JPH09157119A - Antibacterial agent - Google Patents
Antibacterial agentInfo
- Publication number
- JPH09157119A JPH09157119A JP34552095A JP34552095A JPH09157119A JP H09157119 A JPH09157119 A JP H09157119A JP 34552095 A JP34552095 A JP 34552095A JP 34552095 A JP34552095 A JP 34552095A JP H09157119 A JPH09157119 A JP H09157119A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- antibacterial agent
- chlorine
- inorganic ion
- metal
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は抗菌剤に関し、特に
耐光性、耐熱性、抗菌効果の持続性に優れた抗菌剤に関
する。TECHNICAL FIELD The present invention relates to an antibacterial agent, and more particularly to an antibacterial agent excellent in light resistance, heat resistance and durability of antibacterial effect.
【０００２】[0002]
【従来の技術】抗菌剤として有機系抗菌剤と無機系抗菌
剤が知られており、これまで即効性に優れた有機系抗菌
剤が広く利用されていた。しかしながら、有機系抗菌剤
は一般に毒性が強く安全性の面で大きな問題を有してい
た。一方、無機系抗菌剤は有機系抗菌剤に比べ即効性の
面でやや劣るものの、安全性が高く、しかも抗菌作用の
持続性、耐熱性に優れるため、最近の無機系抗菌剤使用
量は大巾に増加してきている。2. Description of the Related Art Organic antibacterial agents and inorganic antibacterial agents are known as antibacterial agents, and organic antibacterial agents having excellent immediate effects have been widely used. However, organic antibacterial agents are generally highly toxic and have a serious problem in terms of safety. On the other hand, although inorganic antibacterial agents are slightly inferior to organic antibacterial agents in terms of immediate effect, they are highly safe and have a long antibacterial action and excellent heat resistance. It is increasing in width.
【０００３】従来より、金、銀、銅、亜鉛等の金属が抗
菌作用を有することは知られており、無機系抗菌剤とし
て、これらの金属（抗菌性金属と呼ぶ。）を利用したも
のが主として用いられている。これらの抗菌性金属がど
のようなメカニズムによって抗菌作用を発現するかは完
全には理解されていないが、金属イオンの触媒作用に
より発生する活性酸素が細菌を死滅させる、金属イオ
ンが細菌の代謝系の酵素を阻害したり、細胞膜に付着し
て物質移動を阻害することで細胞分裂を不可能とし細菌
を死滅させる、金属イオンがマイナスのイオン性を有
する細菌を引き寄せ、細菌の細胞膜を破壊し死滅させ
る、等の考えが示されている。It has been conventionally known that metals such as gold, silver, copper and zinc have an antibacterial action, and those using these metals (called antibacterial metals) as inorganic antibacterial agents. Mainly used. The mechanism by which these antibacterial metals exert their antibacterial action is not completely understood, but active oxygen generated by the catalytic action of metal ions kills bacteria. It inhibits the enzyme of, or attaches to the cell membrane and inhibits mass transfer to make cell division impossible and kills bacteria. Metal ions attract bacteria with negative ionicity, destroy the cell membrane of bacteria and die. The idea of letting, etc. is shown.
【０００４】抗菌性金属の抗菌剤への応用例としては、
例えば硝酸銀溶液の消毒液、点眼剤等としての利用が知
られている。しかしながら、液状の硝酸銀溶液は利用範
囲が限られ、また高濃度にすると毒性が強く取扱いが難
しいという問題がある。一方、抗菌性金属を固体状の無
機物担体に担持させた抗菌剤としては例えば、シリカゲ
ルや活性炭等の多孔質物質を担体とし、これに銀等を担
持させたもの、ゼオライトを担体として銀等を担持させ
たもの（特許第１２８６５４号、特開昭６０−１８１０
０２号等）、メタ珪酸アルミン酸マグネシウム等の無機
オキソ酸塩を担体とし、銀等の抗菌性金属イオンを担体
の金属イオンとイオン交換して担持させたもの（特開平
３−２７５６２７号）等が知られている。Examples of applications of antibacterial metals to antibacterial agents include:
For example, it is known to use a silver nitrate solution as an antiseptic solution, an eye drop and the like. However, the liquid silver nitrate solution has a problem that its range of use is limited, and that when it is used at a high concentration, it is highly toxic and difficult to handle. On the other hand, as an antibacterial agent in which an antibacterial metal is supported on a solid inorganic carrier, for example, a porous material such as silica gel or activated carbon is used as a carrier, and silver or the like is supported thereon, or zeolite is used as a carrier such as silver. What is carried (Patent No. 128654, JP-A-60-1810)
No. 02), an inorganic oxo acid salt such as magnesium aluminometasilicate is used as a carrier, and an antibacterial metal ion such as silver is ion-exchanged with the metal ion of the carrier and carried (JP-A-3-275627). It has been known.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記固
体状の無機物担体に担持させた従来の抗菌剤も、種々の
問題を有していた。例えば、多孔質物質を担体とするも
のは、金属保持力が弱いために水に添加使用した場合、
担持されていた金属の水中への溶出速度が速く、短期間
で抗菌効果が低下してしまうという問題があった。また
アメリカ公衆衛生局では、安全性の見地から水中の銀イ
オンの濃度を５０ｐｐｂ以下と規制しているが、上記多
孔質物質を担体とする抗菌剤を水に添加使用した場合に
は、この安全基準値を超える量の銀イオンが溶出する虞
れがあった。However, the conventional antibacterial agents supported on the above solid inorganic carrier also have various problems. For example, when a porous material is used as a carrier, it has a weak metal-retaining force, so when added to water,
There is a problem in that the carried metal has a high elution rate into water and the antibacterial effect is reduced in a short period of time. In addition, the US Public Health Service regulates the concentration of silver ions in water to 50 ppb or less from the viewpoint of safety, but when an antibacterial agent using the above-mentioned porous substance as a carrier is added to water, this safety There was a possibility that silver ions in an amount exceeding the standard value would be eluted.
【０００６】一方、ゼオライトや無機オキソ酸塩を担体
とする抗菌剤は、多孔質物質を担体とする抗菌剤に比べ
て水中への金属溶出速度は小さいものの、抗菌効果の持
続性はかならずしも十分とは言えなかった。またゼオラ
イトを担体とする抗菌剤の場合、金属が酸化されて経時
的に褐色に変色するという問題があり、特に光の照射に
より変色は著しくなり（耐光性が低い）、樹脂製品の抗
菌処理に用いたり、塗料等に抗菌性を付与するために添
加して用いた場合、抗菌剤の変色が原因で樹脂製品が変
色するという問題があった。一方、無機オキソ酸塩を担
体とする抗菌剤の場合、ゼオライトを担体とする抗菌剤
よりは耐光性が高いが、必ずしも十分な耐光性を有する
とは言い難かった。また樹脂製品を抗菌処理する場合、
樹脂原料を軟化温度以上の温度に加熱して抗菌剤を練り
込む方法が採用されることがあるが、抗菌剤の耐熱性が
低いと抗菌剤を樹脂に練り込む時の熱によって抗菌剤が
変色し、製品価値を低下させる虞れがある。このため耐
熱性が優れることも抗菌剤に必要とされる要件の一つで
ある。On the other hand, an antibacterial agent using zeolite or an inorganic oxoacid salt as a carrier has a smaller metal elution rate into water than an antibacterial agent using a porous substance as a carrier, but the antibacterial effect is not always sufficient. I couldn't say. In the case of an antibacterial agent using zeolite as a carrier, there is a problem that the metal is oxidized and changes its color to brown over time. Especially, the discoloration becomes remarkable by the irradiation of light (the light resistance is low), which is useful for the antibacterial treatment of resin products. When used or added to impart antibacterial properties to paints and the like, there is a problem that the resin product is discolored due to discoloration of the antibacterial agent. On the other hand, an antibacterial agent using an inorganic oxoacid salt as a carrier has higher light resistance than an antibacterial agent using a zeolite as a carrier, but it is difficult to say that it has sufficient light resistance. When antibacterial treatment of resin products,
The method of kneading the antibacterial agent by heating the resin raw material to a temperature above the softening temperature may be adopted, but if the antibacterial agent has low heat resistance, the antibacterial agent discolors due to the heat when kneading the antibacterial agent into the resin. However, the product value may be reduced. Therefore, excellent heat resistance is also one of the requirements for the antibacterial agent.
【０００７】本発明は上記の点に鑑みなされたもので、
耐光性、耐熱性、安全性に優れ、しかも抗菌効果の持続
性に優れた抗菌剤を提供することを目的とする。[0007] The present invention has been made in view of the above points,
It is an object of the present invention to provide an antibacterial agent which is excellent in light resistance, heat resistance, safety, and has a long lasting antibacterial effect.
【０００８】[0008]
【課題を解決するための手段】即ち本発明の抗菌剤は、
無機イオン交換体に、抗菌性金属と塩素とを担持せしめ
たことを特徴とする。本発明の抗菌剤は、抗菌性金属と
塩素とが、抗菌性金属塩化合物として担持されているも
のであっても良い。また塩素を担持した無機イオン交換
体を担体とし、これに抗菌性金属が担持されているもの
であっても良い。That is, the antibacterial agent of the present invention comprises:
It is characterized in that an inorganic ion exchanger is loaded with an antibacterial metal and chlorine. The antibacterial agent of the present invention may carry antibacterial metal and chlorine as an antibacterial metal salt compound. Alternatively, an inorganic ion exchanger carrying chlorine may be used as a carrier on which an antibacterial metal is carried.
【０００９】[0009]
【発明の実施の形態】本発明において抗菌性金属として
は、金、銀、銅、亜鉛、水銀、ビスマス、カドミウム、
コバルト、ニッケル等が挙げられるが、なかでも銀、
銅、水銀が好ましく、特に銀、銅が好ましい。無機イオ
ン交換体としては、例えば珪酸マグネシウム類、珪酸カ
ルシウム類、アルミン酸やアルミン酸塩類、燐酸カルシ
ウム等の燐酸塩類、チタン酸カリウムやチタン酸カルシ
ウム等のチタン酸類、ゼオライト類、酸化アルミニウム
等の金属酸化物類等が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the antibacterial metal, gold, silver, copper, zinc, mercury, bismuth, cadmium,
Cobalt, nickel, etc. may be mentioned, but silver,
Copper and mercury are preferable, and silver and copper are particularly preferable. Examples of the inorganic ion exchanger include magnesium silicates, calcium silicates, aluminates and aluminates, phosphates such as calcium phosphate, titanates such as potassium titanate and calcium titanate, zeolites, and metals such as aluminum oxide. Examples thereof include oxides.
【００１０】本発明の抗菌剤は、上記無機イオン交換体
に、抗菌性金属とともに塩素が担持されている点が大き
な特徴である。本発明の抗菌剤中における塩素は、抗菌
性金属と直接結合している場合（抗菌性金属塩化物とし
て無機イオン交換体に担持されている場合）、抗菌性金
属とは結合せずに無機イオン交換体中のアニオン結合性
部分に担持されている場合、抗菌性金属に直接結合して
いるものと、無機イオン交換体中のアニオン結合性部分
に担持されているものの両方が含まれている場合、のい
ずれであっても良いが、抗菌性金属と塩素との直接結合
割合が高いほど、抗菌効果の持続性に優れている。ま
た、抗菌性金属と塩素とが直接結合している場合、無機
イオン交換体に担持された抗菌性金属に塩素が結合した
構造のものでも、無機イオン交換体に担持された塩素に
抗菌性金属が結合した構造のものでも良い。The antibacterial agent of the present invention is characterized in that chlorine is carried on the inorganic ion exchanger together with the antibacterial metal. When chlorine in the antibacterial agent of the present invention is directly bound to the antibacterial metal (when it is supported on the inorganic ion exchanger as an antibacterial metal chloride), chlorine is not bound to the antibacterial metal and is an inorganic ion. When it is supported on the anion-binding moiety in the exchanger, when it contains both that bound directly to the antibacterial metal and that supported on the anion-binding moiety in the inorganic ion exchanger. However, the higher the direct bonding ratio of the antibacterial metal and chlorine, the more excellent the antibacterial effect is. In addition, when the antibacterial metal and chlorine are directly bonded, even if the structure is such that chlorine is bonded to the antibacterial metal carried on the inorganic ion exchanger, the antibacterial metal is added to the chlorine carried on the inorganic ion exchanger. It may have a structure in which are combined.
【００１１】本発明抗菌剤は、抗菌性金属イオンを含
む溶液と無機イオン交換体とを接触させて無機イオン交
換体に抗菌性金属を担持させ、次いで塩素イオンを含む
溶液と接触させて塩素を担持させる方法、塩素イオン
を含む溶液と無機イオン交換体とを接触させて無機イオ
ン交換体に塩素を担持させ、次いで抗菌性金属イオンを
含む溶液と接触させて抗菌性金属を担持させる方法、
抗菌性金属イオンと塩素イオンとを含む溶液と無機イオ
ン交換体とを接触させて抗菌性金属と塩素とを担持させ
る方法、等によって得ることができる。無機イオン交換
体と抗菌性金属イオンや塩素イオンを含む溶液（以下、
処理液と呼ぶ。）とを接触させるには、上記〜のい
ずれの方法とも、無機イオン交換体を処理液中に浸漬す
るか、無機イオン交換体を充填したカラムに処理液を通
液する方法が採用できる。前者を採用した場合、上記
、の製造方法では抗菌性金属イオンを含む処理液と
塩素イオンを含む処理液を別々に用意して処理を行って
も、一方のイオンを含む処理液で処理した後、該処理液
中に他方のイオンを添加する方法で処理を行っても良
い。In the antibacterial agent of the present invention, a solution containing an antibacterial metal ion is brought into contact with an inorganic ion exchanger to support the antibacterial metal on the inorganic ion exchanger, and then a solution containing a chlorine ion is brought into contact therewith to remove chlorine. A method of supporting, a method of contacting a solution containing a chlorine ion and an inorganic ion exchanger to support chlorine on the inorganic ion exchanger, then a method of contacting with a solution containing an antibacterial metal ion to carry an antibacterial metal,
It can be obtained by a method in which a solution containing antibacterial metal ions and chlorine ions is brought into contact with an inorganic ion exchanger to carry antibacterial metal and chlorine, and the like. A solution containing an inorganic ion exchanger and antibacterial metal ions or chlorine ions (hereinafter,
It is called a processing liquid. In any of the above methods, a method of immersing the inorganic ion exchanger in the treatment liquid or a method of passing the treatment liquid through a column filled with the inorganic ion exchanger can be used to bring the treatment liquid into contact with the). When the former is adopted, in the above manufacturing method, even if the treatment liquid containing antibacterial metal ions and the treatment liquid containing chlorine ions are separately prepared and treated, after the treatment liquid containing one of the ions is treated. Alternatively, the treatment may be performed by a method of adding the other ion to the treatment liquid.
【００１２】従来の抗菌剤に用いられていた無機イオン
交換体は、カチオン交換性のものであるが、近年アニオ
ン交換性を有するものやカチオン交換性とアニオン交換
性の両方を有する無機イオン交換体も知られている。カ
チオン交換性のみを有する無機イオン交換体は、無機イ
オン交換体に担持させた抗菌性金属に塩素が直接結合し
た構造の抗菌剤を製造するのに好適であり、前記の方
法に適用される。またアニオン交換性のみを有する無機
イオン交換体は、無機イオン交換体に塩素を担持させた
ものを担体とし、塩素に抗菌性金属が直接結合した構造
の抗菌剤を製造するのに好適であり、前記の方法に適
用される。またカチオン交換性とアニオン交換性の両方
を有する無機イオン交換体（両性無機イオン交換体と呼
ぶ。）は、主として抗菌性金属と塩素とが直接結合して
おらず、別々に無機イオン交換体に担持された構造の抗
菌剤を製造するのに好適であり、このような抗菌剤は前
記〜のいずれの方法でも製造することができる。The inorganic ion exchangers used in conventional antibacterial agents are cation-exchangeable ones, but in recent years, those having anion-exchangeability and those having both cation-exchangeability and anion-exchangeability have been used. Is also known. The inorganic ion exchanger having only cation exchangeability is suitable for producing an antibacterial agent having a structure in which chlorine is directly bonded to the antibacterial metal supported on the inorganic ion exchanger, and is applied to the above method. Further, the inorganic ion exchanger having only anion exchange property is suitable for producing an antibacterial agent having a structure in which chlorine is supported on the inorganic ion exchanger, and the antibacterial metal is directly bonded to chlorine. Applied to the method described above. Further, an inorganic ion exchanger having both cation exchangeability and anion exchangeability (called an amphoteric inorganic ion exchange) is mainly composed of an antibacterial metal and chlorine that are not directly bonded to each other and are separately separated from each other. It is suitable for producing an antibacterial agent having a supported structure, and such an antibacterial agent can be produced by any of the above methods.
【００１３】無機イオン交換体として両性無機イオン交
換体を使用する場合、両性無機イオン交換体中のカチオ
ン交換能、アニオン交換能に応じて処理液中の抗菌性金
属イオン濃度、塩素イオン濃度を調節することにより、
担持される抗菌性金属と塩素の一部又は全部が直接結合
した構造の抗菌剤とすることもできる。When an amphoteric inorganic ion exchanger is used as the inorganic ion exchanger, the antibacterial metal ion concentration and the chlorine ion concentration in the treatment liquid are adjusted according to the cation exchange ability and the anion exchange ability of the amphoteric inorganic ion exchanger. By doing
It is also possible to use an antibacterial agent having a structure in which a part or all of the carried antibacterial metal and chlorine are directly bonded.
【００１４】即ち、上記の方法で抗菌剤を製造する場
合、両性無機イオン交換体のカチオン交換性部分に抗菌
性金属を担持させた後、塩素イオンを含む処理液で処理
することにより、両性無機イオン交換体のアニオン交換
性部分に塩素が担持されるとともに、先に担持されてい
る抗菌性金属の一部又は全部に塩素が直接結合した構造
の抗菌剤を得ることができる。また上記の方法で製造
する場合、塩素を担持させた両性無機イオン交換体を、
抗菌性金属イオンを含む処理液で処理することにより、
両性無機イオン交換体のカチオン交換性部分に抗菌性金
属が担持されるとともに、先に担持されている塩素の一
部又は全部に抗菌性金属が直接結合した構造の抗菌剤を
得ることができる。That is, when the antibacterial agent is produced by the above-mentioned method, the antibacterial metal is supported on the cation-exchangeable part of the amphoteric inorganic ion exchanger, and then the amphoteric inorganic ion exchanger is treated with a treatment solution containing chloride ions to obtain an amphoteric inorganic substance. It is possible to obtain an antibacterial agent having a structure in which chlorine is supported on the anion-exchangeable part of the ion exchanger and chlorine is directly bonded to a part or all of the antibacterial metal previously supported. Further, when produced by the above method, the amphoteric inorganic ion exchanger supporting chlorine,
By treating with a treatment liquid containing antibacterial metal ions,
It is possible to obtain an antibacterial agent having a structure in which an antibacterial metal is supported on the cation-exchangeable portion of the amphoteric inorganic ion exchanger and the antibacterial metal is directly bonded to a part or all of chlorine previously supported.
【００１５】本発明の抗菌剤において、抗菌性金属は無
機イオン交換体中に、０．０１〜３０重量％担持されて
いることが好ましい。また塩素は、無機イオン交換体に
担持される抗菌性金属１モル当たりに対し、０．５〜５
倍モル担持されていることが好ましい。In the antibacterial agent of the present invention, the antibacterial metal is preferably carried in the inorganic ion exchanger in an amount of 0.01 to 30% by weight. Chlorine is contained in an amount of 0.5 to 5 per mol of the antibacterial metal carried on the inorganic ion exchanger.
It is preferable that the carrier is supported in a double mole.
【００１６】無機イオン交換体に抗菌性金属や塩素を導
入するために用いる抗菌性金属イオンや塩素イオンを含
む処理液は、抗菌性金属の水溶性塩や水溶性の塩素化合
物を水に溶解させることにより調整することができる。
抗菌性金属の水溶性塩としては、金、銀、銅、水銀、ビ
スマス、カドミウム、コバルト、ニッケル等の金属の硫
酸塩、硝酸塩、塩化物、次塩素酸塩、塩素酸塩、過塩素
酸塩等が挙げられる。また水溶性の塩素化合物として
は、塩酸、塩化ナトリウム、塩化カルシウム、塩化マグ
ネシウム、次亜塩素酸ナトリウム等が挙げられる。A treatment liquid containing an antibacterial metal ion or chlorine ion used to introduce an antibacterial metal or chlorine into an inorganic ion exchanger dissolves a water-soluble salt of the antibacterial metal or a water-soluble chlorine compound in water. It can be adjusted.
Water-soluble salts of antibacterial metals include sulfates, nitrates, chlorides, hypochlorates, chlorates, and perchlorates of metals such as gold, silver, copper, mercury, bismuth, cadmium, cobalt, and nickel. Etc. Examples of water-soluble chlorine compounds include hydrochloric acid, sodium chloride, calcium chloride, magnesium chloride, sodium hypochlorite and the like.
【００１７】上記のようにして、無機イオン交換体に抗
菌性金属及び塩素を担持させ脱イオン水で洗浄後、乾燥
することによって本発明の抗菌剤が得られるが、必要に
より乾燥後に焼成することもできる。しかしながら本発
明の抗菌剤は抗菌性金属とともに塩素が担持されている
ことにより、抗菌性金属のみを無機イオン交換体に担持
させた従来の抗菌剤のように抗菌性金属が容易に溶出す
る虞れがないため、必ずしも焼成を行わなくても良い。As described above, the antibacterial metal and chlorine are supported on the inorganic ion exchanger, washed with deionized water, and dried to obtain the antibacterial agent of the present invention. If necessary, baking is performed after drying. You can also However, since the antibacterial agent of the present invention carries chlorine together with the antibacterial metal, the antibacterial metal may be easily eluted as in the conventional antibacterial agent in which only the antibacterial metal is supported on the inorganic ion exchanger. Therefore, the firing does not always have to be performed.
【００１８】本発明の抗菌剤が水と接触すると、抗菌剤
中から水中に極めて微量の抗菌性金属イオンが溶出し、
この溶出した抗菌性金属イオンによって水中の細菌が死
滅し、また水中には微量の抗菌性金属イオンが残存する
ため、その後の細菌の繁殖も妨げられる。また本発明の
抗菌剤が含水している場合、含水水分中に抗菌性金属イ
オンが溶出しているため、抗菌剤と接触した細菌は死滅
する。また本発明の抗菌剤を無水状態で使用した場合で
も、細菌の細胞中には水分が含まれるため、細菌が本発
明抗菌剤と接触すると、細菌の細胞中に抗菌性金属イオ
ンが溶出して細菌を死滅させる。When the antibacterial agent of the present invention comes into contact with water, an extremely small amount of antibacterial metal ion is eluted from the antibacterial agent into water,
The eluted antibacterial metal ions kill bacteria in the water, and a small amount of antibacterial metal ions remain in the water, which also prevents the subsequent propagation of the bacteria. Further, when the antibacterial agent of the present invention contains water, the antibacterial metal ions are eluted in the water content, so that the bacteria that come into contact with the antibacterial agent die. Even when the antibacterial agent of the present invention is used in an anhydrous state, water is contained in the cells of the bacterium, and when the bacterium comes into contact with the antibacterial agent of the present invention, antibacterial metal ions are eluted in the cells of the bacterium. Kill the bacteria.
【００１９】本発明の抗菌剤は、例えば飲料水の殺菌消
毒、水中の藻の増殖抑制、樹脂製品へのカビ等の発生防
止、船底へのフジツボ付着防止、犬猫の糞尿による汚染
防止等を目的として、水や樹脂製品を抗菌処理したり、
船底塗料等の塗料へ添加したり、犬猫の糞尿によって汚
染される虞れのある砂へ添加する等の方法で使用すると
ができ、細菌、バクテリア、カビ、微生物の死滅、発
生、増殖の抑止等を図ることができるが、これらの用途
のみに限定されるものではない。The antibacterial agent of the present invention is used for, for example, sterilizing and disinfecting drinking water, suppressing the growth of algae in water, preventing the formation of mold on resin products, preventing barnacles from adhering to ship bottoms, and preventing contamination by dog and cat excrement. For the purpose, antibacterial treatment of water and resin products,
It can be used by adding it to paint such as ship bottom paint, or adding it to sand that may be contaminated by dog and cat manure, etc., to prevent the death, generation and growth of bacteria, bacteria, molds and microorganisms. However, the present invention is not limited to these applications.
【００２０】本発明抗菌剤により水の抗菌処理を行う方
法としては、本発明抗菌剤を充填したカラムに水を通液
したり、水中に本発明抗菌剤を浸漬する方法等が挙げら
れる。また樹脂製品の抗菌処理に利用する場合には、例
えば原料樹脂中に本発明抗菌剤を練り込む方法を採用す
ることができる。抗菌剤を練り込むための樹脂として
は、可塑性のあるものであれば良く、例えばポリエチレ
ン、ポリプロピレン、ポリスチレン、ＡＢＳ樹脂、ポリ
塩化ビニル、ＭＭＡ樹脂等が挙げられる。抗菌剤の樹脂
中への添加量は任意であり、練り込み効率、抗菌性能、
樹脂強度等を考慮して決定する。Examples of the method for antibacterial treatment of water with the antibacterial agent of the present invention include a method of passing water through a column packed with the antibacterial agent of the present invention and a method of immersing the antibacterial agent of the present invention in water. When used for antibacterial treatment of resin products, for example, a method of kneading the antibacterial agent of the present invention into a raw material resin can be adopted. The resin for kneading the antibacterial agent may be any resin having plasticity, and examples thereof include polyethylene, polypropylene, polystyrene, ABS resin, polyvinyl chloride, MMA resin and the like. The amount of antibacterial agent added to the resin is arbitrary, kneading efficiency, antibacterial performance,
It is determined in consideration of resin strength and the like.
【００２１】抗菌剤を練り込んだ樹脂は、球状、ペレッ
ト状、板状、シート状、繊維状等の任意の形態に成形す
ることができる。例えば板状、シート状、繊維状等に成
形する場合、抗菌剤と樹脂とを予備混合し、エクストリ
ューダー等の混練機中で樹脂の軟化温度以上の温度で混
練し、次いでダイ等からシート状、板状、繊維状等に押
出成形することで抗菌性の樹脂製品が得られる。また抗
菌剤を練り込んだ球状、ペレット状樹脂は、射出成形に
よって所定形状の抗菌性樹脂製品とすることができる。The resin in which the antibacterial agent is kneaded can be molded into any shape such as spherical shape, pellet shape, plate shape, sheet shape and fiber shape. For example, in the case of molding into a plate shape, a sheet shape, a fibrous shape, etc., the antibacterial agent and the resin are premixed, and the mixture is kneaded in a kneader such as an extruder at a temperature equal to or higher than the softening temperature of the resin, and then a sheet from a die or the like An antibacterial resin product can be obtained by extrusion molding into a sheet shape, a plate shape, or a fiber shape. Further, the spherical or pellet-shaped resin in which the antibacterial agent is kneaded can be made into an antibacterial resin product having a predetermined shape by injection molding.
【００２２】また本発明抗菌剤を樹脂製品表面に塗布し
た後、塗布表面をヒートプレスする方法によって、抗菌
性樹脂製品を得ることもできる。It is also possible to obtain an antibacterial resin product by a method of applying the antibacterial agent of the present invention to the surface of the resin product and then heat pressing the applied surface.
【００２３】本発明抗菌剤を船底塗料等の塗料中に添加
する場合、塗料は油性でも水性でも良く、顔料と同様に
して配合し、また水性塗料には薄め水に本発明抗菌剤を
分散させて配合すれば良い。When the antibacterial agent of the present invention is added to a paint such as ship bottom paint, the antibacterial agent may be oily or water-based, and may be blended in the same manner as a pigment. It should be mixed.
【００２４】[0024]
【実施例】以下、実施例を挙げて本発明を更に詳細に説
明する。尚、以下の実施例、比較例において使用した抗
菌剤の種類は、以下の通りである。これらの抗菌剤の調
整には、次の操作方法（１）〜操作方法（３）のいずれ
かの方法を採用した。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. The types of antibacterial agents used in the following Examples and Comparative Examples are as follows. For the preparation of these antibacterial agents, any one of the following operation methods (1) to (3) was adopted.
【００２５】操作方法（１）：無機イオン交換体及び抗
菌性金属の水溶性塩を、脱イオン水１０００重量部に加
え、４０℃にて６時間攪拌後、濾過する。濾過残物を脱
イオン水１０００重量部に添加し、１時間攪拌洗浄した
後、濾過して濾過液のアニオン濃度が１００ｐｐｂ以下
になるまで同様の洗浄、濾過を繰り返し、無機イオン交
換体の抗菌性金属担持物を得る。次いで、これを水溶性
の塩素化合物を溶解した処理液に加え、４０℃で１時間
攪拌後、上記と同様に脱イオン水１０００重量部による
洗浄・濾過をカチオン濃度が１００ｐｐｂ以下になるま
で繰り返す。その後、１２０℃のオーブン中で、水分が
０．１重量％以下となるまで乾燥する。Operation method (1): An inorganic ion exchanger and a water-soluble salt of an antibacterial metal are added to 1000 parts by weight of deionized water, and the mixture is stirred at 40 ° C. for 6 hours and then filtered. The filtration residue is added to 1000 parts by weight of deionized water, washed with stirring for 1 hour and then filtered, and the same washing and filtration are repeated until the anion concentration of the filtrate becomes 100 ppb or less, and the antibacterial property of the inorganic ion exchanger is increased. A metal carrier is obtained. Then, this is added to a treatment liquid in which a water-soluble chlorine compound is dissolved, and the mixture is stirred at 40 ° C. for 1 hour, and then, washing and filtration with 1000 parts by weight of deionized water are repeated until the cation concentration becomes 100 ppb or less as described above. Then, it is dried in an oven at 120 ° C. until the water content becomes 0.1% by weight or less.
【００２６】操作方法（２）：無機イオン交換体及び水
溶性の塩素化合物を、脱イオン水１０００重量部に加
え、４０℃にて６時間攪拌後、濾過する。濾過残物を脱
イオン水１０００重量部に添加し、１時間攪拌洗浄した
後、濾過して濾過液のカチオン濃度が１００ｐｐｂ以下
になるまで同様の洗浄、濾過を繰り返し、無機イオン交
換体の塩素担持物を得る。次いで、これを抗菌性金属の
水溶性塩を溶解した処理液に加え、４０℃で１時間攪拌
後、上記と同様に脱イオン水１０００重量部による洗浄
・濾過をアニオン濃度が１００ｐｐｂ以下になるまで繰
り返す。その後、１２０℃のオーブン中で、水分が０．
１重量％以下となるまで乾燥する。Operation method (2): An inorganic ion exchanger and a water-soluble chlorine compound are added to 1000 parts by weight of deionized water, stirred at 40 ° C. for 6 hours, and then filtered. The filtration residue was added to 1000 parts by weight of deionized water, washed with stirring for 1 hour, and then filtered, and the same washing and filtration were repeated until the cation concentration of the filtrate became 100 ppb or less, and chlorine loading of the inorganic ion exchanger was carried. Get things. Next, this is added to a treatment solution in which a water-soluble salt of an antibacterial metal is dissolved, stirred at 40 ° C. for 1 hour, and then washed and filtered with 1000 parts by weight of deionized water until the anion concentration becomes 100 ppb or less as described above. repeat. After that, in a 120 ° C. oven, the water content is 0.
Dry until less than 1% by weight.
【００２７】操作方法（３）：無機イオン交換体及び抗
菌性金属の水溶性塩を、脱イオン水１０００重量部に加
え、４０℃にて６時間攪拌後、濾過する。濾過残物を脱
イオン水１０００重量部に添加し、１時間攪拌洗浄した
後、濾過して濾過液のアニオン濃度が１００ｐｐｂ以下
になるまで同様の洗浄、濾過を繰り返し、無機イオン交
換体の抗菌性金属担持物を得る。１２０℃のオーブン中
で、水分が０．１重量％以下となるまで乾燥する。Operation method (3): An inorganic ion exchanger and a water-soluble salt of an antibacterial metal are added to 1000 parts by weight of deionized water, and the mixture is stirred at 40 ° C. for 6 hours and then filtered. The filtration residue is added to 1000 parts by weight of deionized water, washed with stirring for 1 hour and then filtered, and the same washing and filtration are repeated until the anion concentration of the filtrate becomes 100 ppb or less, and the antibacterial property of the inorganic ion exchanger is increased. A metal carrier is obtained. Dry in an oven at 120 ° C. until the water content is 0.1% by weight or less.
【００２８】抗菌剤Ａ（本発明品） 下記示性式（ａ）で示されるカチオン交換性の無機イオ
ン交換体１００重量部、硝酸銀３．５重量部、塩化ナト
リウム２．５重量部を用い、操作方法（１）により得た
抗菌剤。Antibacterial agent A (product of the present invention) Using 100 parts by weight of a cation-exchangeable inorganic ion exchanger represented by the following formula (a), 3.5 parts by weight of silver nitrate and 2.5 parts by weight of sodium chloride, The antibacterial agent obtained by the operation method (1).
【００２９】[0029]
【化１】 Ａｌ2 Ｏ3 ・９ＳｉＯ2 ・Ｈ2 Ｏ ・・・（ａ）## STR00001 ## Al 2 O 3 .9SiO 2 .H 2 O ... (a)
【００３０】抗菌剤Ｂ（本発明品） 下記示性式（ｂ）で示されるカチオン交換性の無機イオ
ン交換体１００重量部、硫酸銅５水和物８．０重量部、
塩化カルシウム２水和物３．０重量部を用い、操作方法
（１）により得た抗菌剤。Antibacterial agent B (product of the present invention) 100 parts by weight of a cation-exchangeable inorganic ion exchanger represented by the following formula (b), 8.0 parts by weight of copper sulfate pentahydrate,
An antibacterial agent obtained by the operation method (1) using 3.0 parts by weight of calcium chloride dihydrate.
【００３１】[0031]
【化２】Ａｌ2 Ｏ3 ・・・・（ｂ）[Chemical formula 2] Al 2 O 3 ··· (b)
【００３２】抗菌剤Ｃ（本発明品） 下記示性式（ｃ）で示されるアニオン交換性の無機イオ
ン交換体１００重量部、塩化ナトリウム３．５重量部、
硫酸銀３．０重量部を用い、操作方法（２）により得た
抗菌剤。Antibacterial agent C (product of the present invention) 100 parts by weight of anion-exchangeable inorganic ion exchanger represented by the following rational formula (c), 3.5 parts by weight of sodium chloride,
An antibacterial agent obtained by the operation method (2) using 3.0 parts by weight of silver sulfate.
【００３３】[0033]
【化３】 Ｍｇ9 Ａｌ4 （ＯＨ）26ＣＯ6 ・７Ｈ2 Ｏ ・・・・（ｃ）Embedded image Mg 9 Al 4 (OH) 26 CO 6 / 7H 2 O ... (C)
【００３４】抗菌剤Ｄ（本発明品） 下記示性式（ｄ）で示されるアニオン交換性の無機イオ
ン交換体１００重量部、塩化マグネシウム７．０重量
部、硝酸銅３水和物８．０重量部を用い、操作方法
（２）により得た抗菌剤。Antibacterial agent D (product of the present invention) 100 parts by weight of anion-exchangeable inorganic ion exchanger represented by the following formula (d), 7.0 parts by weight of magnesium chloride, and 8.0 parts of copper nitrate trihydrate. An antibacterial agent obtained by the operation method (2) using parts by weight.
【００３５】[0035]
【化４】 Ｍｇ9 Ａｌ4 （ＯＨ）26ＣＯ6 ・７Ｈ2 Ｏ ・・・・（ｄ）Embedded image Mg 9 Al 4 (OH) 26 CO 6 / 7H 2 O ... (d)
【００３６】抗菌剤Ｅ（本発明品） 下記示性式（ｅ）で示される両性の無機イオン交換体１
００重量部、硝酸銀３．５重量部、塩化ナトリウム５．
０重量部を用い、操作方法（１）により得た抗菌剤。Antibacterial agent E (product of the present invention) Amphoteric inorganic ion exchanger 1 represented by the following formula (e):
00 parts by weight, silver nitrate 3.5 parts by weight, sodium chloride 5.
The antibacterial agent obtained by the operation method (1) using 0 part by weight.
【００３７】[0037]
【化５】 ＭｇＯ6 ＳｉＯ2 ・３Ｈ2 Ｏ ・・・・・（ｅ）[Chemical Formula 5] MgO 6 SiO 2 · 3H 2 O (E)
【００３８】抗菌剤Ｆ（本発明品） 下記示性式（ｆ）で示される両性の無機イオン交換体１
００重量部、塩化カルシウム２水和物１．０重量部、硝
酸銀３．５重量部を用い、操作方法（２）により得た抗
菌剤。Antibacterial agent F (product of the present invention) Amphoteric inorganic ion exchanger 1 represented by the following formula (f):
The antibacterial agent obtained by the operation method (2) using 00 parts by weight, 1.0 part by weight of calcium chloride dihydrate and 3.5 parts by weight of silver nitrate.
【００３９】[0039]
【化６】 Ａｌ（ＯＨ）3 ・ＮａＨＣＯ3 ・・・（ｆ）Embedded image Al (OH) 3 NaHCO 3 (f)
【００４０】抗菌剤Ｇ（従来品） 下記示性式（ｇ）で示されるカチオン交換性の無機イオ
ン交換体１００重量部、硝酸銀３．５重量部を用い、操
作方法（３）により得た抗菌剤。Antibacterial agent G (conventional product) Antibacterial agent obtained by the operation method (3) using 100 parts by weight of a cation-exchangeable inorganic ion exchanger represented by the following rational formula (g) and 3.5 parts by weight of silver nitrate. Agent.
【００４１】[0041]
【化７】 Ａｌ2 Ｏ3 ・９ＳｉＯ2 ・Ｈ2 Ｏ ・・・（ｇ）## STR00007 ## Al 2 O 3 .9SiO 2 .H 2 O ... (g)
【００４２】抗菌剤Ｈ（従来品） 下記示性式（ｈ）で示されるカチオン交換性の無機イオ
ン交換体１００重量部、硝酸銀３．５重量部を用い、操
作方法（３）により得た抗菌剤。Antibacterial agent H (conventional product) Antibacterial agent obtained by the operation method (3) using 100 parts by weight of a cation-exchangeable inorganic ion exchanger represented by the following formula (h) and 3.5 parts by weight of silver nitrate. Agent.
【００４３】[0043]
【化７】Ａｌ2 Ｏ3 ・・・・（ｈ）[Chemical formula 7] Al 2 O 3 ··· (h)
【００４４】実施例１〜６、比較例１〜２ 表１に示す抗菌剤１０ｇを、内径２ｃｍのステンレスカ
ラムに充填し、このカラムに水道水２００ｍｌを連続し
て通水し、１０日後、５０日後、１００日後の通水液中
の金属イオン濃度（銀イオン濃度又は銅イオン濃度）を
原子吸光分析法により測定した。また通水前の抗菌剤を
濃硝酸で処理し、硝酸中に溶出した金属イオン濃度を原
子吸光分析法によって測定し、通水前の抗菌剤中の金属
含有量（重量％）を求めた。これらの結果を表１に示
す。Examples 1 to 6 and Comparative Examples 1 and 2 10 g of the antibacterial agent shown in Table 1 was packed in a stainless steel column having an inner diameter of 2 cm, and 200 ml of tap water was continuously passed through this column, and after 10 days, 50 After 100 days, the metal ion concentration (silver ion concentration or copper ion concentration) in the water flow solution was measured by atomic absorption spectrometry after 100 days. The antibacterial agent before water passing was treated with concentrated nitric acid, and the concentration of metal ions eluted in nitric acid was measured by atomic absorption spectrometry to determine the metal content (% by weight) in the antibacterial agent before water passing. Table 1 shows the results.
【００４５】[0045]
【表１】 [Table 1]
【００４６】また上記抗菌剤２ｇを、ＡＢＳ樹脂１００
ｇに対して練り込んだ後、厚さ１ｍｍのシート状に成形
し、このシートから３０ｍｍ×５０ｍｍのサンプルを作
成した。このサンプルをフェードメーターにセットし、
カーボンアークランプの光を２４時間照射し、サンプル
の色の変化（耐光性）を肉眼で観察した。またサンプル
をギャーオーブン内に吊り下げ、２００℃で１０時間加
熱した際のサンプルの色の変化（耐熱性）を肉眼で観察
した。結果を表１にあわせて示す。2 g of the above antibacterial agent was added to ABS resin 100
After kneading into g, it was formed into a sheet having a thickness of 1 mm, and a sample of 30 mm × 50 mm was prepared from this sheet. Set this sample on the fade meter,
The light from the carbon arc lamp was irradiated for 24 hours, and the change in color (light resistance) of the sample was visually observed. Further, the sample was hung in a gear oven and heated for 10 hours at 200 ° C., and the color change (heat resistance) of the sample was visually observed. The results are shown in Table 1.
【００４７】抗菌剤Ａを練り込んだＡＢＳ樹脂と抗菌剤
Ｂを練り込んだＡＢＳ樹脂とを用い、これら各々を大腸
菌分散溶液に入れて振とう接触し、大腸菌の生菌数の経
時変化を調べた。結果を図１に示す。尚、図１において
○はブランクを、●は抗菌剤Ａを練り込んだＡＢＳ樹脂
の場合を、◎は抗菌剤Ｂを練り込んだＡＢＳ樹脂の場合
を示す。Using the ABS resin in which the antibacterial agent A was kneaded and the ABS resin in which the antibacterial agent B was kneaded, each of them was placed in an Escherichia coli dispersion solution and shake-contacted to examine the change with time of the viable cell count of Escherichia coli. It was The results are shown in FIG. In FIG. 1, ◯ indicates a blank, ● indicates a case of ABS resin in which antibacterial agent A is kneaded, and ∘ indicates a case of ABS resin in which antibacterial agent B is kneaded.
【００４８】[0048]
【発明の効果】以上説明したように、本発明の抗菌剤は
担持されている抗菌性金属が極微量ずつ溶出して抗菌作
用を発現するため、抗菌性金属が多量に溶出して安全性
の問題が生じたりする虞れがなく、しかも長期間に亘っ
て抗菌作用が発現され、抗菌作用の持続性に優れてい
る。また本発明の抗菌剤は耐光性、耐熱性に優れ、樹脂
等に練り込んで用いる場合の熱や、光等によって変色す
る虞れが少ないため、樹脂製品や塗料の抗菌剤として用
いた場合、樹脂製品や塗料の色が変色することがなく、
樹脂製品や塗料の商品価値が高められる効果がある。As described above, in the antibacterial agent of the present invention, the carried antibacterial metal elutes in very small amounts to exert an antibacterial effect, so that a large amount of the antibacterial metal is eluted and safety is improved. There is no risk of problems, and the antibacterial action is exhibited over a long period of time, and the antibacterial action is excellent in sustainability. Further, the antibacterial agent of the present invention is excellent in light resistance, heat resistance, heat when kneaded into a resin or the like, and since there is little risk of discoloration due to light, when used as an antibacterial agent for resin products or paints, The color of resin products and paint does not change,
It has the effect of increasing the commercial value of resin products and paints.
【図１】本発明抗菌剤の経時変化を示すグラフである。FIG. 1 is a graph showing changes with time of the antibacterial agent of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小川 隆 東京都葛飾区堀切４丁目66番１号 ミヨシ 油脂株式会社内 (72)発明者 松本 晁暎 東京都葛飾区堀切４丁目66番１号 ミヨシ 油脂株式会社内 (72)発明者 守屋 雅文 東京都葛飾区堀切４丁目66番１号 ミヨシ 油脂株式会社内 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Takashi Ogawa 4-66-1 Horikiri Katsushika-ku, Tokyo Miyoshi Oil & Fat Co., Ltd. (72) Inventor Akiaki Matsumoto 4-66-1 Horikiri, Katsushika-ku, Tokyo Miyoshi Oils and Fats Co., Ltd. (72) Inventor Masafumi Moriya 4-66-1 Horikiri, Katsushika-ku, Tokyo Miyoshi Oils and Fats Co., Ltd.
Claims (3)
とを担持せしめたことを特徴とする抗菌剤。1. An antibacterial agent comprising an inorganic ion exchanger carrying an antibacterial metal and chlorine.
合物として担持されていることを特徴とする請求項１記
載の抗菌剤。2. The antibacterial agent according to claim 1, wherein the antibacterial metal and chlorine are carried as an antibacterial metal salt compound.
とし、これに抗菌性金属が担持されていることを特徴と
する請求項１又は２記載の抗菌剤。3. The antibacterial agent according to claim 1 or 2, wherein an inorganic ion exchanger carrying chlorine is used as a carrier, and an antibacterial metal is carried on the carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34552095A JP3651992B2 (en) | 1995-12-08 | 1995-12-08 | Antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34552095A JP3651992B2 (en) | 1995-12-08 | 1995-12-08 | Antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09157119A true JPH09157119A (en) | 1997-06-17 |
| JP3651992B2 JP3651992B2 (en) | 2005-05-25 |
Family
ID=18377145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34552095A Expired - Fee Related JP3651992B2 (en) | 1995-12-08 | 1995-12-08 | Antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3651992B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09278615A (en) * | 1996-04-15 | 1997-10-28 | Nittetsu Mining Co Ltd | Antimicrobial titania and its production |
| JP2003529630A (en) * | 1999-12-15 | 2003-10-07 | スィー．アール． バード インコーポレイテッド | Polymer composition containing silver salt colloid |
| JP4837828B2 (en) * | 1998-09-15 | 2011-12-14 | ナノスケール コーポレーション | Reactive nanoparticles as adsorption and removal agents for biological and chemical pollutants |
| JP2020519753A (en) * | 2017-05-12 | 2020-07-02 | インヒビット コーティングズ リミテッド | Composite resin containing silver nanoparticles |
| CN111436459A (en) * | 2019-12-27 | 2020-07-24 | 福建格瑞诗化工科技有限公司 | Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid |
| CN116285067A (en) * | 2023-04-03 | 2023-06-23 | 安徽康然创氧生物科技有限公司 | Antibacterial plastic master batch and application thereof in antibacterial plastic products |
-
1995
- 1995-12-08 JP JP34552095A patent/JP3651992B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09278615A (en) * | 1996-04-15 | 1997-10-28 | Nittetsu Mining Co Ltd | Antimicrobial titania and its production |
| JP4837828B2 (en) * | 1998-09-15 | 2011-12-14 | ナノスケール コーポレーション | Reactive nanoparticles as adsorption and removal agents for biological and chemical pollutants |
| JP2003529630A (en) * | 1999-12-15 | 2003-10-07 | スィー．アール． バード インコーポレイテッド | Polymer composition containing silver salt colloid |
| JP4786848B2 (en) * | 1999-12-15 | 2011-10-05 | スィー．アール． バード インコーポレイテッド | Polymer composition containing silver salt colloid |
| JP2020519753A (en) * | 2017-05-12 | 2020-07-02 | インヒビット コーティングズ リミテッド | Composite resin containing silver nanoparticles |
| CN111436459A (en) * | 2019-12-27 | 2020-07-24 | 福建格瑞诗化工科技有限公司 | Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid |
| CN111436459B (en) * | 2019-12-27 | 2021-12-28 | 福建格瑞诗化工科技有限公司 | Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid |
| CN116285067A (en) * | 2023-04-03 | 2023-06-23 | 安徽康然创氧生物科技有限公司 | Antibacterial plastic master batch and application thereof in antibacterial plastic products |
| CN116285067B (en) * | 2023-04-03 | 2023-10-13 | 安徽康然创氧生物科技有限公司 | Antibacterial plastic master batch and application thereof in antibacterial plastic products |
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| Publication number | Publication date |
|---|---|
| JP3651992B2 (en) | 2005-05-25 |
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