adhesive, etc., as well as various molded products such as films, sheets, plates, containers, fibers, etc., and safety. High antibacterial product.

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masumi Usui 9-15-1, Kameido, Koto-ku, Tokyo Japan Chemical Industry Co., Ltd. Research and Development Headquarters (72) Inventor Konosuke Hiramatsu 1 Nihonbashi Muromachi 1 Chuo-ku, Tokyo 6-3, Koshonai Co., Ltd. (72) Keigo Umemoto, Inventor Keigo Umemoto 1-3-6, Nihonbashi Muromachi, Chuo-ku, Tokyo (72) Inventor Shinji Samukawa, 1-Chome Nihonbashi Muromachi, Chuo-ku, Tokyo No. 6-3 Eishin Kasei Co., Ltd. (56) References JP-A-4-219143 (JP, A) JP-A-5-58620 (JP, A) JP-A-48-22393 (JP, A) 3-269030 (JP, A) JP-A-1-164722 (JP, A) JP-A-1-286913 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01B 39/00 -39/54 A01N 59/16 JICST file JOIS)

Claims (5)

(57) [Claims] 1. An antimicrobial zeolite carrying at least silver ions as antimicrobial ions by ion exchange, on a particle surface of one or more metal hydroxides and / or metal oxides selected from Ti, Zr, Ce or Zn. A zeolite-based antibacterial agent characterized in that it is coated with a substance. 2. An antibacterial zeolite is added to a synthetic zeolite of A-type, P-type, X-type or Y-type crystal system in an amount of 0.5 as Ag.
The zeolite-based antibacterial agent according to claim 1, wherein the zeolite-based antibacterial agent is loaded with 10 to 10 wt%. 3. The coating amount of the metal oxide and / or the metal oxide on the antibacterial zeolite is 5 to 5 in terms of oxide.
The zeolite-based antibacterial agent according to claim 1 or 2, which is in a range of 50% by weight. 4. An antibacterial zeolite carrying at least silver ions by ion exchange, one or more soluble metal salts selected from Ti, Zr, Ce or Zn and an alkali agent are mixed to form a slurry, By performing a neutralization reaction at a pH of the slurry of 4 to 9 to precipitate a fine hydroxide of the metal, and depositing and coating fine particles of the precipitated metal hydroxide on the particle surface of the zeolite. A method for producing a zeolite-based antibacterial agent. 5. The method according to claim 1, wherein 100 parts by weight of the polymer is used.
An antibacterial agent-containing polymer composition comprising 0.1 to 50 parts by weight of a zeolite-based antibacterial agent.