JPH0680526A - Antibacterial material - Google Patents
Antibacterial materialInfo
- Publication number
- JPH0680526A JPH0680526A JP4233726A JP23372692A JPH0680526A JP H0680526 A JPH0680526 A JP H0680526A JP 4233726 A JP4233726 A JP 4233726A JP 23372692 A JP23372692 A JP 23372692A JP H0680526 A JPH0680526 A JP H0680526A
- Authority
- JP
- Japan
- Prior art keywords
- complex salt
- silica gel
- silver complex
- antibacterial material
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
(57)【要約】
【目的】 塩素イオン含有水を変色させない銀錯塩を用
いた抗菌材
【構成】 酢酸銀、亜硫酸ナトリウム、チオ硫酸ナトリ
ウムにて生成したチオスルファト銀錯塩溶液にシリカゲ
ル加えて銀錯塩を担持させる。チオスルファト銀錯塩溶
液とシリカゲルとの混合物から銀錯塩を担持したシリカ
ゲルを分離する。銀錯塩を担持したシリカゲルとポリメ
チルメタアクリレートを粉体表面改質装置を用いて、回
転数１，５００ｒ．ｐ．ｍ．にて５分間処理して、オー
ダードミクスチャーを形成させる。さらに同装置で回転
数１０，０００ｒ．ｐ．ｍ．にて４分間の固定化および
成膜処理を施し、ポリメチルメタアクリレートでコーテ
ィングされた抗菌材を得る。(57) [Summary] [Purpose] An antibacterial material using a silver complex salt that does not discolor chloride ion-containing water. [Constitution] Silver thiosulfato complex salt solution prepared with silver acetate, sodium sulfite and sodium thiosulfate was added to silica gel to form a silver complex salt. Carry it. The silica gel supporting the silver complex salt is separated from the mixture of the thiosulfato silver complex salt solution and the silica gel. Using a powder surface modification device, silica gel supporting silver complex salt and polymethylmethacrylate were rotated at 1,500 rpm. p. m. And process for 5 minutes to form an ordered mixture. Furthermore, with the same device, the rotation speed is 10,000 r.p.m. p. m. Immobilization and film formation are performed for 4 minutes to obtain an antibacterial material coated with polymethylmethacrylate.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銀錯塩をシリカゲルに
担持させた抗菌材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial material having a silver complex salt supported on silica gel.
【０００２】[0002]
【従来の技術】従来より、抗菌抗黴性材料をシリカゲル
等の多孔質粒体に担持させた抗菌材が知られている。こ
れらの抗菌材では、例えば一部有機窒素系抗菌材にて
は、該抗菌材あるいはこれを混合した合成樹脂と接触し
た水などの液中に溶出した抗菌成分が排水環境汚染の原
因となるほか、下水処理の活性汚泥に影響を及ぼすなど
の問題がある。また、このような環境汚染をもたらしに
くい抗菌材として、銀錯塩をシリカゲルに担持させた抗
菌材が提案されている。2. Description of the Related Art Conventionally, an antibacterial material in which an antibacterial and antifungal material is supported on porous particles such as silica gel has been known. Among these antibacterial materials, for example, in some organic nitrogen-based antibacterial materials, the antibacterial component eluted in the liquid such as water that comes into contact with the antibacterial material or the synthetic resin mixed with the antibacterial material causes the pollution of drainage environment. However, there are problems such as affecting the activated sludge of sewage treatment. Further, as an antibacterial material that hardly causes such environmental pollution, an antibacterial material in which a silver complex salt is supported on silica gel has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】ところが、抗菌抗黴性
材料として銀錯塩を使用した抗菌材では、溶出した銀イ
オンが水道水などに含まれている塩素イオンと反応して
水を変色させることがあり、これが新たに問題とされて
いる。However, in an antibacterial material using a silver complex salt as an antibacterial and antifungal material, the eluted silver ions react with chlorine ions contained in tap water and the like to discolor the water. There is a new problem.
【０００４】そこで、本発明は環境汚染の原因となりに
くく、しかも塩素イオン含有水に使用しても水を変色さ
せない抗菌材を提供することを目的とする。Therefore, an object of the present invention is to provide an antibacterial material which is unlikely to cause environmental pollution and does not discolor the water even when used in water containing chlorine ions.
【０００５】[0005]
【課題を解決するための手段及び作用】本発明は、かか
る課題を解決するための手段として次の構成を採用し
た。即ち、本発明の抗菌材は、銀錯塩を担持させたシリ
カゲルの表面に水不溶性ポリマのコーティング層を設け
たことを特徴とする。The present invention adopts the following construction as means for solving the above problems. That is, the antibacterial material of the present invention is characterized in that a coating layer of a water-insoluble polymer is provided on the surface of silica gel supporting a silver complex salt.
【０００６】以下、本発明につき更に詳しく説明する。
本発明で使用するシリカゲルの製造方法には特に限定は
なく、気相法、湿式法など公知の方法で製造可能であ
る。その粒径は特に限定されず、使用目的に応じて、適
宜の粒径のものを選択して使用できる。The present invention will be described in more detail below.
The method for producing the silica gel used in the present invention is not particularly limited, and it can be produced by a known method such as a vapor phase method or a wet method. The particle size is not particularly limited, and one having an appropriate particle size can be selected and used according to the purpose of use.
【０００７】例えば合成樹脂に混合する場合であれば、
その平均粒子径は約０．１〜１００μｍの範囲が好まし
い。この粒径範囲であると合成樹脂との混合効率が特に
良好となり、合成樹脂表面に均等に抗菌効果が得られ
る。抗菌材の粒径をこれ以下にしても合成樹脂表面にて
得られる抗菌効果には大きな差はなく、樹脂中で抗菌材
が凝集しやすく、分散不良になりやすい。また、抗菌材
の粒径が大きくなると、例えば混合した合成樹脂の引張
強度が部分的に下がることがある。したがって、合成樹
脂に混合する場合の抗菌材の粒径は上記の範囲が好まし
い。For example, when mixing with a synthetic resin,
The average particle size is preferably in the range of about 0.1 to 100 μm. Within this particle size range, the mixing efficiency with the synthetic resin becomes particularly good, and the antibacterial effect is evenly obtained on the surface of the synthetic resin. Even if the particle size of the antibacterial material is less than this, there is no great difference in the antibacterial effect obtained on the surface of the synthetic resin, and the antibacterial material is likely to aggregate in the resin, resulting in poor dispersion. Further, if the particle size of the antibacterial material becomes large, for example, the tensile strength of the mixed synthetic resin may partially decrease. Therefore, the particle size of the antibacterial material when mixed with the synthetic resin is preferably within the above range.
【０００８】細孔容積、平均細孔径も、用途に応じて適
宜の範囲を選択し得る。使用可能な銀錯塩の形態には特
に限定はなく、亜硫酸塩、亜硫酸水素塩、両者の混合
物、チオスルファト塩などの形態で用いることができ
る。銀錯塩をシリカゲルに担持させる方法に特に限定は
ないが、上記形態の銀錯塩を溶質とする溶液中にシリカ
ゲルを加えて攪拌し、銀錯塩をシリカゲルに吸着させた
後、濾過あるいは蒸散などにてシリカゲルを溶液から分
離する方法が簡便である。The pore volume and the average pore diameter can be selected in an appropriate range depending on the application. The form of the silver complex salt that can be used is not particularly limited, and it can be used in the form of a sulfite salt, a hydrogen sulfite salt, a mixture of the two, a thiosulfato salt and the like. The method of supporting the silver complex salt on silica gel is not particularly limited, but silica gel is added to a solution containing the silver complex salt of the above-described form as a solute and stirred, and the silver complex salt is adsorbed on the silica gel, followed by filtration or evaporation. The method of separating silica gel from the solution is convenient.
【０００９】水不溶性のポリマに限定はないが、例えば
ポリメチルメタアクリレート、ポリスチレン等が使用可
能である。銀錯塩を担持したシリカゲルに水不溶性のポ
リマのコーティング層を設ける方法も特に限定されな
い。例えば、粉体表面改質装置を用いる方法や、シリカ
ゲルを水に懸濁させて、懸濁液中のシリカゲル表面に沈
着させた難溶性の複塩を重合開始剤としてモノマを重合
させて、シリカゲルの表面上にポリマのコーティング層
を形成する開始剤沈着重合法がある。The water-insoluble polymer is not limited, but polymethylmethacrylate, polystyrene and the like can be used. The method for providing a coating layer of a water-insoluble polymer on silica gel carrying a silver complex salt is not particularly limited. For example, a method using a powder surface modification device, or suspending silica gel in water and polymerizing a monomer by using a sparingly soluble double salt deposited on the silica gel surface in the suspension as a polymerization initiator, There is an initiator deposition polymerization method that forms a coating layer of polymer on the surface of.
【００１０】形成されるコーティング層の厚さは、シリ
カゲルとモノマの比、モノマの重合時間や温度、モノマ
と溶液の比等の反応条件によって調節可能であるが、シ
リカゲル粒子直径の１／１００〜１／５程度の範囲が好
ましい。コーティング層の厚さがシリカゲル粒子直径の
１／１００以下であると、担持された銀錯塩の経時放出
速度が大きくなり、徐放期間すなわち抗菌効果維持期間
が短くなると共に抗菌材が変色しやすくなる。また、コ
ーティング層の厚さがシリカゲル粒子直径の１／５を越
えると、銀錯塩の放出が過剰に制限されることがある。The thickness of the coating layer formed can be adjusted by the reaction conditions such as the ratio of silica gel to the monomer, the polymerization time and temperature of the monomer, the ratio of the monomer to the solution, and the like. The range of about 1/5 is preferable. When the thickness of the coating layer is 1/100 or less of the diameter of the silica gel particles, the time-release rate of the supported silver complex salt is increased, the sustained release period, that is, the antibacterial effect maintenance period is shortened and the antibacterial material is easily discolored. . Further, when the thickness of the coating layer exceeds 1/5 of the silica gel particle diameter, the release of the silver complex salt may be excessively limited.
【００１１】ただし、水不溶性ポリマのコーティング層
の厚さは、使用目的等に応じて適宜選定されればよく、
上記の範囲に限定されるものではない。銀錯塩の大部分
はシリカゲルの細孔に吸着されて担持される。細孔に吸
着された銀錯塩は徐々に放出されて周囲に抗菌効果を及
ぼす。表面に設けられた水不溶性ポリマのコーティング
層が銀錯塩の放出を制限し、長期にわたって抗菌材の効
能を維持する。However, the thickness of the coating layer of the water-insoluble polymer may be appropriately selected according to the purpose of use,
It is not limited to the above range. Most of the silver complex salt is adsorbed and supported by the pores of silica gel. The silver complex salt adsorbed in the pores is gradually released and exerts an antibacterial effect on the surroundings. The water-insoluble polymer coating layer provided on the surface limits the release of the silver complex salt and maintains the efficacy of the antibacterial material for a long period of time.
【００１２】水道水のような塩素イオンを含む水と接触
しても、その水を変色させない理由は明確ではないが、
水不溶性ポリマのコーティング層を設けたことにより疎
水性の表面となり、水と接触しにくくなるためと考えら
れる。It is not clear why the water does not discolor even when it comes into contact with water containing chlorine ions, such as tap water.
It is considered that by providing the coating layer of the water-insoluble polymer, the surface becomes a hydrophobic surface and it becomes difficult to contact with water.
【００１３】[0013]
【実施例】以下に好適な実施例をあげて本発明を詳細に
説明する。 （実施例１）４０℃のイオン交換水３００ｍｌに酢酸銀
２．３２ｇを加えてホモジナイザで約５分間攪拌し、酢
酸銀溶液を得た。この酢酸銀溶液に亜硫酸ナトリウム１
０．０ｇを攪拌しながら加え、溶液が透明になるまで攪
拌を継続した。その後、この溶液にチオ硫酸ナトリウム
６．６ｇを加えて約５分間攪拌し、チオスルファト銀錯
塩溶液を得た。The present invention will be described in detail below with reference to preferred examples. (Example 1) 2.32 g of silver acetate was added to 300 ml of ion-exchanged water at 40 ° C., and the mixture was stirred with a homogenizer for about 5 minutes to obtain a silver acetate solution. Sodium sulfite 1 in this silver acetate solution
0.0 g was added with stirring and stirring was continued until the solution became clear. Then, 6.6 g of sodium thiosulfate was added to this solution and stirred for about 5 minutes to obtain a thiosulfato silver complex salt solution.
【００１４】このチオスルファト銀錯塩溶液に平均粒子
径２．６μｍのシリカゲル（商品名サイロイド＃５５、
富士デヴィソン化学(株)製）５０．０ｇを加えて約１０
分間攪拌し、シリカゲルに銀錯塩を担持させた。続い
て、チオスルファト銀錯塩溶液とシリカゲルとの混合物
をロータリーエバポレータ（商品名ロータリーエバポレ
ーターＲＥ４７、ヤマト科学(株)製）にて、温度約５０
℃、圧力を約３０００Ｐａ以下に保って溶媒成分を蒸発
させて除去し、銀錯塩を担持したシリカゲルを得た。In this thiosulfato silver complex salt solution, silica gel having an average particle size of 2.6 μm (trade name Syloid # 55,
Approximately 10 by adding 50.0 g of Fuji Devison Chemical Co., Ltd.
After stirring for a minute, the silver complex salt was supported on silica gel. Subsequently, the mixture of the thiosulfato silver complex salt solution and silica gel was heated at a temperature of about 50 with a rotary evaporator (trade name: rotary evaporator RE47, manufactured by Yamato Scientific Co., Ltd.).
The solvent component was removed by evaporation by keeping the temperature at 3,000 ° C. and the pressure at about 3000 Pa or less to obtain a silica gel carrying a silver complex salt.
【００１５】上記にて得た銀錯塩を担持したシリカゲル
２５．０ｇと粒径０．５μｍのポリメチルメタアクリレ
ート（商品名ＭＰ−１０００、綜研化学(株)製）１１．
４ｇを粉体表面改質装置（商品名ハイブリダリゼーショ
ンシステムＮＨＳ−Ｏ型、(株)奈良機械製作所製）を用
いて、回転数１，５００ｒ．ｐ．ｍ．にて５分間処理し
て、オーダードミクスチャーを形成させた。さらに同装
置で回転数１０，０００ｒ．ｐ．ｍ．にて４分間の固定
化および成膜処理を施し、抗菌材を得た。11. 25.0 g of the silica gel supporting the silver complex salt obtained above and polymethylmethacrylate having a particle size of 0.5 μm (trade name MP-1000, manufactured by Soken Chemical Industry Co., Ltd.) 11.
Using a powder surface reforming apparatus (trade name: Hybridization System NHS-O type, manufactured by Nara Machinery Co., Ltd.), 4 g of the rotational speed was 1,500 r. p. m. And processed for 5 minutes to form an ordered mixture. Furthermore, with the same device, the rotation speed is 10,000 r.p.m. p. m. Immobilization and film formation were performed for 4 minutes to obtain an antibacterial material.
【００１６】ＳＥＭでの観察では、オーダードミクスチ
ャーの形成、固定化および成膜処理はいずれも良好であ
った。ポリメチルメタアクリレートのコーティング層の
厚さは約０．１〜０．４μｍであった。 （ＭＩＣ（最小発育阻止濃度）の測定）上記実施例１で
得た抗菌材を試料として、以下の方法で最小発育阻止濃
度を測定した。According to the SEM observation, the formation, the immobilization and the film forming process of the ordered mixture were all good. The coating layer of polymethylmethacrylate had a thickness of about 0.1 to 0.4 μm. (Measurement of MIC (Minimum Inhibitory Concentration)) Using the antibacterial material obtained in Example 1 above as a sample, the minimum inhibitory concentration was measured by the following method.
【００１７】即ち、任意濃度にて試料を添加した複数の
寒天平板培地に接種用菌液を接種し培養する。菌が発育
を阻止された際の、試料の最低濃度を最小発育阻止濃度
とした。結果を表１に示す。寒天平板培地の調整、接種
用菌液の調整及び培養は、以下のようになされた。 ・寒天平板培地の調製 滅菌精製水で、次の濃度の試料懸濁液を調整した。試料
濃度は、４０，０００ｐｐｍ、２０，０００ｐｐｍ、１
０，０００ｐｐｍ、５，０００ｐｐｍ、２，５００ｐｐ
ｍ、１，２５０ｐｐｍ、６２５ｐｐｍ、３１３ｐｐｍ、
１５６ｐｐｍ、７８ｐｐｍである。That is, a plurality of agar plate media to which a sample is added at an arbitrary concentration is inoculated with a bacterial solution for inoculation and cultured. The minimum concentration of the sample when the growth of the bacteria was inhibited was defined as the minimum inhibitory concentration. The results are shown in Table 1. The preparation of the agar plate medium, the preparation of the inoculum bacterial solution and the culture were performed as follows. -Preparation of agar plate medium A sample suspension having the following concentration was prepared with sterile purified water. Sample concentration is 40,000ppm, 20,000ppm, 1
50,000ppm, 5,000ppm, 2,500pp
m, 1,250 ppm, 625 ppm, 313 ppm,
It is 156 ppm and 78 ppm.
【００１８】次に、溶解後５０〜６０℃となった感受性
測定用培地（Ｍｕｅｌｌｅｒ−Ｈｉｎｔｏｎ寒天培地
（ＤＩＦＣＯ社製））に、上記の各懸濁液を培地の１／
９量加えて、充分に混合した後、シャーレに分けて固化
させ、寒天平板培地とした。また、実施例１で使用した
のと同じシリカゲルを試料として、上記と同様に寒天平
板培地を調製し、これを比較例１とした。 ・接種用菌液の調製 増菌用培地［ミューラー ヒントン ブロス（Ｍｕｅｌ
ｌｅｒ−ＨｉｎｔｏｎＢｒｏｔｈ）（ＤＩＦＣＯ社
製）］にて、３５℃で一夜培養した試験菌株の菌液を同
培地で希釈し、１ｍｌ当りの菌数が約１０6になるよう
に調製した。使用した試験菌株は以下のとおりである。Next, each of the above suspensions was added to a medium for sensitivity measurement (Mueller-Hinton agar medium (manufactured by DIFCO)) which became 50 to 60 ° C. after thawing to 1 / of the medium.
After adding 9 volumes and thoroughly mixing, the mixture was divided into a petri dish and solidified to obtain an agar plate medium. Further, using the same silica gel as used in Example 1 as a sample, an agar plate medium was prepared in the same manner as above, and this was designated as Comparative Example 1.・ Preparation of bacterial solution for inoculation Enrichment medium [Mueller Hinton Broth (Muel
Ler-Hinton Broth (manufactured by DIFCO)], the bacterial solution of the test strain that had been cultured overnight at 35 ° C. was diluted with the same medium so that the number of bacteria per ml was about 10 6 . The test strains used are as follows.
【００１９】大腸菌：エスケリチャ コーライ（Ｅｓｃ
ｈｅｒｉｃｈｉａ ｃｏｌｉ） ＩＦＯ ３３０１ 黄色ブドウ球菌：スタフィロコッカス オーレオス（Ｓ
ｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ） ＩＦＯ
１２７３２ ・培養 接種用菌液を寒天平板培地に、ニクロム線ループ（内径
約１ｍｍ）で２ｃｍ程度画線塗抹し、３５℃で１日間培
養した。Escherichia coli: Escherichia coli (Esc
herichia coli) IFO 3301 Staphylococcus aureus: Staphylococcus aureus (S
taphylococcus aureus) IFO
12732 ・ Culturing The bacterial solution for inoculation was smeared on an agar plate medium with a nichrome wire loop (internal diameter of about 1 mm) for about 2 cm, and cultured at 35 ° C. for 1 day.
【００２０】[0020]
【表１】 [Table 1]
【００２１】表１から明らかなように、実施例１の抗菌
材を試料として混合した寒天平板培地では、抗菌性成分
として毒性の低い銀錯塩を使用しているにもかかわら
ず、比較例１の寒天平板培地よりもはるかに低い混合濃
度で菌の発育を阻止する。 （実施例２）４０℃のイオン交換水３００ｍｌに酢酸銀
２．３２ｇを加えてホモジナイザで約５分間攪拌し、酢
酸銀溶液を得た。この酢酸銀溶液に亜硫酸ナトリウム１
０．０ｇを攪拌しながら加え、溶液が透明になるまで攪
拌を継続した。その後、この溶液にチオ硫酸ナトリウム
６．６ｇを加えて約５分間攪拌し、チオスルファト銀錯
塩溶液を得た。As is clear from Table 1, in the agar plate medium in which the antibacterial material of Example 1 was mixed as a sample, although the silver complex salt having low toxicity was used as the antibacterial ingredient, Inhibits bacterial growth at a much lower concentration than on agar plates. (Example 2) 2.32 g of silver acetate was added to 300 ml of ion-exchanged water at 40 ° C., and the mixture was stirred with a homogenizer for about 5 minutes to obtain a silver acetate solution. Sodium sulfite 1 in this silver acetate solution
0.0 g was added with stirring and stirring was continued until the solution became clear. Then, 6.6 g of sodium thiosulfate was added to this solution and stirred for about 5 minutes to obtain a thiosulfato silver complex salt solution.
【００２２】このチオスルファト銀錯塩溶液に平均粒子
径２．６μｍのシリカゲル（商品名サイロイド＃５５、
富士デヴィソン化学(株)製）５０．０ｇを加えて約１０
分間攪拌し、シリカゲルに銀錯塩を担持させた。続い
て、チオスルファト銀錯塩溶液とシリカゲルとの混合物
をロータリーエバポレータ（商品名ロータリーエバポレ
ーターＲＥ４７、ヤマト科学(株)製）にて、温度約５０
℃、圧力を約３０００Ｐａ以下に保って溶媒成分を蒸発
させて除去し、銀錯塩を担持したシリカゲルを得た。This thiosulfato silver complex salt solution was added to silica gel having an average particle diameter of 2.6 μm (trade name Syloid # 55,
Approximately 10 by adding 50.0 g of Fuji Devison Chemical Co., Ltd.
After stirring for a minute, the silver complex salt was supported on silica gel. Subsequently, the mixture of the thiosulfato silver complex salt solution and silica gel was heated at a temperature of about 50 with a rotary evaporator (trade name: rotary evaporator RE47, manufactured by Yamato Scientific Co., Ltd.).
The solvent component was removed by evaporation by keeping the temperature at 3,000 ° C. and the pressure at about 3000 Pa or less to obtain a silica gel carrying a silver complex salt.
【００２３】上記にて得た銀錯塩を担持したシリカゲル
２０ｇをイオン交換水５００ｍｌ中に分散させてシリカ
ゲル懸濁液とした。このシリカゲル懸濁液にセチルトリ
メチルアンモニウムブロミド（ＣＴＡＢｒ）２．１３ｇ
を加え、攪拌しながら、さらに過硫酸カリウム０．５４
ｇを加え、生成した難溶性の複塩をシリカゲル表面に沈
着させた。20 g of the silica gel carrying the silver complex salt obtained above was dispersed in 500 ml of deionized water to give a silica gel suspension. 2.13 g of cetyltrimethylammonium bromide (CTABr) in this silica gel suspension
Add 0.54 potassium persulfate with stirring.
g was added, and the generated insoluble double salt was deposited on the surface of silica gel.
【００２４】次いで、該液中にスチレンモノマ６．３１
ｇを加えて、恒温槽中にて５０℃で５時間保持し、スチ
レンを重合させた。その後、クペロンを加えて重合反応
を停止させた。重合反応停止後、吸引濾過にて沈澱物を
分離した。Next, 6.31 of styrene monomer was added to the liquid.
g was added and the mixture was kept at 50 ° C. for 5 hours in a constant temperature bath to polymerize styrene. Then, cuperone was added to stop the polymerization reaction. After stopping the polymerization reaction, the precipitate was separated by suction filtration.
【００２５】沈澱物にイオン交換水洗浄およびメタノー
ル洗浄を施し、常圧乾燥後、真空乾燥機で圧力約３００
０Ｐａ、温度６０℃、１２時間乾燥して抗菌材を得た。
ポリスチレンのコーティング層の厚さは約０．１〜０．
５μｍであった。難溶性の複塩を生成させる素材として
は、上記セチルトリメチルアンモニウムブロミド（ＣＴ
ＡＢｒ）と過硫酸カリウムとの組合せの他に、オクチル
トリメチルアンモニウムブロミド、ラウリルトリメチル
アンモニウムブロミド、ステアリルトリメチルアンモニ
ウムブロミド等のＣ6〜Ｃ18程度の長鎖のアルキルアン
モニウム四級塩と、過硫酸カリウム又は過硫酸アンモニ
ウムのいずれかとの組合せが可能である。The precipitate was washed with ion-exchanged water and methanol, dried under normal pressure, and then dried in a vacuum dryer at a pressure of about 300.
An antibacterial material was obtained by drying at 0 Pa and a temperature of 60 ° C. for 12 hours.
The thickness of the polystyrene coating layer is about 0.1-0.
It was 5 μm. As a material for forming a sparingly soluble double salt, the above cetyltrimethylammonium bromide (CT
ABr) in combination with potassium persulfate, octyltrimethylammonium bromide, lauryltrimethylammonium bromide, stearyl trimethylammonium bromide and other long-chain alkylammonium quaternary salts of about C 6 to C 18 and potassium persulfate or A combination with either ammonium persulfate is possible.
【００２６】また、上記長鎖のアルキルアンモニウム四
級塩と過硫酸カリウム又は過硫酸アンモニウムとのモル
比を、１：２〜１：４に設定すると、反応が好適に行わ
れ、均一な被覆が行われるので望ましい。上記難溶性の
複塩とは、例えば、過硫酸ジ（セチルトリメチルアンモ
ニウム）｛［Ｃ16Ｈ33Ｎ+（ＣＨ3）3］2Ｓ2Ｏ8｝であ
る。When the molar ratio of the long-chain alkylammonium quaternary salt to potassium persulfate or ammonium persulfate is set to 1: 2 to 1: 4, the reaction is favorably carried out and uniform coating is performed. It is desirable because it will be seen. The poorly soluble double salt is, for example, di (cetyltrimethylammonium persulfate) {[C 16 H 33 N + (CH 3 ) 3 ] 2 S 2 O 8 }.
【００２７】なお、重合反応の促進は、加熱によってな
されてもよいし、レドックス系の開始剤として還元剤を
添加してもよい。レドックス系の開始剤を用いる場合の
還元剤としては、ＮａＨＳＯ3やアミン類が好適であ
る。 （ＭＩＣ（最小発育阻止濃度）の測定）上記実施例２で
得た抗菌材を試料として、上記実施例１におけると同様
の方法で最小発育阻止濃度を測定した。また、下記にて
調製した抗菌材を比較例２として同様に最小発育阻止濃
度を測定した。 （比較例２）イオン交換水６０ｍｌを４０℃に加熱し、
それに酢酸銀０．４６ｇを加え、４０〜５０℃で約５分
間攪拌した後濾紙（Ｎｏ．２）で濾過し、未溶解の酢酸
銀を除去する。こうして得られた溶液に、亜硫酸ナトリ
ウム２．０ｇを攪拌しながら加えた。亜硫酸ナトリウム
を加えて白く濁った溶液が透明になるまで攪拌し、その
後、チオ硫酸ナトリウム１．３２ｇを加えて攪拌し、シ
リカゲル（製品名「サイロイド＃５５」：富士デヴィソ
ン化学(株)製）を１０．０ｇ加えて、１０分間攪拌し、
シリカゲルに銀錯塩を担持させた。この後、このチオス
ルファト銀錯塩溶液とシリカゲルとの混合物を、ロータ
リエバポレータ（製品名「ロータリーエバポレーターＲ
Ｅ４７」：ヤマト科学(株)製）に入れて温度５０℃、約
３０００Ｐａ以下にて溶媒成分を蒸発させ除去した。そ
の後、得られたシリカゲルを更にロータリエバポレータ
にて温度５０℃、約３０００Ｐａ以下のもとで１２時間
真空乾燥した。The polymerization reaction may be accelerated by heating, or a reducing agent may be added as a redox initiator. NaHSO 3 and amines are suitable as the reducing agent when a redox type initiator is used. (Measurement of MIC (Minimum Inhibitory Concentration)) Using the antibacterial material obtained in Example 2 above as a sample, the minimum inhibitory concentration was measured in the same manner as in Example 1 above. In addition, the antibacterial material prepared below was used as Comparative Example 2 and the minimum inhibitory concentration was measured in the same manner. (Comparative Example 2) 60 ml of ion-exchanged water was heated to 40 ° C,
0.46 g of silver acetate is added thereto, and the mixture is stirred at 40 to 50 ° C. for about 5 minutes and then filtered through a filter paper (No. 2) to remove undissolved silver acetate. 2.0 g of sodium sulfite was added to the solution thus obtained with stirring. Sodium sulfite was added and stirred until the white turbid solution became transparent, then 1.32 g of sodium thiosulfate was added and stirred, and silica gel (product name "Cyroid # 55": manufactured by Fuji Devison Chemical Co., Ltd.) was added. Add 10.0 g and stir for 10 minutes,
A silver complex salt was supported on silica gel. Then, the mixture of this thiosulfato silver complex salt solution and silica gel was mixed with a rotary evaporator (product name "rotary evaporator R
E47 ": manufactured by Yamato Scientific Co., Ltd.) and the solvent component was removed by evaporation at a temperature of 50 ° C. and about 3000 Pa or less. Then, the obtained silica gel was further vacuum-dried for 12 hours at a temperature of 50 ° C. and about 3000 Pa or less by a rotary evaporator.
【００２８】こうして得られた銀錯塩を担持したシリカ
ゲルに、以下のようにしてコーティングを施した。ま
ず、メチルアルコール１０ｍｌ、テトラエトキシシラン
１０ｍｌ、銀錯塩を担持したシリカゲル１０ｇおよびイ
オン交換水０．２ｍｌとをロータリエバポレータにいれ
て、温度５０℃、約３０００Ｐａ以下にて溶媒成分の除
去を行うと同時にシリカコーティングを施す。固化した
ものをロータリエバポレータにて、温度５０℃、約３０
００Ｐａ以下にて１２時間真空乾燥させ、抗菌材を得
た。The silica gel carrying the silver complex salt thus obtained was coated as follows. First, 10 ml of methyl alcohol, 10 ml of tetraethoxysilane, 10 g of silica gel supporting a silver complex salt and 0.2 ml of ion-exchanged water are put in a rotary evaporator to remove solvent components at a temperature of 50 ° C. and about 3000 Pa or less. Apply silica coating. The solidified product was rotovapped at a temperature of 50 ° C and a temperature of about 30
An antibacterial material was obtained by vacuum drying at 00 Pa or less for 12 hours.
【００２９】実施例２の抗菌材および比較例２の抗菌材
による最小発育阻止濃度の測定結果を表２に示す。ただ
し、使用した菌株は次のものであるが、その培養は上記
実施例１と同様に行った。 黄色ブドウ球菌：スタフィロコッカス オーレオス（Ｓ
ｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ） ＩＦＯ
１２７３２Table 2 shows the measurement results of the minimum inhibitory concentration of the antibacterial material of Example 2 and the antibacterial material of Comparative Example 2. However, although the strains used were as follows, the culture was performed in the same manner as in Example 1 above. Staphylococcus aureus: Staphylococcus aureus (S
taphylococcus aureus) IFO
12732
【００３０】[0030]
【表２】 [Table 2]
【００３１】表２から明らかなように、実施例２の抗菌
材を試料として混合した寒天平板培地では、比較例２の
寒天平板培地よりもはるかに低い混合濃度で菌の発育を
阻止する。 （水変色試験）実施例１および実施例２の抗菌材をそれ
ぞれ充填したカラムに水道水を通過、接触させて水の変
色をテストした。As is clear from Table 2, the agar plate medium containing the antibacterial material of Example 2 as a sample inhibits the growth of bacteria at a much lower concentration than the agar plate medium of Comparative Example 2. (Water Discoloration Test) Tap water was passed through and brought into contact with the columns filled with the antibacterial materials of Example 1 and Example 2 to test the discoloration of water.
【００３２】実施例１の抗菌材カラムおよび実施例２の
抗菌材カラムともに、カラムを通過した水道水に変色は
認められなかった。なお、上記実施例１および実施例２
にては、銀錯塩源としてチオスルファト銀錯塩を用いた
が、亜硫酸塩、亜硫酸水素塩、両者の混合物などを用い
ることができる。銀イオン源としても酢酸銀の他に各種
の銀塩を用いることができる。In both the antibacterial material column of Example 1 and the antibacterial material column of Example 2, no discoloration was observed in the tap water passing through the columns. In addition, the above-mentioned Example 1 and Example 2
In the above, thiosulfato silver complex salt was used as the silver complex salt source, but sulfite salt, bisulfite salt, a mixture of the two or the like can be used. As the silver ion source, various silver salts other than silver acetate can be used.
【００３３】[0033]
【発明の効果】以上述べたように、本発明の抗菌材は抗
菌抗黴材料として銀錯塩を用いているので環境汚染の原
因となりにくい。しかも塩素イオンを含有する水に使用
しても水を変色させない。As described above, since the antibacterial material of the present invention uses the silver complex salt as the antibacterial and antifungal material, it is unlikely to cause environmental pollution. Moreover, even when used in water containing chlorine ions, the water does not discolor.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西野 敦 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 矢口 和彦 愛知県春日井市高蔵寺町２丁目1846番地 富士デヴィソン化学株式会社内 (72)発明者 山本 耕造 愛知県春日井市高蔵寺町２丁目1846番地 富士デヴィソン化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Nishino 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Kazuhiko Yaguchi, 2846 Kozoji Town, Kasugai City, Aichi Prefecture Fuji Devison Chemical Co., Ltd. (72) Inventor Kozo Yamamoto 2-1846 Kozoji-cho, Kasugai-shi, Aichi Fuji-Davison Chemical Co., Ltd.
Claims (3)
水不溶性ポリマのコーティング層を設けたことを特徴と
する抗菌材。1. An antibacterial material, characterized in that a coating layer of a water-insoluble polymer is provided on the surface of silica gel supporting a silver complex salt.
アクリレートであることを特徴とする請求項１記載の抗
菌材。2. The antibacterial material according to claim 1, wherein the water-insoluble polymer is polymethylmethacrylate.
あることを特徴とする請求項１記載の抗菌材。3. The antibacterial material according to claim 1, wherein the water-insoluble polymer is polystyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4233726A JPH07108847B2 (en) | 1992-09-01 | 1992-09-01 | Antibacterial material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4233726A JPH07108847B2 (en) | 1992-09-01 | 1992-09-01 | Antibacterial material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0680526A true JPH0680526A (en) | 1994-03-22 |
| JPH07108847B2 JPH07108847B2 (en) | 1995-11-22 |
Family
ID=16959612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4233726A Expired - Fee Related JPH07108847B2 (en) | 1992-09-01 | 1992-09-01 | Antibacterial material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07108847B2 (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01283204A (en) * | 1988-05-09 | 1989-11-14 | Shinagawa Nenryo Kk | Antimicrobial aluminosilicate |
| JPH02292201A (en) * | 1989-05-02 | 1990-12-03 | Yoshio Ichikawa | Antibacterial silica gel and antibacterial resin |
| JPH0466512A (en) * | 1990-06-29 | 1992-03-02 | Sintokogio Ltd | Inorganic antimicrobial agent surface-coated with polyurethane resin, its production and antimicrobial resin composition |
-
1992
- 1992-09-01 JP JP4233726A patent/JPH07108847B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01283204A (en) * | 1988-05-09 | 1989-11-14 | Shinagawa Nenryo Kk | Antimicrobial aluminosilicate |
| JPH02292201A (en) * | 1989-05-02 | 1990-12-03 | Yoshio Ichikawa | Antibacterial silica gel and antibacterial resin |
| JPH0466512A (en) * | 1990-06-29 | 1992-03-02 | Sintokogio Ltd | Inorganic antimicrobial agent surface-coated with polyurethane resin, its production and antimicrobial resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07108847B2 (en) | 1995-11-22 |
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