【０００１】[0001]
【発明の属する技術分野】本発明は抗菌・抗カビ剤に関
する。[0001] The present invention relates to an antibacterial and antifungal agent.
【０００２】[0002]
【従来の技術】抗菌・抗カビ剤として有機系のものと無
機系のものとが知られており、これまで即効性に優れた
有機系の抗菌・抗カビ剤が広く利用されていた。しかし
ながら、有機系の抗菌・抗カビ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、無機系の抗
菌・抗カビ剤は有機系の抗菌・抗カビ剤に比べ即効性の
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、近年、無機系の抗菌・抗
カビ剤の使用量は大巾に増加してきている。2. Description of the Related Art Organic and inorganic antibacterial agents are known as antibacterial and antifungal agents. Until now, organic antibacterial and antifungal agents having excellent immediate action have been widely used. However, organic antibacterial and antifungal agents are generally toxic and have serious problems in terms of safety. On the other hand, inorganic antibacterial and antifungal agents are slightly inferior to organic antibacterial and antifungal agents in terms of immediate effect, but are highly safe, and have excellent antibacterial action persistence and heat resistance. The use of inorganic antibacterial and antifungal agents has been greatly increasing.
【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・抗カ
ビ剤として、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類を死滅させる、
金属イオンが細菌類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
可能とし細菌類を死滅させる、金属イオンがマイナス
のイオン性を有する細菌類を引き寄せ、細菌類の細胞膜
を破壊し死滅させる、等の考えが示されている。It has been known that metals such as gold, silver, copper, and zinc have an antibacterial effect, and these metals (called antibacterial metals) are used as inorganic antibacterial and antifungal agents. Are used mainly. The mechanism by which these antimicrobial metals exert their antimicrobial action is not completely understood, but active oxygen generated by the catalytic action of metal ions kills bacteria,
Bacteria with negative ionicity, in which metal ions inhibit enzymes in the metabolic system of bacteria or attach to cell membranes and inhibit mass transfer, making cell division impossible and killing bacteria. And destroying and killing bacterial cell membranes.
【０００４】抗菌性金属の抗菌・抗カビ剤への応用例と
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
体状の無機担体に担持させた抗菌・抗カビ剤としては例
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
６０−１８１００２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。As an application example of an antibacterial metal to an antibacterial and antifungal agent, it is known to use a silver nitrate solution as a disinfectant, an eye drop or the like. However, a liquid silver nitrate solution has a problem that the range of use is limited, and if the concentration is high, it is highly toxic and difficult to handle. On the other hand, as an antibacterial and antifungal agent in which an antibacterial metal is supported on a solid inorganic carrier, for example, a porous substance such as silica gel or activated carbon is used as a carrier,
A carrier in which silver or the like is supported thereon, a carrier in which silver or the like is supported using zeolite as a carrier (Japanese Patent No. 128654, JP-A-60-181002, etc.), or an inorganic oxoacid salt such as magnesium aluminate metasilicate is used as a carrier. An antibacterial metal ion such as silver ion-exchanged with a metal ion of a carrier and supported (JP-A-3-275627) is 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・抗カビ剤
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・抗カビ剤を水に
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。一方、ゼオライトや無
機オキソ酸塩を担体とする抗菌・抗カビ剤は、多孔質物
質を担体とする抗菌・抗カビ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。However, the conventional antibacterial and antifungal agents supported on the solid inorganic carrier also have various problems. For example, when a porous substance is used as a carrier, the metal retention power is weak, and when added to water, the rate of elution of the supported metal into water is high, and the antibacterial effect is reduced in a short period of time. There was a problem. In addition, the U.S. Public Health Service regulates the concentration of silver ions in water to be 50 ppb or less from the viewpoint of safety. However, when an antibacterial / antifungal agent using the above porous substance as a carrier is added to water, it is used. There was a risk that silver ions in an amount exceeding this safety standard value would elute. On the other hand, antibacterial and antifungal agents using zeolites and inorganic oxoacid salts as carriers have a lower metal elution rate into water than antibacterial and antifungal agents using porous materials as carriers, but have a sustained antibacterial effect. It was not always enough.
【０００６】更に、ゼオライトを担体とする抗菌・抗カ
ビ剤の場合、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（耐候性が低い）、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・抗カビ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。また無機オキソ酸塩を担体とする抗菌
・抗カビ剤の場合、ゼオライトを担体とする抗菌・抗カ
ビ剤よりは耐候性が高いが、必ずしも十分な耐候性を有
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・
抗カビ剤を練り込む方法が採用されることがあるが、抗
菌・抗カビ剤の耐熱性が低いと樹脂に練り込む時の熱に
よって抗菌・抗カビ剤が変色し、製品価値を低下させる
虞れがあり、無機物担体に抗菌性金属を担持させた従来
の抗菌・抗カビ剤も、耐熱性は充分とは言い難かった。Further, in the case of an antibacterial / antifungal agent using zeolite as a carrier, there is a problem that the metal is oxidized and discolors to brown with time, and in particular, the discoloration becomes remarkable by light irradiation (weather resistance is low). , Used for antibacterial treatment of resin products,
When used to add antibacterial properties to paints, etc.,
There has been a problem that resin products are discolored due to discoloration of antibacterial and antifungal agents. In the case of an antibacterial / antifungal agent using an inorganic oxo acid salt as a carrier, weather resistance is higher than that of an antibacterial / antifungal agent using a zeolite as a carrier, but it is hard to say that it has sufficient weather resistance. When a resin product is subjected to antibacterial treatment, the resin material is heated to a temperature equal to or higher than the softening temperature to prevent
A method of kneading an antifungal agent may be adopted, but if the antibacterial / antifungal agent has low heat resistance, heat during kneading into the resin may cause the antibacterial / antifungal agent to discolor and reduce the product value. Therefore, conventional antibacterial and antifungal agents having an antibacterial metal supported on an inorganic carrier have not been said to have sufficient heat resistance.
【０００７】無機物担体に抗菌性金属を担持させた抗菌
・抗カビ剤の耐熱性を向上するものとして、銀塩等をシ
リカゲルに担持吸着させて焼成した後、反応性有機珪素
化合物の加水分解物でコーティングしたものも提案され
ている（特開平６−８７７１１号公報）。しかしなが
ら、銀塩等をシリカゲルに担持吸着させた後に焼成する
と、担持されている銀が溶融して中性金属状態（電荷を
持たない所謂メタル状態）となって無機担体に強固に固
着し、この結果、銀が溶出し難くなって抗菌性が低下す
る虞れがあった。一方、シリカゲルは焼成しないと、担
持されている銀等の抗菌性金属の保持性が弱く、抗菌効
果の持続性が不充分となるため焼成せざるを得ず、上記
のような問題が生じることを避けることはできなかっ
た。In order to improve the heat resistance of an antibacterial and antifungal agent having an antibacterial metal supported on an inorganic carrier, a silver salt or the like is adsorbed on silica gel and calcined, followed by hydrolysis of a reactive organic silicon compound. (Japanese Patent Application Laid-Open No. 6-87711). However, when the silver salt or the like is calcined after being carried and adsorbed on silica gel, the carried silver is melted to be in a neutral metal state (a so-called metal state having no charge) and firmly fixed to the inorganic carrier. As a result, there is a possibility that silver is difficult to elute and the antibacterial property is reduced. On the other hand, if the silica gel is not fired, the retention of the antibacterial metal such as silver carried thereon is weak, and the persistence of the antibacterial effect becomes insufficient, so that the firing has to be performed, and the above-described problem occurs. Could not be avoided.
【０００８】本発明は上記の点に鑑みなされたもので、
耐候性、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・抗カビ剤を提供することを目的とす
る。[0008] The present invention has been made in view of the above points,
An object of the present invention is to provide an antibacterial and antifungal agent which is excellent in weather resistance, heat resistance and safety, and has excellent durability of antibacterial effect.
【０００９】[0009]
【課題を解決するための手段】即ち本発明の抗菌・抗カ
ビ剤は、アルミニウムを含む無機担体に抗菌性金属が担
持され、且つ該無機担体にシランカップリング剤が結合
していることを特徴とする。また本発明の抗菌・抗カビ
剤のいま一つは、アルミニウムを含む無機担体に抗菌性
金属が担持されているとともに、該無機担体にシランカ
ップリング剤が結合し、且つ該シランカップリング剤に
有機物が結合していることを特徴とする。The antibacterial and antifungal agent of the present invention is characterized in that an antibacterial metal is supported on an inorganic carrier containing aluminum, and a silane coupling agent is bonded to the inorganic carrier. And Another one of the antibacterial and antifungal agents of the present invention is that an antibacterial metal is supported on an inorganic carrier containing aluminum, a silane coupling agent is bonded to the inorganic carrier, and the silane coupling agent is It is characterized in that an organic substance is bonded.
【００１０】[0010]
【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、これらは２種以上を
混合して用いることもできる。これら抗菌性金属のうち
銀、銅、水銀が好ましく、特に銀、銅が好ましい。これ
ら抗菌性金属が担持されるアルミニウムを含む無機担体
としては、結晶構造固有の細孔を持つ多孔体（例えばゼ
オライト、アルミノリン酸塩等）、層状化合物多孔体
（例えばカオリナイト族、スメクタイト族等の層状粘度
鉱物）等が挙げられる。これらのうち、ゼオライト、層
状粘度鉱物が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, antibacterial metals include gold, silver, copper, zinc, mercury, bismuth, cadmium,
Cobalt, nickel and the like can be mentioned, and these can be used as a mixture of two or more. Among these antibacterial metals, silver, copper and mercury are preferable, and silver and copper are particularly preferable. Examples of the inorganic carrier containing aluminum on which these antibacterial metals are supported include porous bodies having pores specific to the crystal structure (eg, zeolite, aluminophosphate, etc.) and layered compound porous bodies (eg, kaolinite group, smectite group, etc.). Layered viscous mineral). Among them, zeolite and layered clay mineral are preferred.
【００１１】本発明の抗菌・抗カビ剤は、上記無機担体
に抗菌性金属が担持されているとともに、シランカップ
リング剤が結合していることが特徴である。無機担体と
結合するシランカップリグン剤は（１）式で示される。The antibacterial and antifungal agent of the present invention is characterized in that an antibacterial metal is supported on the inorganic carrier and a silane coupling agent is bound thereto. The silane coupling agent bonded to the inorganic carrier is represented by the formula (1).
【００１２】[0012]
【化１】ＲＳｉＸ3 ・・・・（１）Embedded image RSix3 ... (1)
【００１３】上記（１）式において、Ｒは例えばビニル
基、アミノ基、ハロゲノ基、水酸基、チオール基、ウレ
イド基、エポキシ基、メタクリロイル基、エポキシシク
ロヘキシル基、アルキル基、ポリエーテル基を含む有機
官能性基であり、Ｘは例えばハロゲン、アルコキシ基、
ケト基等の加水分解性基を示す。In the above formula (1), R is an organic functional group containing, for example, a vinyl group, an amino group, a halogeno group, a hydroxyl group, a thiol group, a ureido group, an epoxy group, a methacryloyl group, an epoxycyclohexyl group, an alkyl group and a polyether group. X is, for example, a halogen, an alkoxy group,
Shows a hydrolyzable group such as a keto group.
【００１４】本発明の抗菌・抗カビ剤は、後述するよう
に更に上記シランカップリング剤に有機物が結合してい
るものであっても良い。この場合、無機担体に結合する
シランカップリング剤としては、上記（１）式における
Ｒが有機物との反応性を有する基であることが必要であ
る。The antibacterial / antifungal agent of the present invention may be one in which an organic substance is further bound to the silane coupling agent as described later. In this case, as the silane coupling agent bonded to the inorganic carrier, R in the above formula (1) needs to be a group having reactivity with an organic substance.
【００１５】上記シランカップリング剤の具体例として
は、例えばγ−（２−アミノエチル）アミノプロピルト
リメトキシシラン、γ−（２−アミノエチル）アミノプ
ロピルメチルジメトキシシラン、γ−メタクリロキシプ
ロピルトリメトキシシラン、Ｎ−β−（Ｎ−ビニルベン
ジルアミノエチル）−γ−アミノプロピルトリメトキシ
シラン塩酸塩、γ−グリシドキシプロピルトリメトキシ
シラン、γ−メルカプトプロピルトリメトキシシラン、
メチルトリメトキシシラン、メチルトリエトキシシラ
ン、ビニルトリアセトキシシラン、γ−クロロプロピル
トリメトキシシラン、ヘキサメチルジシラザン、γ−ア
ミノプロピルトリメトキシシラン、ビニルトリメトキシ
シラン、ジメチルジメトキシシラン、オクタデシルジメ
チル（３−（トリメトキシシリル）プロピル）アンモニ
ウムクロライド、γ−メルカプトプロピルメチルジメト
キシシラン、ヒドロキシプロピルトリメトキシシラン、
γ−ウレイドプロピルトリエトキシシラン、γ−ジブチ
ルアミノプロピルトリメトキシシラン、フェニルトリメ
トキシシラン、ジメチルジエトキシシラン、トリメチル
メトキシシラン、ｎ−デシルトリメトキシシラン、イソ
ブチルトリメトキシシラン、トリメチルエトキシシラ
ン、γ−ジアリルアミノプロピルトリメトキシシラン、
ｎ−ヘキサデシルトリメトキシシラン、ｎ−オクタデシ
ルトリメトキシシラン、γ−メタクリロキシプロピルメ
チルジメトキシシラン等が挙げられる。これらシランカ
ップリング剤は２種以上を混合して用いることができ
る。Specific examples of the silane coupling agent include, for example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane Silane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, octadecyldimethyl (3- (Trimethoxysilyl) propyl) ammonium chloride, γ-mercaptopropylmethyldimethoxysilane, hydroxypropyltrimethoxysilane,
γ-ureidopropyltriethoxysilane, γ-dibutylaminopropyltrimethoxysilane, phenyltrimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, n-decyltrimethoxysilane, isobutyltrimethoxysilane, trimethylethoxysilane, γ-diallyl Aminopropyltrimethoxysilane,
Examples include n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane. These silane coupling agents can be used as a mixture of two or more kinds.
【００１６】本発明の抗菌・抗カビ剤を樹脂に練り込ん
で用いる場合、樹脂中での分散性を高めるため、無機担
体に結合しているシランカップリング剤が更に有機物と
結合していることが好ましい。また無機担体に結合した
シランカップリング剤に更に有機物が結合していると、
樹脂に対する分散性が向上するとともに、更に抗菌・抗
カビ剤の安定性、例えば紫外線や酸化に対する安定性も
向上する。When the antibacterial and antifungal agent of the present invention is used by kneading it into a resin, the silane coupling agent bound to the inorganic carrier must be further bound to an organic substance in order to enhance dispersibility in the resin. Is preferred. Also, when an organic substance is further bonded to the silane coupling agent bonded to the inorganic carrier,
The dispersibility in the resin is improved, and the stability of the antibacterial and antifungal agent, for example, the stability against ultraviolet rays and oxidation is also improved.
【００１７】シランカップリング剤と結合可能な有機物
は、前記（１）式におけるＲの種類によって異なる。例
えばＲがアミノ基を含む官能性基の場合、結合可能な有
機物としては、モノハロゲン化カルボン酸類、カルボン
酸類が挙げられ、Ｒがエポキシ基を含む官能性基の場合
には結合可能な有機物として、例えばカルボン酸類、ア
ルコール類、アミン類等が挙げられ、Ｒが水酸基やチオ
ール基を含む官能性基の場合には結合可能な有機物とし
て、例えばカルボン酸類、アルコール類が挙げられる。The organic substance that can be bonded to the silane coupling agent differs depending on the type of R in the above formula (1). For example, when R is a functional group containing an amino group, examples of the organic substance that can be bound include monohalogenated carboxylic acids and carboxylic acids, and when R is a functional group containing an epoxy group, the organic substance that can be bound is Examples thereof include carboxylic acids, alcohols, and amines. When R is a functional group containing a hydroxyl group or a thiol group, examples of the bondable organic substance include carboxylic acids and alcohols.
【００１８】シランカップリング剤にどのような有機物
が結合したものを選択するかは、抗菌・抗カビ剤を添加
しようとする樹脂の種類に応じ、分散性等を考慮して決
定すれば良い。What kind of organic substance is bonded to the silane coupling agent may be selected in consideration of the dispersibility and the like according to the type of the resin to which the antibacterial / antifungal agent is to be added.
【００１９】本発明抗菌・抗カビ剤は、抗菌性金属イ
オンを含む溶液と無機担体とを接触させて無機担体に抗
菌性金属を担持させ、次いでシランカップリング剤と接
触させて無機担体にシランカップリング剤を結合させる
方法、シランカップリング剤と無機担体とを反応させ
て無機担体にシランカップリング剤を結合させた後、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無
機担体に担持させる方法、抗菌性金属イオンとシラン
カップリング剤を含む溶液と無機担体とを接触させて抗
菌性金属を無機担体に担持させるとともに、無機担体に
シランカップリング剤を結合させる方法、等によって得
ることができ、これら〜の製造方法から、無機担体
の種類、抗菌性金属の種類、シランカップリング剤の種
類等に応じて、好ましい方法を適宜選択する。またシラ
ンカップリング剤に更に有機物が結合した構造の抗菌・
抗カビ剤も、無機担体の種類、抗菌性金属の種類、シラ
ンカップリング剤の種類及び有機物の種類等に応じて上
記〜に示す製造工程中の任意の位置でシランカップ
リング剤と有機物を反応させるか、有機物と反応させた
シランカップリング剤を、無機担体に結合させた後、無
機担体に抗菌性金属を担持させたり、有機物と反応させ
たシランカップリング剤を、予め抗菌性金属を担持させ
た無機担体に結合させたり、或いは有機物と反応させた
シランカップリング剤と抗菌性金属イオンとを含む溶液
に無機担体を接触させて、無機担体に有機物を結合した
シランカップリング剤を結合させるとともに抗菌性金属
を担持させる等の方法で製造することができる。The antibacterial / antifungal agent of the present invention is obtained by bringing a solution containing an antibacterial metal ion into contact with an inorganic carrier to support the antibacterial metal on the inorganic carrier, and then contacting the silane coupling agent with a silane coupling agent. The method of binding the coupling agent, after the silane coupling agent is reacted with the inorganic carrier to bind the silane coupling agent to the inorganic carrier, and then contacted with a solution containing an antibacterial metal ion to convert the antibacterial metal into the inorganic carrier A method of supporting the antibacterial metal on the inorganic carrier by bringing the solution containing the antibacterial metal ion and the silane coupling agent into contact with the inorganic carrier, and bonding the silane coupling agent to the inorganic carrier, etc. Depending on the type of the inorganic carrier, the type of the antibacterial metal, the type of the silane coupling agent, etc., a preferable method can be obtained from Suitably selected. In addition, antibacterial and
The antifungal agent also reacts with the silane coupling agent and the organic substance at any position in the above-described manufacturing process depending on the type of the inorganic carrier, the type of the antibacterial metal, the type of the silane coupling agent and the type of the organic substance After the silane coupling agent reacted with the organic substance is bonded to the inorganic carrier, the antibacterial metal is supported on the inorganic carrier, or the silane coupling agent reacted with the organic substance is pre-loaded with the antibacterial metal. The inorganic carrier is contacted with a solution containing a silane coupling agent reacted with an organic substance and an antibacterial metal ion, or an inorganic substance is contacted with the inorganic carrier, and the organic substance is bound to the inorganic carrier. In addition, it can be manufactured by a method such as supporting an antibacterial metal.
【００２０】上記抗菌性金属イオンを含む溶液は、例え
ば抗菌性金属の水溶性塩を水に溶解させることにより調
製することができる。また、抗菌性金属イオンを含む溶
液のｐＨを調節するために、抗菌性金属の水溶性塩をリ
ン酸緩衝液等に溶解して用いることもできる。本発明の
抗菌・抗カビ剤を製造するに当たり、抗菌性金属イオン
を含む溶液は、無機担体１００重量部当たりに対し、抗
菌性金属０．１〜２０重量部を含むように調整すること
が好ましい。シランカップリング剤は無機担体１００重
量部当たりに対し、０．０１〜１０重量部を反応させる
ことが好ましい。また有機物はシランカップリング剤１
００重量部当たりに対し、０．００１〜１．０重量部を
反応させることが好ましい。The solution containing the antibacterial metal ion can be prepared, for example, by dissolving a water-soluble salt of the antibacterial metal in water. Further, in order to adjust the pH of the solution containing the antibacterial metal ion, a water-soluble salt of the antibacterial metal can be used by dissolving it in a phosphate buffer or the like. In producing the antibacterial and antifungal agent of the present invention, the solution containing the antibacterial metal ion is preferably adjusted to contain 0.1 to 20 parts by weight of the antibacterial metal per 100 parts by weight of the inorganic carrier. . It is preferable to react 0.01 to 10 parts by weight of the silane coupling agent with respect to 100 parts by weight of the inorganic carrier. Organic substances are silane coupling agent 1
It is preferable to react 0.001 to 1.0 part by weight per 00 parts by weight.
【００２１】抗菌性金属の水溶性塩としては、金、銀、
亜鉛、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、次亜塩素酸
塩、塩素酸塩、過塩素酸塩、リン酸塩、水酸化物等が挙
げられる。無機担体に担持された抗菌性金属は、上記無
機担体に抗菌性金属を担持させるために用いた抗菌性金
属イオンを含む処理液中の共存イオンの違いや、担持さ
せた後の保持状態の違い（例えば保持雰囲気温度、湿度
等の違い）によって、無機担体中においてイオン状、中
性金属状態、酸化物、水酸化物、錯化合物等の種々の状
態で存在していると考えられる。本発明の抗菌・抗カビ
剤は、無機担体に担持された金属が中性金属状態になっ
ていたとしても、無機担体に抗菌性金属を担持させた後
に焼成するものと異なり、金属が無機担体に強固に固着
することがないため抗菌効果が低下する虞れがない。The water-soluble salts of antibacterial metals include gold, silver,
Sulfates, nitrates, chlorides, hypochlorites, chlorates, perchlorates, phosphates, hydroxides, and the like of metals such as zinc, copper, mercury, bismuth, cadmium, cobalt, and nickel Can be The antibacterial metal supported on the inorganic carrier is different in coexisting ions in the processing solution containing the antibacterial metal ion used for supporting the antibacterial metal on the inorganic carrier, and the difference in the retention state after the support is performed. It is considered that the inorganic carrier exists in various states such as an ionic state, a neutral metal state, an oxide, a hydroxide, and a complex compound depending on (for example, a difference in holding atmosphere temperature and humidity). The antibacterial and antifungal agents of the present invention are different from those that are fired after the antibacterial metal is supported on the inorganic carrier, even if the metal supported on the inorganic carrier is in a neutral metal state. There is no possibility that the antibacterial effect is reduced because the antibacterial effect is not firmly fixed.
【００２２】本発明の抗菌・抗カビ剤は水と接触する
と、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類が死
滅し、また水中には微量の抗菌性金属イオンが残存する
こととなるため、その後の細菌類の繁殖も妨げられる。
また本発明の抗菌・抗カビ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・
抗カビ剤と接触した細菌類は死滅する。また本発明の抗
菌・抗カビ剤を無水状態で使用した場合でも、細菌類の
細胞中には水分が含まれるため、細菌類が本発明抗菌・
抗カビ剤と接触すると、細菌類の細胞中に抗菌性金属イ
オンが溶出して細菌類を死滅させることができる。When the antibacterial and antifungal agent of the present invention comes in contact with water, a very small amount of antibacterial metal ions are eluted in the water, and the eluted antibacterial metal ions kill bacteria in the water, Since a small amount of antibacterial metal ions remain, the subsequent propagation of bacteria is also prevented.
Further, when the antibacterial and antifungal agent of the present invention contains water, the antibacterial metal ions are eluted in the water content,
Bacteria that come into contact with the antifungal agent die. Further, even when the antibacterial and antifungal agent of the present invention is used in an anhydrous state, the cells of the bacteria contain water, so that the bacteria can be treated with the antibacterial and antifungal of the present invention.
Upon contact with an antifungal agent, antibacterial metal ions are eluted into bacterial cells and can kill the bacteria.
【００２３】本発明の抗菌・抗カビ剤は、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
用することができ、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 and antifungal agents of the present invention include, for example, sterilization and disinfection of drinking water, suppression of the growth of algae in water, prevention of mold and the like on resin products, prevention of barnacles from adhering to ship bottoms, and contamination of dogs and cats with manure. For the purpose of prevention, etc., water and resin products can be used by antibacterial treatment, added to paint such as ship bottom paint, or added to sand that may be contaminated by dog and cat manure. It is possible to suppress the death, generation, and proliferation of bacteria, bacteria, molds, and microorganisms, but it is not limited to these applications.
【００２４】本発明抗菌・抗カビ剤により水の抗菌処理
を行う方法としては、本発明抗菌・抗カビ剤を充填した
カラムに水を通液したり、水中に本発明抗菌・抗カビ剤
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
・抗カビ剤を練り込む方法を採用することができる。抗
菌・抗カビ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・抗カビ剤の樹脂中へ
の添加量は、練り込み効率、抗菌性能、樹脂強度等を考
慮して決定される。As a method for carrying out the antibacterial treatment of water with the antibacterial / antifungal agent of the present invention, water can be passed through a column filled with the antibacterial / antifungal agent of the present invention, or the antibacterial / antifungal agent of the present invention can be used in water. An immersion method and the like can be mentioned. When used for antibacterial treatment of a resin product, for example, a method of kneading the antibacterial and antifungal agent of the present invention into a raw material resin can be adopted. As the resin for kneading the antibacterial and antifungal agents, any resin having plasticity may be used. For example, polyethylene, polypropylene, polystyrene, ABS resin, polyvinyl chloride,
MMA resin and the like can be mentioned. The amount of the antibacterial / antifungal agent added to the resin is determined in consideration of the kneading efficiency, antibacterial performance, resin strength and the like.
【００２５】抗菌・抗カビ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
維状等の場合、抗菌・抗カビ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方法が採用される。また抗菌・抗
カビ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 into which the antibacterial / antifungal agent has been kneaded can be formed into an arbitrary form such as a sphere, a pellet, a plate, a sheet, and a fiber. For example, in the case of plate, sheet, fiber, etc., the antibacterial / antifungal agent and the resin are premixed,
A method in which the resin is kneaded in a kneading machine such as an extruder at a temperature equal to or higher than the softening temperature of the resin and then extruded from a die or the like into a sheet, plate, fiber or the like is employed. The spherical or pellet resin into which the antibacterial / antifungal agent is kneaded can be made into an antibacterial resin product having a predetermined shape by injection molding.
【００２６】また本発明抗菌・抗カビ剤を樹脂製品表面
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。The antimicrobial resin product can also be obtained by applying the antibacterial / antifungal agent of the present invention to the surface of the resin product and then heat pressing the applied surface.
【００２７】本発明抗菌・抗カビ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・抗カビ剤を分散させて配合すれば良い。When the antibacterial / antifungal agent of the present invention is added to paints such as ship bottom paints, the paints may be oily or water-based, and are blended in the same manner as pigments. What is necessary is just to mix | blend and mix an antifungal agent.
【００２８】[0028]
【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・抗カビ剤は以下のようにして製造した。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. The antibacterial and antifungal agents used in the following Examples and Comparative Examples were produced as follows.
【００２９】抗菌・抗カビ剤Ａ（本発明品） リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中に、ゼオライト１００グラムを添加して室温で１時
間攪拌した後、硝酸銀３．２ｇ（ゼオライトに対する銀
の割合は２％）を添加して室温で１時間攪拌し、更に硝
酸亜鉛６水和物４５．５ｇ（ゼオライトに対する亜鉛の
割合は１０％）を添加して更に室温で１時間攪拌して濾
過した。この濾過物をリン酸ナトリウム１２水和物の
０．７％水溶液１リットル中で室温下に１時間攪拌して
洗浄した後、イオン交換水１リットル中に添加し、更に
オクタデシルトリメトキシシラン１ｇを添加して８０℃
で１時間攪拌した後、濾過した。濾過物をリン酸ナトリ
ウム１２水和物の０．７％水溶液１リットル中で室温下
に１時間攪拌して洗浄し、濾過して得た濾過物を１２０
℃で３日間減圧乾燥したものを抗菌・抗カビ剤Ａとし
た。Antibacterial and antifungal agent A (product of the present invention) 100 g of zeolite was added to 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, and the mixture was stirred at room temperature for 1 hour. 2 g (the ratio of silver to zeolite is 2%) was added thereto, and the mixture was stirred at room temperature for 1 hour. Further, 45.5 g of zinc nitrate hexahydrate (the ratio of zinc to zeolite was 10%) was added, and further added at room temperature. Stirred for hours and filtered. The filtrate was washed by stirring at room temperature for 1 hour in 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, added to 1 liter of ion-exchanged water, and further added with 1 g of octadecyltrimethoxysilane. 80 ℃
After stirring for 1 hour, the mixture was filtered. The filtrate was washed by stirring at room temperature for 1 hour in 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, and the filtrate was filtered.
What was dried under reduced pressure at 3 ° C. for 3 days was used as an antibacterial / antifungal agent A.
【００３０】抗菌・抗カビ剤Ｂ（本発明品） リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中に、カオリン１００グラムを添加して室温で１時間
攪拌した後、硝酸銀３．２ｇ（カオリンに対する銀の割
合は２％）を添加して室温で１時間攪拌し、更に硝酸亜
鉛６水和物４５．５ｇ（カオリンに対する亜鉛の割合は
１０％）を添加して更に室温で１時間攪拌して濾過し
た。この濾過物をリン酸ナトリウム１２水和物の０．７
％水溶液１リットル中で室温下に１時間攪拌して洗浄し
た後、イオン交換水１リットル中に添加し、更にオクタ
デシルトリメトキシシラン１ｇを添加して８０℃で１時
間攪拌した後、濾過した。濾過物をリン酸ナトリウム１
２水和物の０．７％水溶液１リットル中で室温下に１時
間攪拌して洗浄し、濾過して得た濾過物を１２０℃で３
日間減圧乾燥したものを抗菌・抗カビ剤Ｂとした。Antibacterial / antifungal agent B (product of the present invention) 100 g of kaolin was added to 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate and stirred at room temperature for 1 hour. 2 g (the ratio of silver to kaolin is 2%) was added, and the mixture was stirred at room temperature for 1 hour. Further, 45.5 g of zinc nitrate hexahydrate (the ratio of zinc to kaolin was 10%) was added, and further added at room temperature. Stirred for hours and filtered. The filtrate was washed with 0.7% sodium phosphate dodecahydrate.
After washing for 1 hour at room temperature in 1 liter of a 1% aqueous solution, the solution was added to 1 liter of ion-exchanged water, 1 g of octadecyltrimethoxysilane was further added, the mixture was stirred at 80 ° C. for 1 hour, and then filtered. Filter the filtrate with sodium phosphate 1
The mixture was washed by stirring in 1 liter of a 0.7% aqueous solution of dihydrate at room temperature for 1 hour and filtered.
The product dried under reduced pressure for one day was designated as an antibacterial / antifungal agent B.
【００３１】抗菌・抗カビ剤Ｃ（本発明品） リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中に、ゼオライト１００グラムを添加して室温で１時
間攪拌した後、硝酸銅０．７６ｇを添加して室温で１時
間攪拌し、更に硝酸亜鉛６水和物１１３．７５ｇを添加
して更に室温で１時間攪拌して濾過した。この濾過物を
リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中で室温下に１時間攪拌して洗浄した後、イオン交換
水１リットル中に添加し、更にγ−アミノプロピルトリ
エトキシシラン１ｇを添加して８０℃で１時間攪拌した
後、濾過した。濾過物をリン酸ナトリウム１２水和物の
０．７％水溶液１リットル中で室温下に１時間攪拌して
洗浄し、濾過して得た濾過物を１２０℃で３日間減圧乾
燥したものを抗菌・抗カビ剤Ｃとした。Antibacterial / antifungal agent C (product of the present invention) 100 g of zeolite was added to 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate and stirred at room temperature for 1 hour. After adding 0.76 g, the mixture was stirred at room temperature for 1 hour, and 113.75 g of zinc nitrate hexahydrate was further added, and the mixture was further stirred at room temperature for 1 hour and filtered. The filtrate was washed by stirring at room temperature for 1 hour in 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, added to 1 liter of ion-exchanged water, and further added with γ-aminopropyltriethoxy. After adding 1 g of silane and stirring at 80 ° C. for 1 hour, the mixture was filtered. The filtrate was stirred in 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate at room temperature for 1 hour, washed and filtered, and the filtrate was dried under reduced pressure at 120 ° C. for 3 days to obtain an antibacterial agent. -It was set as antifungal agent C.
【００３２】抗菌・抗カビ剤Ｄ（本発明品） リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中に、ゼオライト１００グラムを添加して室温で１時
間攪拌した後、硝酸銀３．２ｇを添加して室温で１時間
攪拌し、更に硝酸亜鉛６水和物４５．５ｇを添加して更
に室温で１時間攪拌して濾過した。この濾過物をリン酸
ナトリウム１２水和物の０．７％水溶液１リットル中で
室温下に１時間攪拌して洗浄した後、イオン交換水１リ
ットル中に添加し、更にヒドロキシプロピルトリメトキ
シシラン１ｇを添加して８０℃で１時間攪拌した後、濾
過した。濾過物をリン酸ナトリウム１２水和物の０．７
％水溶液１リットル中で室温下に１時間攪拌して洗浄
し、濾過して得た濾過物を１２０℃で３日間減圧乾燥し
たものを抗菌・抗カビ剤Ｄとした。Antibacterial / antifungal agent D (product of the present invention) 100 g of zeolite was added to 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate and stirred at room temperature for 1 hour. 2 g was added and the mixture was stirred at room temperature for 1 hour, 45.5 g of zinc nitrate hexahydrate was further added, and the mixture was further stirred at room temperature for 1 hour and filtered. The filtrate was stirred in 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate at room temperature for 1 hour, washed and then added to 1 liter of ion-exchanged water, and 1 g of hydroxypropyltrimethoxysilane was further added. Was added and stirred at 80 ° C. for 1 hour, followed by filtration. The filtrate was washed with 0.7% sodium phosphate dodecahydrate.
% Aqueous solution was stirred at room temperature for 1 hour, washed, filtered, and the filtrate obtained was dried under reduced pressure at 120 ° C. for 3 days to obtain an antibacterial / antifungal agent D.
【００３３】抗菌・抗カビ剤Ｅ（本発明品） γ−アミノプロピルトリエトキシシラン１ｇ、ピリジン
０．１８ｇを、テトラヒドロフラン５０ミリリットル中
に添加し１０℃で１０分間攪拌した後、これにラウリン
酸クロライド０．５ｇを滴下し、滴下終了後室温下で５
時間攪拌した。次いで減圧して溶媒を除去した後、予め
ゼオライト１００ｇを添加した１リットルのイオン交換
水中に攪拌下に添加し、更に室温で１時間攪拌後、水
洗、濾過した。濾過物をリン酸ナトリウム１２水和物の
０．７％水溶液１リットル中に添加し、これに硝酸銀
３．２ｇを添加して室温で１時間攪拌し、更に硝酸亜鉛
６水和物４５．５ｇを添加して室温で１時間攪拌後、濾
過した。濾過物をリン酸ナトリウム１２水和物の０．７
％水溶液１リットル中で室温下に１時間攪拌した後、水
洗して濾過し、濾過物を１２０℃で３日間減圧乾燥した
ものを抗菌・抗カビ剤Ｅとした。Antibacterial and antifungal agent E (product of the present invention) 1 g of γ-aminopropyltriethoxysilane and 0.18 g of pyridine were added to 50 ml of tetrahydrofuran, stirred at 10 ° C. for 10 minutes, and then added with lauric chloride. 0.5 g was added dropwise, and after completion of the addition, 5 g was added at room temperature.
Stirred for hours. Then, the solvent was removed by reducing the pressure, and the mixture was added with stirring to 1 liter of ion-exchanged water to which 100 g of zeolite had been previously added. After further stirring at room temperature for 1 hour, the mixture was washed with water and filtered. The filtrate was added to 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, and 3.2 g of silver nitrate was added thereto. The mixture was stirred at room temperature for 1 hour, and 45.5 g of zinc nitrate hexahydrate was further added. Was added and stirred at room temperature for 1 hour, followed by filtration. The filtrate was washed with 0.7% sodium phosphate dodecahydrate.
After stirring for 1 hour at room temperature in 1 liter of a 1% aqueous solution, the mixture was washed with water, filtered, and the filtrate was dried under reduced pressure at 120 ° C. for 3 days to obtain an antibacterial / antifungal agent E.
【００３４】抗菌・抗カビ剤Ｆ（本発明品） γ−アミノプロピルトリエトキシシラン１ｇを、メタノ
ール５０ミリリットル中に添加して１０℃で１０分間攪
拌した後、これに１−ブロモドデカン０．５６ｇを滴下
し、滴下終了後、還流下で２時間攪拌した。次いで減圧
して溶媒を除去した後、予めゼオライト１００ｇを添加
した１リットルのイオン交換水中に攪拌下に添加し、更
に室温で１時間攪拌後、水洗、濾過した。濾過物をリン
酸ナトリウム１２水和物の０．７％水溶液１リットル中
に添加し、これに硝酸銅０．７６ｇを添加して室温で１
時間攪拌し、更に硝酸亜鉛６水和物９１．０ｇを添加し
て室温で１時間攪拌後、濾過した。濾過物をリン酸ナト
リウム１２水和物の０．７％水溶液１リットル中で室温
下に１時間攪拌した後、水洗して濾過し、濾過物を１２
０℃で３日間減圧乾燥したものを抗菌・抗カビ剤Ｆとし
た。Antimicrobial / antifungal agent F (product of the present invention) 1 g of γ-aminopropyltriethoxysilane was added to 50 ml of methanol, stirred at 10 ° C. for 10 minutes, and 0.56 g of 1-bromododecane was added thereto. Was added dropwise, and after completion of the addition, the mixture was stirred under reflux for 2 hours. Then, the solvent was removed by reducing the pressure, and the mixture was added with stirring to 1 liter of ion-exchanged water to which 100 g of zeolite had been previously added. After further stirring at room temperature for 1 hour, the mixture was washed with water and filtered. The filtrate was added to 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, and 0.76 g of copper nitrate was added thereto.
After stirring for 1 hour, 91.0 g of zinc nitrate hexahydrate was further added, and the mixture was stirred at room temperature for 1 hour and then filtered. The filtrate was stirred at room temperature for 1 hour in 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, washed with water and filtered.
What was dried under reduced pressure at 0 ° C. for 3 days was defined as an antibacterial / antifungal agent F.
【００３５】抗菌・抗カビ剤Ｇ（従来品） リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中に、ゼオライト１００ｇを添加して室温で１時間攪
拌した後、硝酸銀３．２ｇを添加して室温で１時間攪拌
し、更に硝酸亜鉛６水和物４５．５ｇを添加して室温で
１時間攪拌後、濾過した。濾過物をリン酸ナトリウム１
２水和物の０．７％水溶液１リットル中で室温下に１時
間攪拌して洗浄した後、濾過し、１２０℃で３日間減圧
乾燥したものを抗菌・抗カビ剤Ｇとした。Antibacterial / antifungal agent G (conventional product) To 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate, 100 g of zeolite was added, and the mixture was stirred at room temperature for 1 hour. The mixture was stirred at room temperature for 1 hour, and 45.5 g of zinc nitrate hexahydrate was further added. The mixture was stirred at room temperature for 1 hour and filtered. Filter the filtrate with sodium phosphate 1
After washing with stirring for 1 hour at room temperature in 1 liter of a 0.7% aqueous solution of dihydrate, the solution was filtered and dried under reduced pressure at 120 ° C. for 3 days to obtain an antibacterial / antifungal agent G.
【００３６】抗菌・抗カビ剤Ｈ（従来品） リン酸ナトリウム１２水和物の０．７％水溶液１リット
ル中に、カオリン１００ｇを添加して室温で１時間攪拌
した後、硝酸銀３．２ｇを添加して室温で１時間攪拌
し、更に硝酸亜鉛６水和物４５．５ｇを添加して室温で
１時間攪拌後、濾過した。濾過物をリン酸ナトリウム１
２水和物の０．７％水溶液１リットル中で室温下に１時
間攪拌して洗浄した後、濾過し、１２０℃で３日間減圧
乾燥したものを抗菌・抗カビ剤Ｈとした。Antibacterial and antifungal agent H (conventional product) To 1 liter of a 0.7% aqueous solution of sodium phosphate dodecahydrate was added 100 g of kaolin, and the mixture was stirred at room temperature for 1 hour. The mixture was stirred at room temperature for 1 hour, and 45.5 g of zinc nitrate hexahydrate was further added. The mixture was stirred at room temperature for 1 hour and filtered. Filter the filtrate with sodium phosphate 1
After washing with stirring in 1 liter of a 0.7% aqueous solution of dihydrate at room temperature for 1 hour, the solution was filtered and dried under reduced pressure at 120 ° C. for 3 days to obtain an antibacterial / antifungal agent H.
【００３７】実施例１〜６、比較例１〜２ 抗菌・抗カビ剤２ｇを、樹脂１００ｇに対して練り込ん
だ後、厚さ２ｍｍのシート状に成形し、このシートから
４４ｍｍ×６４ｍｍのサンプルを作成した。練り込む樹
脂としては、ポリエチレン（ＰＥ）とＡＢＳの２種類を
用いた。耐熱性は、抗菌・抗カビ剤を樹脂に練り込む際
の熱による着色を肉眼で観察し、抗菌・抗カビ剤を添加
していないブランクと比較して以下の基準により評価し
た。結果を表１に示す。Examples 1 to 6 and Comparative Examples 1 to 2 After 2 g of an antibacterial and antifungal agent was kneaded into 100 g of a resin, the mixture was molded into a sheet having a thickness of 2 mm, and a 44 mm × 64 mm sample was prepared from the sheet. It was created. As the resin to be kneaded, two types of polyethylene (PE) and ABS were used. The heat resistance was evaluated by visually observing coloring due to heat when kneading the antibacterial / antifungal agent into the resin, and comparing with a blank to which no antibacterial / antifungal agent was added, according to the following criteria. Table 1 shows the results.
【００３８】耐熱性評価基準 ○・・ブランク（抗菌・抗カビ剤無添加）と同等。 △・・ブランクと比較してやや着色あり。 ×・・ブランクと比較してかなり着色あり。Evaluation criteria for heat resistance ・: Equivalent to blank (no antibacterial / antifungal agent added) Δ: Slightly colored compared to blank. ×: considerably colored compared to blank.
【００３９】また上記のようにして調製したサンプルに
ついて、紫外線照射による耐候性、及び抗菌性の試験を
行った。耐候性はサンプルに、紫外線ランプにより紫外
線を２４時間照射し、サンプルの色調の変化を肉眼で観
察し、抗菌・抗カビ剤を添加していないブランクと比較
して以下の基準で評価した。結果を表１に示す。また抗
菌性は、滅菌シャーレに上記サンプルを入れ、この上に
大腸菌懸濁液０．５ミリリットルを滴下した後、サンプ
ル表面に滅菌ポリエチレンフィルムを密着させて３５
℃、湿度９０％以上で２４時間培養した後、ＳＣＬＰ培
地１０ミリリットルで滅菌シャーレ中に菌液を洗い出
し、更に駒込ピペットによりポリエチレンフィルムとサ
ンプル面に洗液を３回注いで洗い出し、洗液中に洗い出
された生菌を標準寒天培地による寒天希釈平板培養法に
よって培養し、生菌数の測定結果で示した。結果を表１
にあわせて示す。Further, the samples prepared as described above were tested for weather resistance and antibacterial property by ultraviolet irradiation. The weather resistance was evaluated by irradiating the sample with an ultraviolet ray for 24 hours using an ultraviolet lamp, observing the change in the color tone of the sample with the naked eye, and comparing it with a blank to which no antibacterial / antifungal agent was added. Table 1 shows the results. The antibacterial property was measured by placing the above sample in a sterile petri dish, dropping 0.5 ml of the E. coli suspension onto the sample, and then adhering a sterile polyethylene film to the sample surface.
After culturing for 24 hours at 90 ° C. and a humidity of 90% or more, the bacterial solution is washed out in a sterile petri dish with 10 ml of SCLP medium, and then the washing solution is poured out onto the polyethylene film and the sample surface three times with a Komagome pipette, and washed out. The washed viable cells were cultured by an agar dilution plate culture method using a standard agar medium, and the number of viable cells was measured. Table 1 shows the results
Shown along with.
【００４０】耐候性評価基準 ○・・ブランク（抗菌・抗カビ剤無添加）と同等の色
調。 △・・ブランクと比較してやや色調の変化あり。 ×・・ブランクと比較してかなり色調の変化あり。Evaluation criteria for weather resistance ○: Color tone equivalent to blank (no antibacterial / antifungal agent added) △ ・ ・ There is a slight change in the color tone compared to the blank. X: There is a considerable change in the color tone as compared to the blank.
【００４１】[0041]
【表１】[Table 1]
【００４２】[0042]
【発明の効果】以上説明したように、本発明の抗菌・抗
カビ剤は、担持されている抗菌性金属が細菌等を死滅さ
せるに必要な極微量ずつ長期間に亘って溶出するため、
抗菌性金属の溶出不足によって抗菌効果が不充分となっ
たり、抗菌性金属が一度に多量に溶出して安全性の問題
が生じたり、抗菌作用が短期間で低下する等の虞れがな
く、長期間に亘って優れた抗菌・抗カビ作用が発現され
る。また本発明の抗菌・抗カビ剤は耐候性、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・
抗カビ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, the antibacterial / antifungal agent of the present invention elutes the supported antibacterial metal over a long period of time in trace amounts necessary for killing bacteria and the like.
Insufficient elution of the antibacterial metal causes the antibacterial effect to be insufficient, there is no risk that the antibacterial metal elutes in large quantities at a time, causing safety problems, and the antibacterial action is reduced in a short period of time, Excellent antibacterial and antifungal effects are exhibited over a long period of time. Further, the antibacterial and antifungal agent of the present invention has excellent weather resistance and heat resistance, and is less likely to be discolored by heat or light when kneaded into a resin or the like.
When used as an antifungal agent, there is an effect that the commercial value of the resin product or the paint is enhanced without the color of the resin product or the paint being discolored.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ａ０１Ｎ 59/20 Ａ０１Ｎ 59/20 Ｚ (72)発明者 細田 和夫 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────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl.6 Identification symbol FI A01N 59/20 A01N 59/20 Z (72) Inventor Kazuo Hosoda 4-66-1, Horikiri, Katsushika-ku, Tokyo Miyoshi Oil & Fats Co., Ltd. (72) Inventor Masafumi Moriya Miyoshi Yushi Co., Ltd. 4-66-1, Horikiri, Katsushika-ku, Tokyo
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20378797AJPH1129425A (en) | 1997-07-14 | 1997-07-14 | Antibacterial and antifungal agent |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20378797AJPH1129425A (en) | 1997-07-14 | 1997-07-14 | Antibacterial and antifungal agent |
| Publication Number | Publication Date |
|---|---|
| JPH1129425Atrue JPH1129425A (en) | 1999-02-02 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20378797APendingJPH1129425A (en) | 1997-07-14 | 1997-07-14 | Antibacterial and antifungal agent |
| Country | Link |
|---|---|
| JP (1) | JPH1129425A (en) |
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|---|---|---|---|---|
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| CN110219065A (en)* | 2019-06-06 | 2019-09-10 | 广东彩艳股份有限公司 | A kind of Modified Cu ion antibacterial agent and preparation method thereof, antibacterial matrices and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242279A (en)* | 2008-03-31 | 2009-10-22 | Nagasaki Prefecture | Clay mineral-based composite material and method for controlling sustainedly releasing property thereof |
| CN110219065A (en)* | 2019-06-06 | 2019-09-10 | 广东彩艳股份有限公司 | A kind of Modified Cu ion antibacterial agent and preparation method thereof, antibacterial matrices and preparation method thereof |
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