JPH08165211A - Production of antimicrobial agent and antimicrobial agent - Google Patents
Production of antimicrobial agent and antimicrobial agentInfo
- Publication number
- JPH08165211A JPH08165211A JP33353394A JP33353394A JPH08165211A JP H08165211 A JPH08165211 A JP H08165211A JP 33353394 A JP33353394 A JP 33353394A JP 33353394 A JP33353394 A JP 33353394A JP H08165211 A JPH08165211 A JP H08165211A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- antibacterial
- antibacterial agent
- silver
- raw material
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌・抗カビ効果の持
続性が改良された抗菌性の金属を含有するポリマー粒子
からなる抗菌剤の製造方法及び抗菌剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antibacterial agent comprising polymer particles containing an antibacterial metal having improved antibacterial / antifungal effect persistence and an antibacterial agent.
【０００２】[0002]
【従来の技術】従来から微量の銀、銅、亜鉛等の金属イ
オンが抗菌・抗カビ効果を有することはよく知られてお
り、このような抗菌性の金属イオンは、例えば硝酸銀の
ような金属塩の形態で殺菌剤、消毒剤等に添加され各種
分野で広く使用されている。しかし、このような金属塩
は、水溶液状態で取り扱うことからその用途が限定さ
れ、また硝酸銀にあっては人体への強い粘膜刺激性があ
り、その安全性にも問題が多い。2. Description of the Related Art It has been well known that minute amounts of metal ions such as silver, copper and zinc have an antibacterial / antifungal effect, and such antibacterial metal ions are, for example, metals such as silver nitrate. It is widely used in various fields by being added to germicides, disinfectants, etc. in the form of salt. However, such a metal salt is limited in its use because it is handled in an aqueous solution, and silver nitrate has a strong mucosal stimulus to the human body, and its safety is also problematic.
【０００３】このような状況より、近年銀等の抗菌性金
属イオンを各種の担体に担持させ、取扱操作性の改善と
抗菌活性の持続性を向上させる検討が行われている。例
えば、このような担体として活性炭(特公昭52-38666
号)、ゼオライト(特公昭63-54013号)、非晶質アルミノ
珪酸塩(特開平3-23960号)等を使用し、これら各種の担
体に抗菌性金属イオンを担持させた例が開示されてい
る。しかしながら、このような担体は何れも無機化合物
の担体であることから、有機系ポリマーを基材とする樹
脂や塗料等への分散性が悪く、自ずとその用途が限定さ
れている。Under such circumstances, studies have recently been made to improve antibacterial metal ions such as silver on various carriers to improve handling operability and durability of antibacterial activity. For example, as such a carrier, activated carbon (Japanese Patent Publication No.
No.), zeolite (Japanese Examined Patent Publication No. 63-54013), amorphous aluminosilicate (JP-A No. 3-23960), etc. are used, and examples of carrying antibacterial metal ions on these various carriers are disclosed. There is. However, since all such carriers are inorganic compound carriers, their dispersibility in resins and paints based on organic polymers is poor, and their use is naturally limited.
【０００４】従って、有機系ポリマー樹脂等に使用でき
る抗菌剤として、有機系ポリマーを基材とする抗菌剤の
開発が要望され、各種の抗菌剤が検討されている。例え
ば、抗菌性の金属イオンを界面活性剤の塩の形態で使用
する方法(特開平3-141205号)が開示されているが、この
ような抗菌剤は、抗菌性金属イオンが単なる界面活性剤
の塩として担持されていることから、金属イオンが容易
に溶出するという問題がある。Therefore, as an antibacterial agent that can be used in organic polymer resins and the like, development of an antibacterial agent based on an organic polymer has been demanded, and various antibacterial agents have been studied. For example, a method of using an antibacterial metal ion in the form of a salt of a surfactant is disclosed (Japanese Patent Laid-Open No. 3-141205). Since it is supported as a salt of the above, there is a problem that metal ions are easily eluted.
【０００５】このような状況の中で、本願出願人のひと
りは抗菌性金属イオンを有機系ポリマー粒子に担持させ
る方法について検討を行い、先に特開平4-173712号とし
て抗菌活性の持続性を有する抗菌剤及びその製法技術を
開示した。この抗菌剤は、担体が有機系ポリマーである
ことから他のポリマー樹脂との相溶性に優れている。こ
の技術は、担体ポリマーを水を分散媒とする乳化重合に
よって得た後、これに抗菌性金属イオンを混合して反応
させることによって抗菌剤を製造するものである。この
方法について更に検討を重ねた結果、この抗菌剤は抗菌
性金属が担体表面に分布し、抗菌性金属が離脱し易いこ
とからその溶出速度が早くなり、抗菌効果の持続性が未
だ充分でないことが明らかとなった。更にこの抗菌剤
は、乳化重合に使用する原料にスルホン酸基を有するラ
ジカル重合性の乳化剤原料を使用するが、このような原
料中のスルホン酸基の存在により、得られたポリマーの
耐熱性が非常に低下し、他の樹脂材料との溶融混合の際
に容易にその熱分解によって樹脂の着色の現象を招来
し、その用途が非常に制限されているという欠点があ
る。従って、有機系ポリマーを担体とする抗菌剤とし
て、各種のポリマーに均一に混合が可能であり、しかも
抗菌活性の持続性と幅広い用途分野で使用できるような
抗菌剤の耐熱性と分散性に優れた抗菌剤の開発が要望さ
れている。Under these circumstances, one of the applicants of the present application investigated a method for supporting antibacterial metal ions on organic polymer particles, and first disclosed in JP-A No. 4-173712 that the antibacterial activity was maintained. An antibacterial agent having the same and a method for producing the same have been disclosed. This antibacterial agent has excellent compatibility with other polymer resins because the carrier is an organic polymer. According to this technique, an antibacterial agent is produced by obtaining a carrier polymer by emulsion polymerization using water as a dispersion medium, and then mixing this with an antibacterial metal ion to react them. As a result of further study on this method, the antibacterial agent has an antibacterial metal distributed on the surface of the carrier, and the antibacterial metal is easily released. Became clear. Further, this antibacterial agent uses a radical-polymerizable emulsifier raw material having a sulfonic acid group as a raw material used for emulsion polymerization. Due to the presence of the sulfonic acid group in the raw material, the heat resistance of the obtained polymer is improved. It is extremely low, and when melt-mixed with other resin materials, the thermal decomposition thereof easily causes a phenomenon of coloring of the resin, and its use is very limited. Therefore, as an antibacterial agent using an organic polymer as a carrier, it can be uniformly mixed with various polymers, and the antibacterial agent is excellent in heat resistance and dispersibility so that it can be used in a wide range of fields with long-lasting antibacterial activity. There is a demand for the development of antibacterial agents.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは前述の実
状に鑑み、抗菌剤の耐熱性と各種ポリマーへの分散性が
優れ、しかも抗菌活性の持続性に優れた抗菌剤を得るべ
く鋭意検討を重ねた。その結果、アクリル酸エステル系
の原料と銀、銅、亜鉛から選ばれたアクリル酸塩又はメ
タクリル酸塩とを有機溶媒の存在下で重合を行うことに
より、得られる抗菌性金属を含有するポリマーが、前述
の課題を解決する優れた抗菌剤となることを見出し、係
る知見に基づき本発明を完成したものである。DISCLOSURE OF THE INVENTION In view of the above-mentioned circumstances, the present inventors have earnestly sought to obtain an antibacterial agent which is excellent in heat resistance of the antibacterial agent and dispersibility in various polymers, and which is excellent in durability of antibacterial activity. I examined it repeatedly. As a result, a polymer containing an antibacterial metal obtained by polymerizing an acrylate-based raw material and an acrylate or methacrylate selected from silver, copper, and zinc in the presence of an organic solvent is obtained. The present invention has been completed based on the finding that it is an excellent antibacterial agent that solves the above-mentioned problems.
【０００７】[0007]
【課題を解決するための手段】即ち本発明は、重合用原
料アクリル酸エステル又はメタクリル酸エステル、及
び／又はジ又はトリアクリル酸エステル又はジ又はト
リメタクリル酸エステルと、銀、銅、亜鉛から選ばれ
たアクリル酸塩又はメタクリル酸塩とを、有機溶媒の存
在下で共重合反応させることを特徴とする抗菌剤の製造
方法に関し、更にこのような製造方法で得られる抗菌剤
に関する。Means for Solving the Problems That is, according to the present invention, a raw material for polymerization acrylic acid ester or methacrylic acid ester, and / or di- or triacrylic acid ester or di- or trimethacrylic acid ester, and silver, copper or zinc are selected. The present invention relates to a method for producing an antibacterial agent, which comprises subjecting the obtained acrylate or methacrylate to a copolymerization reaction in the presence of an organic solvent, and further to an antibacterial agent obtained by such a production method.
【０００８】[0008]
【作用】以下本発明について更に詳述する。本発明の抗
菌剤は、重合用原料アクリル酸エステル又はメタクリ
ル酸エステル、及び／又はジ又はトリアクリル酸エス
テル又はジ又はトリメタクリル酸エステルと銀、銅、
亜鉛から選ばれたアクリル酸塩又はメタクリル酸塩と
を、有機溶媒の存在下で共重合反応させることにより得
られるものである。従って、本発明ではその原料にスル
ホン酸基を有するラジカル重合性の原料を使用しないた
め、得られる抗菌剤の耐熱性は非常に優れたものとな
る。また本発明で重要な点は、抗菌性金属元素である
銀、銅、亜鉛から選ばれたアクリル酸塩又はメタクリル
酸塩を、有機溶媒中でアクリル酸エステル系の重合用原
料と共重合反応させることにある。このような共重合反
応によって、抗菌性金属元素はポリマー中に均一且つ強
固に取り込まれ、結果として得られる抗菌剤が、抗菌活
性を長期間にわたり維持できるものとなる。The present invention will be described in more detail below. The antibacterial agent of the present invention is a raw material for polymerization acrylic acid ester or methacrylic acid ester, and / or di- or tri-acrylic acid ester or di- or trimethacrylic acid ester and silver, copper,
It is obtained by a copolymerization reaction with an acrylate or methacrylate selected from zinc in the presence of an organic solvent. Therefore, in the present invention, since a radical-polymerizable raw material having a sulfonic acid group is not used as the raw material, the heat resistance of the obtained antibacterial agent becomes very excellent. Further, an important point in the present invention is to copolymerize an acrylic acid salt or a methacrylate salt selected from silver, copper and zinc, which are antibacterial metal elements, with an acrylic acid ester-based raw material for polymerization in an organic solvent. Especially. By such a copolymerization reaction, the antibacterial metal element is uniformly and strongly incorporated into the polymer, and the resulting antibacterial agent can maintain the antibacterial activity for a long period of time.
【０００９】本発明で用いる重合用原料について更に詳
記すると、重合用原料のアクリル酸エステル又はメタ
クリル酸エステルの例としては、例えば、メチルアクリ
レート、エチルアクリレート、ブチルアクリレート、２
−エチルヘキシルアクリレート、メチルメタクリレー
ト、エチルメタクリレート、ブチルメタクリレート、オ
クチルアクリレート、オクチルメタクリレート等の脂肪
族アルコールの各種アクリル酸エステル、メタクリル酸
エステル、シクロヘキシルアクリレート、シクロヘキシ
ルメタクリレート、シクロヘキシルメチルアクリレー
ト、シクロヘキシルメチルメタクリレート等の脂環式ア
ルコールのアクリル酸エステル、メタクリル酸エステル
がある。更に、フェニルアクリレート、フェニルメタク
リレート、ベンジルアクリレート、ベンジルメタクリレ
ート等の芳香族アクリル酸エステル、メタクリル酸エス
テルがある。更に、２−ヒドロキシエチルアクリレー
ト、２−ヒドロキシエチルメタクリレート等の水酸基を
含有したもの、或いは４−ブロモフェニルアクリレー
ト、４−クロルフェニルメタクリレート等のハロゲンを
含有したアクリル酸エステルやメタクリル酸エステル等
も挙げることが出来る。しかし、これらに限定されるも
のではない。The polymerization raw material used in the present invention will be described in more detail. Examples of the acrylic acid ester or methacrylic acid ester as the polymerization raw material include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, and 2
-Acrylic esters such as ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, etc. There are acrylic acid esters and methacrylic acid esters of formula alcohols. Further, there are aromatic acrylic acid esters and methacrylic acid esters such as phenyl acrylate, phenyl methacrylate, benzyl acrylate and benzyl methacrylate. Furthermore, those containing a hydroxyl group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, or halogen-containing acrylic acid ester and methacrylic acid ester such as 4-bromophenyl acrylate and 4-chlorophenyl methacrylate are also included. Can be done. However, it is not limited to these.
【００１０】次に、重合用原料のジ又はトリアクリル
酸エステル又は、ジ又はトリメタクリル酸エステルの例
としては、エチレングリコールジアクリレート、エチレ
ングリコールジメタクリレート、プロピレングリコール
ジアクリレート、プロピレングリコールジメタクリレー
ト、ジエチレングリコールジアクリレート、ジエチレン
グリコールジメタクリレート、ポリエチレングリコール
ジアクリレート、ポリエチレングリコールジメタクリレ
ート、１，３−ジアクリロキシ−２−プロパノール、
１，３−ジメタクリロキシ−２−プロパノール等の二官
能性ジアクリル酸エステル、ジメタクリル酸エステルの
他、グリセリンのトリアクリレート、トリメタクリレー
トやトリメチロールプロパンのトリアクリレートやトリ
メタクリレート等の三官能アクリル酸エステルやメタク
リル酸エステル等も用いることができるが、これらに限
定されるものではない。Next, examples of di- or tri-acrylic acid ester or di- or tri-methacrylic acid ester as a raw material for polymerization include ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate and diethylene glycol. Diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,3-diacryloxy-2-propanol,
In addition to difunctional diacrylates and dimethacrylates such as 1,3-dimethacryloxy-2-propanol, trifunctional acrylates such as glycerin triacrylate and trimethacrylate and trimethylolpropane triacrylate and trimethacrylate. Methacrylic acid ester and the like can be used, but are not limited thereto.
【００１１】本発明ではこのような重合用原料及び／
又はの原料の他、これら重合用原料に共重合可能な他
の単量体も用いることができる。このような単量体の使
用は、本発明の抗菌剤を他の樹脂と混合させる場合に、
樹脂との相溶性が増加する等で有用である。このような
単量体の例としては、スチレン、ジビニルベンゼン、ジ
アリルフタレート、トリアクリルシアヌレート、塩化ビ
ニル、酢酸ビニル、アクリロニトリル、α−メチルスチ
レン、ブタジエン等が目的に応じて使用できる。In the present invention, such a raw material for polymerization and / or
In addition to the above raw materials, other monomers copolymerizable with these polymerization raw materials can also be used. The use of such a monomer, when the antibacterial agent of the present invention is mixed with another resin,
It is useful because it increases compatibility with resins. Examples of such a monomer include styrene, divinylbenzene, diallyl phthalate, triacryl cyanurate, vinyl chloride, vinyl acetate, acrylonitrile, α-methylstyrene, butadiene and the like depending on the purpose.
【００１２】次に、本発明で使用する重合用原料銀、
銅、亜鉛から選ばれたアクリル酸塩又はメタクリル酸塩
について詳述する。このような重合用原料は、次のよ
うな方法によって容易に製造することができる。即ち、
先ずアクリル酸又はメタクリル酸のナトリウム塩、カリ
ウム塩等を水やメタノール等の溶媒に溶解させ、これに
抗菌性金属塩として硝酸銀、硝酸銅、硫酸銅、酢酸銅、
硝酸亜鉛、硫酸亜鉛等の水溶液を加え、アクリル酸又は
メタクリル酸の銀、銅、亜鉛からなる塩として析出させ
る。次いで、この析出物をろ過、洗浄、乾燥することに
より得ることができる。Next, the raw material silver for polymerization used in the present invention,
The acrylate or methacrylate selected from copper and zinc will be described in detail. Such a raw material for polymerization can be easily produced by the following method. That is,
First, sodium or potassium salt of acrylic acid or methacrylic acid is dissolved in a solvent such as water or methanol, and silver nitrate, copper nitrate, copper sulfate, copper acetate as an antibacterial metal salt is dissolved in this.
An aqueous solution of zinc nitrate, zinc sulfate or the like is added to precipitate as a salt of acrylic acid or methacrylic acid, which is composed of silver, copper and zinc. Then, this precipitate can be obtained by filtering, washing and drying.
【００１３】次に、本発明の抗菌剤の製造方法について
詳記すると、本発明は先ず重合用原料及び／又はを
有機溶媒中に溶解させ、更にこれに前述の重合用原料
を溶解あるいは分散させる。使用できる有機溶媒の種類
としては、酢酸エチル、エチルプロピオネート、エチル
−ｎ−ヘキサネート、ヘキサン、メチルイソブチルケト
ン、メチルエチルケトン、アセトン、ベンゼン、トルエ
ン、キシレン、ジメチルスルホキシド、ジメチルホルム
アミド等が挙げられる。本発明ではこのような有機溶媒
の存在下で共重合反応を行うことにより、これによって
抗菌性金属塩がポリマー担体中に均一に分布した抗菌剤
が得られる。Next, the method for producing the antibacterial agent of the present invention will be described in detail. In the present invention, the raw material for polymerization and / or the organic raw material is first dissolved in an organic solvent, and the raw material for polymerization is dissolved or dispersed therein. . Examples of the organic solvent that can be used include ethyl acetate, ethyl propionate, ethyl-n-hexanate, hexane, methyl isobutyl ketone, methyl ethyl ketone, acetone, benzene, toluene, xylene, dimethyl sulfoxide, and dimethyl formamide. In the present invention, the copolymerization reaction is carried out in the presence of such an organic solvent, whereby an antibacterial agent in which the antibacterial metal salt is uniformly distributed in the polymer carrier can be obtained.
【００１４】本発明の重合用原料及び／又はの使用
割合は、目的とする抗菌剤の組成当たり、原料のアク
リル酸エステル又はメタクリル酸エステルは0〜95重量
％、特に好ましくは20〜70重量％、原料のジ又はトリ
アクリル酸エステル又はジ又はトリメタクリル酸エステ
ルは0〜95重量％、特に好ましくは20〜70％である。
尚、原料との使用割合は、得ようとする抗菌剤に柔
軟さを必要とする場合には、主として原料の使用量を
多くし、逆に堅さを必要とする場合には、原料の使用
量を多くすればよい。The raw material for polymerization of the present invention and / or the use ratio thereof is 0 to 95% by weight, particularly preferably 20 to 70% by weight, based on the composition of the desired antibacterial agent, the raw material acrylic ester or methacrylic ester. The raw material di- or triacrylic acid ester or di- or trimethacrylic acid ester is 0 to 95% by weight, particularly preferably 20 to 70%.
The proportion of the raw material used is such that when the antibacterial agent to be obtained requires flexibility, the amount of the raw material used is increased, and conversely, when hardness is required, the use of the raw material is increased. You can increase the amount.
【００１５】また、原料銀、銅、亜鉛から選ばれたア
クリル酸塩又はメタクリル酸塩の使用量は、ポリマー担
体中に担持する抗菌性金属量と比例関係にあり、これは
所望する抗菌剤の抗菌活性とも相関し、その量はこれら
原料の単量体の総量に対して少なくとも2重量％以上、
好ましくは5重量％以上を使用する。しかし、その上限
に関しては30重量％であり、これを越えるとポリマー担
体中への抗菌性金属塩の取り込みが困難となり、また抗
菌性金属が不均一に分散することから、長期間での抗菌
活性の維持が困難となるため好ましくない。有機溶媒の
使用量について云えば、原料及び／又はとの総量
に対して2〜20倍量程度が好ましい。The amount of the acrylate or methacrylate selected from the raw materials silver, copper and zinc is proportional to the amount of the antibacterial metal supported on the polymer carrier, which is a desired antibacterial agent. It also correlates with antibacterial activity, and its amount is at least 2% by weight or more with respect to the total amount of these raw material monomers
Preferably, 5% by weight or more is used. However, the upper limit is 30% by weight, and if it exceeds this range, it will be difficult to incorporate the antibacterial metal salt into the polymer carrier, and the antibacterial metal will be non-uniformly dispersed, resulting in long-term antibacterial activity. Is difficult to maintain, which is not preferable. As for the amount of the organic solvent used, it is preferably about 2 to 20 times the total amount of the raw materials and / or.
【００１６】重合反応は、このような原料溶液に重合開
始剤を添加し、還流下、攪拌を行いながら反応系を50〜
80℃に加熱し概ね2〜20時間行う。重合開始剤として
は、有機過酸化物やアゾ系化合物が使用でき、例えば過
酸化ベンゾイル等が使用できる。重合の進行と共に、抗
菌性金属塩が担持された本発明の抗菌剤は平均粒子径が
0.5〜50μm程度の粒子状となって析出する。反応の停止
後、析出した重合体粒子を濾過等で分離し、必要ならば
有機溶媒や水を用いて洗浄した後、乾燥を行うことによ
り粉末状の本発明抗菌剤を得ることができる。The polymerization reaction is carried out by adding a polymerization initiator to such a raw material solution and stirring the reaction system under reflux at 50 to 50%.
Heat to 80 ℃ and perform for approximately 2 to 20 hours. As the polymerization initiator, an organic peroxide or an azo compound can be used, and for example, benzoyl peroxide or the like can be used. With the progress of polymerization, the antibacterial agent of the present invention carrying an antibacterial metal salt has an average particle size of
Precipitates in the form of particles of about 0.5 to 50 μm. After stopping the reaction, the precipitated polymer particles are separated by filtration or the like, washed with an organic solvent or water if necessary, and then dried to obtain the antibacterial agent of the present invention in powder form.
【００１７】[0017]
【実施例】以下に本発明の実施例を掲げ更に説明を行
う。尚、本実施例に於いて、％は特に断らない限り全て
重量％を示す。EXAMPLES The examples of the present invention will be further described below. In this example, all percentages are by weight unless otherwise specified.
【００１８】（実施例１）メタクリル酸17.2gをメタノ
ール700gに溶解し、これに20％水酸化ナトリウム水溶液
40gを添加してメタクリル酸をナトリウム塩とした後、
これに攪拌下40％硝酸銀水溶液87gを添加、反応させる
ことによりメタクリル酸銀の懸濁液を得た。この懸濁液
を吸引ろ過により懸濁粒子を分取し、これをメタノール
で洗浄した後、真空乾燥を行うことにより、メタクリル
酸銀36gを得た。Example 1 17.2 g of methacrylic acid was dissolved in 700 g of methanol, and a 20% aqueous sodium hydroxide solution was added to the solution.
After adding 40g to make methacrylic acid sodium salt,
A suspension of silver methacrylate was obtained by adding 87 g of 40% silver nitrate aqueous solution with stirring and reacting. Suspended particles were collected from this suspension by suction filtration, washed with methanol, and vacuum dried to obtain 36 g of silver methacrylate.
【００１９】攪拌機を備えた1L容の4ツ口フラスコに、有
機溶媒としてメチルイソブチルケトン500gを入れ、これ
にメタクリル酸メチル45.0gとジエチレングリコールジ
メタクリレート5.0gを添加溶解させた。次に、この溶液
に上記のメタクリル酸銀5.5gを添加して懸濁液とし、更
に重合触媒として過酸化ベンゾイル1.0gを添加した。次
いで、この溶液を窒素置換により脱気を行いながら攪拌
下、反応系を60℃に加熱しながら4時間、更に80℃で6時
間の反応を行い本発明抗菌剤の懸濁液を得た。In a 1 L 4-necked flask equipped with a stirrer, 500 g of methyl isobutyl ketone was placed as an organic solvent, and 45.0 g of methyl methacrylate and 5.0 g of diethylene glycol dimethacrylate were added and dissolved therein. Next, 5.5 g of the above-mentioned silver methacrylate was added to this solution to make a suspension, and 1.0 g of benzoyl peroxide was added as a polymerization catalyst. Next, this solution was reacted for 4 hours while stirring the reaction system while heating the reaction system at 60 ° C while degassing by nitrogen substitution, and further for 6 hours at 80 ° C to obtain a suspension of the antibacterial agent of the present invention.
【００２０】反応後、この懸濁液を吸引ろ過によって懸
濁粒子を分取し、これをメチルイソブチルケトンで洗浄
した後真空乾燥を行い、更にこれを水で洗浄して真空乾
燥を行うことにより本発明の抗菌剤49.0gを得た。得ら
れた本発明の抗菌剤中の銀含有量を原子吸光法によって
測定した結果3.4％であった。また、この抗菌剤を超音
波洗浄器を用いて水に分散し、これを遠心沈降式粒度分
布測定装置を使用して遠心沈降法で粒子径を測定した結
果、平均粒子径は4μmであった。After the reaction, the suspension particles are separated from the suspension by suction filtration, washed with methyl isobutyl ketone and vacuum dried, and further washed with water and vacuum dried. 49.0 g of the antibacterial agent of the present invention was obtained. The silver content in the obtained antibacterial agent of the present invention was measured by an atomic absorption method and was found to be 3.4%. Further, this antibacterial agent was dispersed in water using an ultrasonic cleaner, and the particle size was measured by the centrifugal sedimentation method using a centrifugal sedimentation type particle size distribution measuring device.As a result, the average particle diameter was 4 μm. .
【００２１】（実施例２）実施例１のメタクリル酸に代
えてアクリル酸14.4gを使用し、同様の操作によってア
クリル酸銀28gを得た。実施例１で用いたメタクリル酸
メチルを使用せず、ジエチレングリコールジメタクリレ
ートの50gを使用し、更にメタクリル酸銀に代えてアク
リル酸銀5.0gを使用し、実施例１と同様に重合反応を行
い本発明の抗菌剤47.5gを得た。この抗菌剤の銀含有量
及び平均粒子径を測定した結果、銀含有量は2.4％であ
り、平均粒子径は3μmであった。(Example 2) 14.4 g of acrylic acid was used in place of methacrylic acid of Example 1, and 28 g of silver acrylate was obtained by the same operation. The methyl methacrylate used in Example 1 was not used, 50 g of diethylene glycol dimethacrylate was used, and 5.0 g of silver acrylate was used in place of silver methacrylate. 47.5 g of the antibacterial agent of the invention was obtained. As a result of measuring the silver content and the average particle size of this antibacterial agent, the silver content was 2.4% and the average particle size was 3 μm.
【００２２】（実施例３）実施例１の硝酸銀水溶液に代
えて20％硫酸銅水溶液80gを使用し、同様の操作によっ
てメタクリル酸銅22gを得た。実施例１で用いたメタク
リル酸メチルを使用せず、ジエチレングリコールジメタ
クリレートの50gを使用し、更にメタクリル酸銀に代え
てメタクリル酸銅6.7gを使用し、実施例１と同様に重合
反応を行い本発明の抗菌剤48.0gを得た。この抗菌剤の
銅含有量及び平均粒子径を測定した結果、銅含有量は1.
3％であり、平均粒子径は15μmであった。(Example 3) In place of the silver nitrate aqueous solution of Example 1, 80 g of 20% copper sulfate aqueous solution was used, and 22 g of copper methacrylate was obtained by the same operation. The methyl methacrylate used in Example 1 was not used, 50 g of diethylene glycol dimethacrylate was used, 6.7 g of copper methacrylate was used in place of silver methacrylate, and a polymerization reaction was carried out in the same manner as in Example 1 48.0 g of the antibacterial agent of the invention was obtained. As a result of measuring the copper content and the average particle size of this antibacterial agent, the copper content is 1.
3% and the average particle size was 15 μm.
【００２３】（実施例４）実施例１の硝酸銀水溶液に代
えて40％硝酸亜鉛水溶液47.5gを使用し、同様の操作を
行うことによってメタクリル酸亜鉛22.5gを得た。実施
例１で用いたメタクリル酸メチルを使用せず、ジエチレ
ングリコールジメタクリレートの50gを使用し、更に実
施例１で用いたメタクリル酸銀に代えてメタクリル酸亜
鉛6.8gを使用し、実施例１と同様に反応を行い本発明の
抗菌剤48.5gを得た。この抗菌剤の亜鉛含有量及び平均
粒子径を測定した結果、亜鉛含有量は1.2％であり、平
均粒子径は20μmであった。Example 4 In place of the silver nitrate aqueous solution of Example 1, 47.5 g of 40% zinc nitrate aqueous solution was used, and the same operation was performed to obtain 22.5 g of zinc methacrylate. As in Example 1, except that the methyl methacrylate used in Example 1 was not used, 50 g of diethylene glycol dimethacrylate was used, and 6.8 g of zinc methacrylate was used in place of the silver methacrylate used in Example 1. Then, 48.5 g of the antibacterial agent of the present invention was obtained. As a result of measuring the zinc content and the average particle size of this antibacterial agent, the zinc content was 1.2% and the average particle size was 20 μm.
【００２４】（比較例１）攪拌機を備えた1L容の4ツ口フ
ラスコに水500gを入れ、これにスルホン酸ナトリウム基
を有するラジカル重合性乳化剤31.4g(三洋化成工業(株)
製,商品名JS-2,38％水溶液)、メタクリル酸メチル42.5g
及びジエチレングリコールジメタクリレート4.7gを添加
し、更に重合触媒として過硫酸カリウム0.2gを添加し、
温度50℃で10時間の乳化重合反応を行った。反応後、得
られたエマルションポリマーを多量の10％硝酸銀水溶液
に入れて攪拌を行うことにより析出物を得、これをろ
過、水洗、凍結乾燥することにより、銀含有量4.5％の
抗菌剤54gを得た。Comparative Example 1 500 g of water was placed in a 1 L 4-necked flask equipped with a stirrer, and 31.4 g of a radical-polymerizable emulsifier having a sodium sulfonate group (Sanyo Chemical Co., Ltd.).
Made, brand name JS-2, 38% aqueous solution), methyl methacrylate 42.5 g
And 4.7 g of diethylene glycol dimethacrylate, and 0.2 g of potassium persulfate as a polymerization catalyst,
The emulsion polymerization reaction was carried out at a temperature of 50 ° C. for 10 hours. After the reaction, the resulting emulsion polymer was placed in a large amount of 10% silver nitrate aqueous solution and stirred to obtain a precipitate, which was filtered, washed with water, and freeze-dried to obtain 54 g of an antibacterial agent having a silver content of 4.5%. Obtained.
【００２５】＜抗菌性評価試験１＞実施例１〜４で得た
抗菌剤を使用し、各種試験菌による最小発育阻止濃度
(ＭＩＣ)を測定することにより抗菌剤の抗菌性能を評価
した。尚、試験菌としてエシェリキア・コリ(Escherich
ia coli IFO-3301)(大腸菌)、シュードモナス・エルジ
ノーサ(Pseudomonas aeruginosa IFO-13275)(緑膿菌)及
びスタフィロコッカス・アウレウス(Staphylococcus au
reus IFO-12732)(黄色ブドウ球菌)を用いた。<Antibacterial Evaluation Test 1> Using the antibacterial agents obtained in Examples 1 to 4, the minimum inhibitory concentration by various test bacteria was used.
The antibacterial performance of the antibacterial agent was evaluated by measuring (MIC). Escherichia coli (Escherichia coli)
ia coli IFO-3301) (Escherichia coli), Pseudomonas aeruginosa IFO-13275 (Pseudomonas aeruginosa) and Staphylococcus aureus (Staphylococcus au)
reus IFO-12732) (Staphylococcus aureus) was used.
【００２６】抗菌性評価試験の方法は、先ず滅菌水で抗
菌剤試料検体の4000μg/ml懸濁液を調製した後、更にこ
れに滅菌水を加え２倍希釈系列溶液を調製した。次に、
滅菌処理を行い50〜60℃に保持した感受性測定用培地(M
ueller Hinton medium(Difco))に、前記の各希釈系列溶
液を各10重量％添加し、充分に混合を行った後、これら
をシャーレに分注、固化させて感受性測定用平板とし
た。また、前記試験菌の接種用菌液の調製は、継代培養
した試験菌を増菌用培地(Mueller Hinton Broth (Difc
o))に接種し、これを35℃で20時間培養した後、菌数が1
06/mlとなるように増殖用培地で希釈し、これを接種用
菌液とした。次に、前記の感受性測定用平板に接種用菌
液をニクロム線ループ(内径約1mm)を用いて1〜2cm程度
に画線塗抹し、これを35℃で20時間培養し、発育が阻止
された最小濃度を以て試験菌に対する抗菌剤のＭＩＣ値
とした。各抗菌剤を用いてＭＩＣ値を測定した結果を表
１に示した。In the method of the antibacterial property evaluation test, a 4000 μg / ml suspension of an antibacterial agent sample specimen was first prepared with sterilized water, and then sterilized water was added thereto to prepare a 2-fold dilution series solution. next,
Susceptibility-measuring medium (M
To the ueller Hinton medium (Difco), 10% by weight of each of the above-mentioned diluted series solutions was added and thoroughly mixed, and then these were dispensed into a petri dish and solidified to obtain a plate for sensitivity measurement. In addition, the bacterial solution for inoculation of the test strain was prepared by subculturing the test strain (Mueller Hinton Broth (Difc
o)) was inoculated and incubated at 35 ° C for 20 hours.
It was diluted with a growth medium so as to be 0 6 / ml, and this was used as a bacterial solution for inoculation. Next, a nichrome wire loop (inner diameter of about 1 mm) was used to streak the bacterial solution for inoculation on the above-mentioned plate for measuring sensitivity to about 1 to 2 cm, and this was cultured at 35 ° C for 20 hours to prevent development. The MIC value of the antibacterial agent against the test bacteria was defined as the minimum concentration. The results of measuring the MIC value using each antibacterial agent are shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】＜抗菌性評価試験２＞実施例１〜４で得た
抗菌剤を使用し、抗菌剤の抗菌活性の持続性について評
価を行った。また比較のために、比較例１で得た抗菌剤
について同様に評価を行った。抗菌性評価試験の方法
は、先ず滅菌水で抗菌剤試料検体の1％懸濁液を調製
し、これを30℃の恒温振とう器で所定時間(１、２、４
週間)振とうした後ろ過を行い、乾燥させて検体試料を
調製した。次いでこの検体試料を使用し、抗菌性評価試
験１と同様の操作で試験菌エシェリキア・コリに対する
ＭＩＣ値を測定することにより、抗菌活性の持続性を評
価した。尚、比較例１の抗菌剤は、上記懸濁液のろ過が
困難なために、これを遠心分離器(回転数:10000rpm以
上)で分離した後、沈降物を乾燥させた試料を検体試料
とした。抗菌活性(ＭＩＣ値)の持続性評価結果を表２に
示した。<Antibacterial Evaluation Test 2> The antibacterial agents obtained in Examples 1 to 4 were used to evaluate the persistence of the antibacterial activity of the antibacterial agents. For comparison, the antibacterial agent obtained in Comparative Example 1 was similarly evaluated. The antibacterial property evaluation test method is as follows. First, prepare a 1% suspension of the antibacterial agent sample sample with sterilized water, and use a 30 ° C constant temperature shaker for a predetermined time (1, 2, 4).
After shaking, the mixture was filtered and dried to prepare a specimen sample. Then, using this sample sample, the MIC value for the test bacterium Escherichia coli was measured by the same operation as in the antibacterial property evaluation test 1 to evaluate the persistence of the antibacterial activity. In addition, since the antibacterial agent of Comparative Example 1 is difficult to filter the suspension, it is separated with a centrifuge (rotation speed: 10,000 rpm or more), and a sample obtained by drying the precipitate is used as a sample sample. did. The results of antibacterial activity (MIC value) sustainability evaluation are shown in Table 2.
【００２９】[0029]
【表２】 [Table 2]
【００３０】＜耐熱性評価試験＞実施例１及び比較例１
で得た抗菌剤を使用し、抗菌剤の耐熱性を評価した。評
価方法は、粉末状の抗菌剤の各々約0.5gをアルミ箔上に
薄く散布し、この上を更にアルミ箔で覆った。これらを
220℃に昇温させた電気炉中に入れ、5分間これを保持し
た。電気炉よりアルミ箔を取り出し、アルミ箔上に散布
した抗菌剤の状態を観察した結果、本発明の抗菌剤(実
施例１)は、色、形状共に殆ど変化が無かったが、比較
例１の抗菌剤は、黒褐色に着色して熱分解を起こしてい
た。<Heat Resistance Evaluation Test> Example 1 and Comparative Example 1
The heat resistance of the antibacterial agent was evaluated using the antibacterial agent obtained in. As an evaluation method, about 0.5 g of each of the powdery antibacterial agents was thinly sprayed on an aluminum foil, and this was further covered with the aluminum foil. these
It was placed in an electric furnace heated to 220 ° C. and held for 5 minutes. The aluminum foil was taken out of the electric furnace and the state of the antibacterial agent sprayed on the aluminum foil was observed. As a result, the antibacterial agent of the present invention (Example 1) showed almost no change in color and shape, but in Comparative Example 1 The antibacterial agent was colored blackish brown and caused thermal decomposition.
【００３１】[0031]
【発明の効果】本発明の抗菌剤は、アクリル系ポリマー
が抗菌性金属の担体であるため、各種ポリマー基材への
相溶性に優れ、しかも微細な粒子状であるために分散性
にも優れている。またこの抗菌剤は、抗菌性金属である
銀、銅、亜鉛がアクリル酸又はメタクリル酸の塩として
ポリマー担体内部に強固に且つ均一に分布しているた
め、抗菌性金属は徐々に担体より放出され、その結果抗
菌活性が長期間にわたり持続する性能を有する。The antibacterial agent of the present invention is excellent in compatibility with various polymer substrates because the acrylic polymer is a carrier of antibacterial metal, and is also excellent in dispersibility because it is in the form of fine particles. ing. In this antibacterial agent, the antibacterial metals silver, copper and zinc are firmly and uniformly distributed inside the polymer carrier as salts of acrylic acid or methacrylic acid, so that the antibacterial metal is gradually released from the carrier. As a result, the antibacterial activity has the ability to last for a long period of time.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｆ 220/12 ＭＭＢ 220/20 ＭＭＣ 8619−4Ｊ (72)発明者 吉見 幸彦 茨城県つくば市吾妻４−16−４番地 (72)発明者 井筒 史子 茨城県つくば市梅園２丁目２−20番地─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08F 220/12 MMB 220/20 MMC 8619-4J (72) Inventor Yukihiko Yoshimi 4 Azuma, Tsukuba, Ibaraki Prefecture -16-4 Address (72) Inventor Fumiko Izutsu 2-2-20 Umezono, Tsukuba City, Ibaraki Prefecture
Claims (2)
タクリル酸エステル、及び／又は、ジ又はトリアクリ
ル酸エステル又はジ又はトリメタクリル酸エステルと、
銀、銅、亜鉛から選ばれたアクリル酸塩又はメタクリ
ル酸塩とを、有機溶媒の存在下で共重合反応させること
を特徴とする抗菌剤の製造方法。1. A raw material for polymerization acrylic acid ester or methacrylic acid ester, and / or di- or triacrylic acid ester or di- or trimethacrylic acid ester,
A method for producing an antibacterial agent, which comprises subjecting an acrylic acid salt or a methacrylic acid salt selected from silver, copper and zinc to a copolymerization reaction in the presence of an organic solvent.
タクリル酸エステル、及び／又は、ジ又はトリアクリ
ル酸エステル又はジ又はトリメタクリル酸エステルと、
銀、銅、亜鉛から選ばれたアクリル酸塩又はメタクリ
ル酸塩とを、有機溶媒の存在下で共重合反応させてなる
抗菌剤。2. A polymerization raw material acrylic acid ester or methacrylic acid ester, and / or di- or triacrylic acid ester or di- or trimethacrylic acid ester,
An antibacterial agent obtained by copolymerizing an acrylate or a methacrylate selected from silver, copper and zinc in the presence of an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33353394A JPH08165211A (en) | 1994-12-14 | 1994-12-14 | Production of antimicrobial agent and antimicrobial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33353394A JPH08165211A (en) | 1994-12-14 | 1994-12-14 | Production of antimicrobial agent and antimicrobial agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08165211A true JPH08165211A (en) | 1996-06-25 |
Family
ID=18267115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33353394A Pending JPH08165211A (en) | 1994-12-14 | 1994-12-14 | Production of antimicrobial agent and antimicrobial agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08165211A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245421A (en) * | 1997-03-05 | 1998-09-14 | Nippon Shokubai Co Ltd | (meth)acrylic crosslinked elastomer and its production |
| KR20170012023A (en) * | 2015-07-23 | 2017-02-02 | 제록스 코포레이션 | Anti-bacterial aqueous ink compositions comprising metal ion composite ionomer resins |
| JP2017214325A (en) * | 2016-05-31 | 2017-12-07 | 株式会社日本触媒 | Antibacterial agent |
| WO2019074121A1 (en) * | 2017-10-12 | 2019-04-18 | イビデン株式会社 | Antiviral substrate, antiviral composition, method for manufacturing antiviral substrate, antimicrobial substrate, antimicrobial composition and method for manufacturing antimicrobial substrate |
| JP2020083934A (en) * | 2018-11-16 | 2020-06-04 | イビデン株式会社 | Antifungal/antibacterial substrate, antifungal/antibacterial composition and production method of antifungal/antibacterial substrate |
| JP2021038237A (en) * | 2020-11-10 | 2021-03-11 | イビデン株式会社 | Antifungal/antibacterial substrate, antifungal/antibacterial composition and production method of antifungal/antibacterial substrate |
| WO2022181492A1 (en) * | 2021-02-26 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Polymerizable composition and antibacterial material |
-
1994
- 1994-12-14 JP JP33353394A patent/JPH08165211A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10245421A (en) * | 1997-03-05 | 1998-09-14 | Nippon Shokubai Co Ltd | (meth)acrylic crosslinked elastomer and its production |
| KR20170012023A (en) * | 2015-07-23 | 2017-02-02 | 제록스 코포레이션 | Anti-bacterial aqueous ink compositions comprising metal ion composite ionomer resins |
| JP2017025303A (en) * | 2015-07-23 | 2017-02-02 | ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ | Anti-bacterial aqueous ink compositions comprising metal ion composite ionomer resins |
| JP2017214325A (en) * | 2016-05-31 | 2017-12-07 | 株式会社日本触媒 | Antibacterial agent |
| JP2020040942A (en) * | 2017-10-12 | 2020-03-19 | イビデン株式会社 | Antiviral substrate, antiviral composition, method for manufacturing antiviral substrate, antimicrobial substrate, antimicrobial composition and method for manufacturing antimicrobial substrate |
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| WO2019074121A1 (en) * | 2017-10-12 | 2019-04-18 | イビデン株式会社 | Antiviral substrate, antiviral composition, method for manufacturing antiviral substrate, antimicrobial substrate, antimicrobial composition and method for manufacturing antimicrobial substrate |
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| CN113383794A (en) * | 2017-10-12 | 2021-09-14 | 揖斐电株式会社 | Antiviral substrate, antimicrobial substrate, methods for producing them, antiviral composition, and antimicrobial composition |
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| US11517020B2 (en) | 2017-10-12 | 2022-12-06 | Ibiden Co., Ltd. | Antiviral substrate, antiviral composition, method for manufacturing antiviral substrate, antimicrobial substrate, antimicrobial composition and method for manufacturing antimicrobial substrate |
| CN113383794B (en) * | 2017-10-12 | 2024-01-30 | 揖斐电株式会社 | Antiviral substrate, antimicrobial substrate, method for producing the same, antiviral composition, and antimicrobial composition |
| JP2020083934A (en) * | 2018-11-16 | 2020-06-04 | イビデン株式会社 | Antifungal/antibacterial substrate, antifungal/antibacterial composition and production method of antifungal/antibacterial substrate |
| JP2021038237A (en) * | 2020-11-10 | 2021-03-11 | イビデン株式会社 | Antifungal/antibacterial substrate, antifungal/antibacterial composition and production method of antifungal/antibacterial substrate |
| WO2022181492A1 (en) * | 2021-02-26 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Polymerizable composition and antibacterial material |
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