JP4252250B2

JP4252250B2 - Antibacterial / antifungal agent for closed space and antibacterial / antifungal method for closed space

Info

Publication number: JP4252250B2
Application number: JP2002088995A
Authority: JP
Inventors: 英二竹村; 由起子高橋; 章土信田
Original assignee: Nippon Soda Co Ltd
Current assignee: Nippon Soda Co Ltd
Priority date: 2002-03-27
Filing date: 2002-03-27
Publication date: 2009-04-08
Anticipated expiration: 2022-03-27
Also published as: JP2003286114A

Description

【０００１】
【発明の属する技術分野】
本発明は、洗濯機の洗濯槽、下駄箱、流し台下の収納庫等、通気性の悪い閉鎖された空間で湿気が多く細菌や黴等の微生物が繁殖しやすい場所であり、かつ衣類、靴、調理器具等への臭い移りが嫌われるために臭気の強い薬剤を使用できない場所に使用される無臭又は微臭性の閉鎖空間用防菌防黴剤及びこれを用いた閉鎖空間の防菌防黴方法に関する。
【０００２】
【従来の技術】
洗濯機の洗濯槽、特に全自動洗濯機の洗濯槽は手の届かない空間が多く、洗濯汚水や洗剤カスを栄養源にして黴が繁殖し問題となっており、塩素系洗剤や過炭酸塩等からなる黴除去剤が販売されているが、洗濯槽の構造が複雑である上、裏面に発生した黴に濃厚液を直接かけることは困難である。このため、洗濯槽に水を張り、殺菌剤等の薬剤を溶かして一定時間放置する方法が採られているが、このような方法では、洗濯槽の容量が大きく、薬剤濃度を上げることが困難であり、また長時間放置する必要があり作業に時間がかかり面倒であった。また、水を貯留することができない洗濯槽上部の黴の除去はできないという問題もあった。
【０００３】
また、下駄箱には靴やブーツ等が収納されているが、汗や濡れた靴からの水分で多湿状態となっているため、細菌が繁殖して不快臭を発生するとともに、繁殖した細菌や黴が靴の寿命を縮めてしまうという問題があった。また、流し台下の収納部には鍋やフライパン等の調理器具が収納される場合が多いが、多湿状態で細菌や黴が繁殖した状態となっているため、不快であるとともに衛生上も問題となっていた。これらの場所の防菌防黴方法としては、一般的に乾燥剤が使用されているが、効果は不充分であり細菌や黴の繁殖を防止しうるものではなかった。
【０００４】
昇華性あるいは気化性の防菌防黴剤を封入した容器を、フッ素樹脂やポリウレタン系の数μ以下の微細な孔を有する微多孔膜や、シリコーン樹脂やポリアミノウレタン系樹脂のようなガスを透過させる分子間隙を有する非多孔質膜等で形成し、ガスの透過を担保させた容器を冷蔵庫内に配設して、庫内の腐敗細菌の増殖抑制効果を図った冷蔵庫が知られている（特開平３−１６４６８１号公報）。また、ホスト化合物に精油成分を包接させた化合物をポリエチレン等の発泡体に担持させた脱臭、抗菌、害虫忌避発泡体（特開平８−２４３２１号公報）や、ヒノキチオール類を含むサイクロデキストリン包接化合物をポリプロピレン等に含有させた層を有する食品包装用抗菌性ストレッチフィルム（特開平４−３５９０２９号公報）も知られている。
【０００５】
しかしながら、このような防菌防黴剤は、冷蔵庫内のように低温度であり微生物の繁殖力の弱い場所や、包装フィルム全面から抗菌剤が気化しかつ完全密封とできる食品包装フィルムでは効果を発揮するが、洗濯機の洗濯槽、下駄箱、流し台下収納庫のように高温多湿で微生物の繁殖力が強く、防菌防黴剤を設置できる面積も小さく、かつ密封性が低くて気化した防菌防黴剤が系外にもれるような場所での微生物の繁殖を防ぐことは困難であった。
【０００６】
一方、本発明者らによって、天然精油成分等の気化性防菌防黴成分を有効成分とする洗濯機用の防菌防黴剤（特願２００１−３６９０８２）が提案されている。また、芳香族イソチオシアネートを有効成分とする洗面台下の収納庫等の閉鎖空間用防黴剤（特開２００１−２２０３０４号公報）や、フマル酸ジメチル、フマル酸モノメチル、又はフマル酸ジエチルを通気性包材に収納した腐敗性廃棄物の防菌・防臭方法（特開平１１−２１２０２号広報）も知られている。しかし、これらの薬剤は防菌防黴剤としては有効であるが、いずれも薬剤特有の強い臭気を有しており、洗濯機に使用した場合には衣類への臭気付着、下駄箱に使用した場合には靴への臭気付着、流し台下収納庫に使用した場合には収納物への臭気付着があるばかりでなく、使用者が蓋や扉を開けた際にも強い臭気を感じたりするため実用に供することは困難であった。
【０００７】
【発明が解決しようとする課題】
本発明の課題は、気化性の防菌防黴剤を使用することによって、洗濯機内の洗濯槽の裏側、下駄箱内の靴内部、流し台下収納庫等、通常の殺菌剤や殺黴剤の使用が困難な場所でも菌類や黴類が発生するのを抑制することができ、しかも微臭性の気化性防菌防黴剤を有効成分とすることによって、洗濯衣類、下駄箱の靴、流し台下収納庫の収納物等に臭いを付着させず、これらの使用者にも不快臭を感じさせない閉鎖空間用防菌防黴剤や閉鎖空間用防菌防黴方法を提供することにある。
【０００８】
【課題を解決するための手段】
本発明者らは、複雑な形状の洗濯機内部、靴やブーツを収納している下駄箱、調理器具や食品等を収納している流し台下収納庫等の防菌防黴を効率よく行うためには、複雑な形状の空間の隅部にまで拡散、浸透し、低濃度で効果を発揮する気化性防菌防黴剤が適しており、特に、洗濯衣類や収納物等に防菌防黴剤の臭気を付着させない無臭又は微臭性の気化性防菌防黴剤が適していることに着目した。そこで、(１)気化性防菌防黴化合物を有効成分とし、気化性物質の気化速度を制御すると、防菌防黴効果を長期間にわたって得ることができること、(２) 一般家庭では洗濯機の使用時間は１日１〜２時間程度、下駄箱や流し台下収納庫の開閉は一日数回程度であり、夜間や日中等長時間にわたり閉鎖空間状態が継続する場合であっても、防菌防黴成分を無駄なく有効に使用し、人体や周辺へ影響を及ぼすことがないこと、(３)洗濯機の蓋裏、下駄箱、流し台下収納庫の天井や壁面等に簡単に装着しうること、（４）洗濯衣類、下駄箱、流し台下収納庫の収納物に気化性防菌防黴剤の臭気が付着せず、しかも蓋や扉の開放時に不快臭を感じさせないことをコンセプトとして研究した結果、気化性であって、無臭又は微臭性の防菌防黴剤、好ましくは該成分を多分子包接化合物として含有する防菌防黴剤を、洗濯機の蓋の裏側、下駄箱や流し台下収納庫の天井や壁面に、粘着剤又は接着剤で固定・使用することにより、洗濯機の洗濯槽、下駄箱内や流し台下収納庫内において顕著な防菌防黴効果が得られ、しかも洗濯衣類や靴等の収納物に防菌防黴剤の臭気が付着しないことを見い出した。さらに本発明者らは、防菌防黴剤を通気性のフィルムもしくは防菌防黴剤成分を透過させるフィルムを有する袋に収納したり、フィルムに挟持してシート状にしたり、繊維と混合してシート状又は板状に形成したり、通気性容器に収納したりすることにより、防菌防黴作用が長時間にわたって得られること、防菌防黴剤の臭気をより低減することができること、洗濯機の蓋の裏側、下駄箱や流し台下収納庫の天井や壁面等に固定しやすいこと、さらには洗濯水の飛沫が飛散する等の水に濡れる状況で使用した場合でも充分な防菌防黴効果を得ることができることを見い出し、本発明を完成するに至った。
【０００９】
すなわち本発明は、（１）シリカゲル微粉末又は珪藻土と均一混合状態で存在する無臭又は微臭性気化性防菌防黴成分を含有することを特徴とする閉鎖空間用防菌防黴剤や、（２）一般式［Ｉ］
【００１０】
【化２】

【００１１】
（式中、Ｘは、（ＣＨ₂）_nを表し、ｎは、０、１、２又は３であり、Ｒ¹〜Ｒ⁸は、同一又は相異なってもいてもよく、水素原子、Ｃ１〜Ｃ６のアルキル基、置換基を有していてもよいフェニル基、ハロゲン原子又はＣ１〜Ｃ６のアルコキシ基を示す。）で示されるテトラキスフェノールをホスト化合物とする多分子包接化合物である無臭又は微臭性気化性防菌防黴成分が含有されていることを特徴とする閉鎖空間用防菌防黴剤や、（３）ホスト化合物が、１，１，２，２−テトラキス（ヒドロキシフェニル）エタン又は１，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニル）エタンであることを特徴とする（２）記載の閉鎖空間用防菌防黴剤や、（４）無臭又は微臭性気化性防菌防黴成分が、フマル酸ジアルキル、炭素数６〜２０の高級アルコール、サリチル酸から選ばれる１種又は２種以上の成分であることを特徴とする（１）〜（３）のいずれかに記載の閉鎖空間用防菌防黴剤や、（５）フマル酸ジアルキルがフマル酸ジメチル、フマル酸ジノルマルブチル、フマル酸ジヘプチル、フマル酸ジヘキシル、フマル酸ジオクチルから選ばれる１種又は２種以上の成分であることを特徴とする（４）記載の閉鎖空間用防菌防黴剤や、（６）少なくとも一部が無臭又は微臭性気化性防菌防黴成分を透過させるフィルムで形成された袋に収納されていることを特徴とする（１）〜（５）のいずれかに記載の閉鎖空間用防菌防黴剤や、（７）無臭又は微臭性気化防菌防黴成分が、フマル酸ジメチルであることを特徴とする（６）に記載の閉鎖空間用防菌防黴剤や、（８）少なくとも一部が無臭又は不快臭を感じない程度の強さの微臭性気化性防菌防黴成分の蒸気を通過させる通気性フィルムで形成された袋に収納されていることを特徴とする（１）〜（７）のいずれかに記載の閉鎖空間用防菌防黴剤や、（９）通気性フィルムが通気・非通水性フィルムであることを特徴とする（８）記載の閉鎖空間用防菌防黴剤や、（１０）通気性収納容器に収納されていることを特徴とする（１）〜（９）のいずれかに記載の閉鎖空間用防菌防黴剤や、（１１）通気性収納容器内に微臭性気化性防菌防黴剤の蒸発を促進する加温体が設置されていることを特徴とする（１０）に記載の閉鎖空間用防菌防黴剤に関する。
【００１２】
また、本発明は、（１２）粘着剤又は接着剤で固定して使用することを特徴とする（１）〜（１１）のいずれかに記載の閉鎖空間用防菌防黴剤や、（１３）粘着剤又は接着剤で固定する防菌防黴剤の面の材質が無臭又は微臭性防菌防黴成分を透過又は蒸気を通気しないものである事を特徴とする（１２）に記載の閉鎖空間用防菌防黴剤や、（１４）閉鎖空間が、洗濯機内空間であることを特徴とする（１）〜（１３）のいずれかに記載の閉鎖空間用防菌防黴剤や、（１５）閉鎖空間が、下駄箱内空間であることを特徴とする（１）〜（１３）のいずれかに記載の閉鎖空間用防菌防黴剤や、（１６）閉鎖空間が、流し台下の収納庫内空間であることを特徴とする（１）〜（１３）のいずれかに記載の閉鎖空間用防菌防黴剤や、（１７）（１）〜（１６）のいずれかに記載の閉鎖空間用防菌防黴剤を用いたことを特徴とする閉鎖空間の防菌防黴方法に関する。
【００１３】
【発明の実施の形態】
本発明の閉鎖空間用防菌防黴剤としては、無臭又は微臭性で気化性の防菌防黴成分を含有し、洗濯機の蓋の裏側、下駄箱や流し台下収納庫の天井や壁面等に固定して使用しうるように構成されているものであればどのようなものでもよいが、気化性防菌防黴成分が、固体形態の多分子包接化合物として含有されているものが好ましい。
【００１４】
本発明における無臭又は微臭性気化性防菌防黴成分としては、気化した蒸気が防菌防黴作用を有するものであり、その臭気が無臭又は不快臭を感じない程度の強さの微臭性ものであれば、天然抽出物や合成化合物であってもよい。具体的にはフマル酸ジアルキル、炭素数６〜２０の高級アルコール、サリチル酸等を挙げることができ、特にフマル酸ノルマルブチル、フマル酸ジペンチル、フマル酸ジヘキシル、フマル酸ジヘプチル、フマル酸ジオクチル等を好適に例示することができる。フマル酸ジメチルは上記薬剤に比べると若干臭気が強いため、そのままの形態で使用すると不快臭を発生するが、防菌防黴効果が強く、固体であるために薬剤残量が目視判定できる等の利点があるため、透過性フィルムの厚みを選定して蒸気濃度をコントロールしたり、多分子包接化合物として、閉鎖空間でのフマル酸ジメチルの飽和蒸気濃度を低下させる等の手段を講じることにより好適に使用することができる。また、炭素数６〜２０の高級アルコールとしては、ヘキシルアルコール、オクチルアルコール、ドデシルアルコール（ラウリルアルコール）オクタデシルアルコール（ステアリルアルコール）等を挙げることができる。
【００１５】
上記の気化性防菌防黴成分は、防菌防黴作用が長時間にわたって得られることから、多分子包接化合物として含有されるものが好ましい。気化性防菌防黴成分の気化の速度は、包装材や、容器の開口面積等の構成により調整することができ、また、溶剤やゲル中に溶解させ気化速度を遅延させ、あるいは樹脂と共に混練成形したり、防菌防黴成分をマイクロカプセル化することにより、気化速度を遅延させ、防菌防黴効果を持続させることもできるが、多分子包接化合物とすることにより、ホスト化合物から放出された余剰の気化性防菌防黴成分は、ホスト化合物に再度包接されて飽和平衡状態を維持するため、ゲスト化合物の飽和蒸気圧は、ゲスト化合物本来の飽和蒸気圧に比べて、１〜数１０分の１に低減される。このため、長時間閉鎖された状態となる洗濯機、下駄箱、流し台下収納庫のような場所では、防菌防黴剤の有効期間を大幅に延長できるという優れた特性を発揮する。例えば、通常の家庭で１日１回、小人数の家庭では２〜７日に１回しか使用されず、長時間蓋が閉められた状態で放置される洗濯機内では、大部分の時間帯が気化防菌防黴成分が飽和蒸気圧となるため、気化防菌防黴成分を多分子包接化合物とすることにより、気化性防菌防黴成分の気体の飽和濃度自体を低減させることができ、気化性防菌防黴効果時間を数倍〜数１０倍延長することができる。特に、ホスト化合物とゲスト化合物との組み合わせからなる多分子包接化合物を選択することにより、気化性防菌防黴成分の無駄な消失を防止しつつ、長期にわたり気化性防菌防黴効果を持続することができる。更に、気化性防菌防黴成分の消失量の低減に伴い、洗濯機外への漏洩する気化性防菌防黴成分量も低減されるため、人体等への影響を回避することができる。
【００１６】
このように気化性防菌防黴成分を多分子包接化合物とする場合のゲスト化合物を包接するホスト化合物としては、多分子包接化合物を形成することができる公知のホスト化合物であれば特に制限されるものではないが、一般式［Ｉ］で表されるテトラキスフェノールが好ましい。式［Ｉ］中、Ｘは、（ＣＨ₂）_nを表し、ｎは、０、１、２又は３であり、Ｒ¹〜Ｒ⁸は、互いに同一又は相異なってもよく、水素原子、低級アルキル基、置換基を有していてもよいフェニル基、ハロゲン原子又は低級アルコキシ基を示す。上記低級アルキル基としては、例えば、メチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ｎ−ヘキシル基、シクロヘキシル基等のＣ１〜Ｃ６のアルキル基を挙げることができ、フェニル基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子やＣ１〜Ｃ６の低級アルキル基等を挙げることができ、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等を挙げることができ、低級アルコキシ基としては、メトキシ基、エトキシ基、ｔ−ブトキシ基等のＣ1〜Ｃ6の低級アルコキシ基等を挙げることができる。
【００１７】
上記一般式〔Ｉ〕で表される化合物としては、具体的に、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３，５−ジメチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−クロロ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３，５−ジクロロ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−ブロモ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３，５−ジブロモ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−ｔ−ブチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−フルオロ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３，５−ジフルオロ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−メトキシ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３，５−ジメトキシ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−クロロ−５−メチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−ブロモ−５−メチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−メトキシ−５−メチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−クロロ−５−ブロモ−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−クロロ−５−フェニル−４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス［（４−ヒドロキシ−３−フェニル）フェニル］エタン、１，１，３，３−テトラキス（４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３−メチル−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３，５−ジメチル−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３−クロロ−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３，５−ジクロロ−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３−ブロモ−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３−フェニル−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３，５−ジフェニル−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３−メトキシ−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３，５−ジメトキシ−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３−ｔ−ブチル−４−ヒドロキシフェニル）プロパン、１，１，３，３−テトラキス（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロパン、１，１，４，４−テトラキス（４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３−メチル−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３，５−ジメチル−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３−クロロ−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３，５−ジクロロ−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３−メトキシ−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３，５−ジメトキシ−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３−ブロモ−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３，５−ジブロモ−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３−ｔ−ブチル−４−ヒドロキシフェニル）ブタン、１，１，４，４−テトラキス（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）ブタン等を挙げることができるが、中でも１，１，２，２−テトラキス（ヒドロキシフェニル）エタンや、１，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニルエタン）が好ましい。これらのテトラキスフェノール化合物はそれぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
【００１８】
本発明における無臭又は微臭性気化性防菌防黴成分は他の造形剤や香料等と混合して、錠剤、粉末状の防菌防黴薬剤として成形することができる。また、上記気化性防菌防黴剤を解砕パルプや、繊維と共に紙状に成形したり、気化性防菌防黴成分を繊維と混合して厚めの不織布等、板状に成形することもできる。
【００１９】
本発明の無臭又は微臭性気化性防菌防黴成分を含有する防菌防黴薬剤を洗濯機の蓋の裏側、下駄箱や流し台下収納庫の天井や壁面に固定して使用しうるようにする方法としては、目的の場所に設置・配置できる方法であればいずれの方法であってもよく、防菌防黴薬剤を直接クリップ等で挟み固定したり、あるいは粘着テープで貼り付けてもよいが、洗濯機の蓋の裏側に設置する場合には、洗濯水が飛散して気化性防菌防黴薬剤の気化が阻害されないように、片面又は両面等少なくともその一部を防菌防黴成分が透過するフィルム又は通気性フィルムで挟んでシート状に成形した防菌防黴薬剤を、粘着剤や接着剤で固定して使用する方法や、片面又は両面等少なくともその一部を防菌防黴成分が透過するフィルム又は通気性フィルムで成形された袋に収納した防菌防黴薬剤を、粘着剤や接着剤で固定して使用する方法等を挙げることができ、更に、上記通気性フィルムを通気・非通水フィルムとすることにより、洗濯水の飛沫が防菌防黴剤と接触することを防止することができ、気化性防菌防黴薬成分の気化の阻害を回避することができるため好ましい。その他、気化性防菌防黴成分を、繊維と均一に混合し通気性のシート又は板状に成形したものを、粘着剤、接着剤等により固定して使用する方法、また、上記防菌防黴薬成分や、これを収納した袋や、気化性防菌防黴成分を含有するシート状又は板状に形成されたものを、通気性の収納容器に収納し、粘着剤や接着剤等で固定して使用する方法によることもできる。
【００２０】
なお、本発明において、粘着剤や接着剤で防菌防黴成分が透過するフィルム又は通気性フィルムの袋やシートを目的とする場所に固定する場合には、粘着剤や接着剤を使用する側の袋やシートの面は、防菌防黴成分が透過したり蒸気が通気しない材質のフィルムや板で形成することが好ましい。一般に、防菌防黴成分には粘着剤や接着剤を溶解する溶剤としての作用を有するものが多いため、防菌防黴成分を透過又は蒸気を通気させるフィルムを粘着剤や接着剤を使用する側に使用すると、本発明の防菌防黴剤が固定した場所から剥離離脱するトラブルを発生する事となる。また、防菌防黴成分をフィルムの袋やシートに収納して使用する場合には、防菌防黴成分を時間の経過に関わらず一定に気化させるために、防菌防黴成分が液体の場合にはシリカゲル微粉末や粘土鉱物微粉末に均一に含浸させて使用することが好ましく、防菌防黴成分が固体の場合においても気化速度が遅い化合物の場合や低融点の化合物の場合は防菌防黴成分の融点より高い温度でシリカゲル微粉末や粘土鉱物微粉末と均一混合するか、防菌防黴成分をシリカゲル微粉末や粘土鉱物微粉末と混合後に混合物を気流粉砕することによって微細粒子を安定化させると、防菌防黴成分の気化を時間の経過にかかわらず一定に行わせる事が可能となる。
【００２１】
本発明の閉鎖空間の防菌防黴方法としては、上述の本発明の閉鎖空間用防菌防黴剤を用いた方法であれば特に制限されるものではないが、ホスト化合物からの放出・包接により閉鎖空間において平衡状態になったときの気化性防菌防黴成分の濃度が防菌防黴有効濃度となるような、ホスト化合物とゲスト化合物との組み合わせからなる多分子包接化合物を用いる方法が好ましい。
【００２２】
本発明の閉鎖空間用防菌防黴剤を使用する本発明の閉鎖空間の防菌防黴方法によれば、防菌防黴成分が空気より重いため、洗濯機の蓋の裏側、下駄箱や流し台下収納庫の天井や壁面に固定した気化性防菌防黴成分が気化して、閉鎖空間内の空気と混合しながら閉鎖空間の低部へ移動し、複雑な形状の空間の隅々にまで拡散、浸透し、防菌防黴効果が得られる。また、気化性防菌防黴成分を多分子包接化合物として用いた場合には、気化性防菌防黴成分の気化速度を制御することができ、また、ゲスト化合物である気化性防菌防黴成分が一旦放出された後、再度ホスト化合物に包接されて飽和平衡状態を維持するため、気体の飽和蒸気圧が低減され、すなわち閉鎖空間ないの気化性防菌防黴成分の飽和濃度が低減され、気化性防菌防黴成分の消失量の低減を図ることができる。特に、洗濯機は使用時間が短く、長時間蓋を閉めた状態で放置される場合が多いため、気化性防菌防黴剤が低濃度で飽和状態が維持され、防菌防黴効果を長期間にわたって得ることができると共に、洗濯機から漏洩する気化性防菌防黴剤の量も低減され、人体等への影響を抑制し、少量で最大の効果を得ることができる。更に、水に濡れる状況で使用した場合でも、通気・非通水フィルム等を用いた場合は、洗濯水の飛沫の接触を防止することができるため、気化性防菌防黴成分の気化が妨げられず、洗濯機を使用する際に、防菌防黴剤を取り出し、洗濯終了時に再度固定する動作の反復を回避できる。
【００２３】
以下、本発明の閉鎖空間用防菌防黴剤を、洗濯機に使用した場合について、図面を参照して説明するが、この発明の範囲はこれらの例示に限定されるものではない。
本発明の洗濯機用防菌防黴剤は、図１に示すように、気化したとき空気より重い気体の気化性防菌防黴成分を固体として含有する防菌防黴薬剤Ｍが、洗濯機１の蓋１ａの裏側に設置されるものである。
【００２４】
防菌防黴薬剤Ｍは、固形又は粉末状であり、図２及び図３に示すように、洗濯機１の内側に対向する面が通気・非通水性フィルム２ａで、蓋１ａ側に対向する面が非通気性フィルム２ｂで形成された袋２に収納されている。通気・非通水性フィルム２ａは、疎水性フィルムに１〜５μの微細な孔が形成され、気体粒子はこの孔を透過できるが、水粒子は透過し得ないものであり、袋２に洗濯水の飛沫が付着しても、収納された防菌防黴薬剤Ｍが水と接触するのを防止する。通気・非通水性フィルム２ａとしては、タイベックフィルム（商品名：デュポン社製）や、ＮＦシート（商品名：トクヤマ（株）社製）等を例示することができる。袋２は接着剤Ｓにより洗濯機１の蓋１ａに固定される。
【００２５】
また、図４に示すように、洗濯機用防菌防黴剤を、気化性防菌防黴成分をそのまま、あるいは、防菌防黴薬剤Ｍを不織布３ａで挟持し、格子状の接着部３ｂで接着して形成されたシート３と構成してもよい。その他、洗濯機用防菌防黴剤として、解砕パルプに粉末の防菌防黴薬剤Ｍや気化性防菌防黴成分を添加混合し、紙に漉き乾燥させた板紙、原料繊維と気化性防菌防黴成分を混合し厚めに形成した不織布、板紙に防菌防黴薬成分を溶解した溶剤を含浸させて乾燥した厚めの不織布、あるいはこれらを袋２に収納したものも用いることができる。
【００２６】
また、図５には、防菌防黴薬剤Ｍを収納する通気性収納容器４の一例が示されており、かかる通気性収納容器４は、接着剤Ｓにより洗濯機の蓋１ａに固定される固定部４ｃと、この固定部４ｃに着脱自在に設けられる収納部４ａとを有し、収納部４ａの底面は、それぞれ、複数のスリット状の外側開口部４ｄと内側開口部４ｅとが交互に位置するように設けられた２枚の通気板４ｂで構成され、図６に示すように、２枚の通気板４ｂは、スリット状の開口部４ｄ，４ｅの位置が一致しないように設置され、且つ、平行に収納部４ａに装着される。通気板４ｂに設けられた開口部４ｄ，４ｅにより、気化した気化性防菌防黴成分の洗濯機１内への拡散を可能とし、且つ、洗濯水の飛沫が収納容器４内に収納される防菌防黴薬剤Ｍ等に直接接触しないようになっている。かかる収納容器４に収納される防菌防黴薬剤が消費されたとき、収納部４ａを固定部４ｃから取り外し、防菌防黴薬剤Ｍ等を新しいものに交換することができる。
【００２７】
更に、上記防菌防黴薬剤Ｍを収納した袋２、シート３、収納容器４、板状に形成した防菌防黴薬剤等の可視部には、上記気化性防菌防黴剤と反応し着色、変色等変化が認識できる物質からなるシグナルマーカー等を設けておき、その変化を目視することにより、気化性防菌防黴成分が消費されたことを検出できるものとしてもよい。その他、防菌防黴薬剤Ｍを収納した袋２、シート３、収納容器４を洗濯機の蓋に固定する方法として接着剤に限らず、粘着テープを使用したり、接着面に取着された離型紙を除いて洗濯機の蓋に接着するようにしてもよい。
【００２８】
【実施例】
＜防菌防黴剤の調製＞
本発明の無臭又は微臭性気化性防菌防黴成分及び比較対照の気化性防菌防黴成分を含む、表１に示される組成の防菌防黴剤を調製した。防菌防黴剤の調製は、気化性防菌防黴成分をシリカゲル微粉末及び／又は珪藻土と混合し、粉末状とすることにより調製した。気化性防菌防黴成分を多分子包接化合物として用いる場合には、メタノール５００ｍＬに、ホスト化合物として１，１，２，２−テトラキス（ヒドロキシフェニル）エタン（ＴＥＰ）５０ｇを加え、６０℃に加熱し溶解させ、これに表１に記載するゲスト化合物１００ｇを徐々に加え６０℃で３０分間、撹拌し反応させ、不溶解物を濾過し除去した。濾過液を１夜室温で放置し、得られた結晶を濾過し、メタノールで洗浄後、４０℃で１時間真空乾燥し多分子包接化合物を得た。表１中、ＴＥＰ−フマル酸ジメチルはＴＥＰ：フマル酸ジメチル＝１：２（モル）であった。
【００２９】
【表１】

【００３０】
評価試験１（防菌防黴効果評価試験Ａ：洗濯槽想定）
実施例１で得られた１１種類の各防菌防黴薬剤の所定量（気化性防菌防黴剤５ｇ相当、表１記載）を、片面が通気・非通水性フィルム（ＮＦシート：（株）トクヤマ社製；通気度５０秒／１００ｍ）としたフィルムＡ、又は透過性フィルム（低密度ポリエチレンフィルム、厚さ０．０５ｍｍ）としたフィルムＢ、もう片面をナイロン０．０６ｍｍと低密度ポリエチレン０．０５のラミネートフィルムとした１００ｍｍ×１２０ｍｍの袋に収納し、周囲をヒートシールして、薬剤収納サンプル１〜１１を調製した。次に、７０Ｌの蓋付ポリバケツ内に上部、中間部、底部に黒黴（Aspergillus niger IFO No442）胞子懸濁液０．１ｍＬを接種したポテトデキストロール寒天培地のシャーレを設置し、蓋の裏面に上記薬剤収納サンプル１〜１１を通気・非通水フィルム（フィルムＡ）又は透過性フィルム（フィルムＢ）を下向きにして粘着テープで固定した。ポリバケツ底には水を張った大型シャーレを置いて、湿気を保った状態で蓋をして放置した。１日１回１時間（２週間以上は土、日曜日は蓋をしたまま放置）蓋を取り除いた状態で恒温室（２０〜２７℃）で放置し、黴の発生状態を２週間までは２日間隔、２週間以上は１週間間隔で観察した。なお、シャーレは各２個設置し、培地の乾燥を防ぐため1週間経過ごとに新品と交換した。結果を表１に示す。表中、上、中、底のいずれのシャーレにも黴が発生しない期間を有効期間として表示した。なお、防菌防黴薬剤を用いない場合を対照とした。表１には、蓋を開いた直後の臭気を２週間間隔で官能検査により下記4段階評価した結果も併せて示す。
◎：防菌防黴剤の臭気を感じない
○：防菌防黴剤の臭気をわずかに感じるが不快ではない
△：防菌防黴剤の臭気を明らかに感じ、若干不快である。
×：防菌防黴剤の臭気を強く感じ、不快である。
【００３１】
評価試験２（防菌防黴効果評価試験Ｂ：下駄箱想定）
評価試験１で調製したサンプル１〜１１を、巾７００ｍｍ×高さ７５０ｍｍ×奥行き４００ｍｍの木製、引き戸式、4段棚の下駄箱の最上階天井に評価試験１と同一の方法で設置し、評価シャーレを各段に2個ずつ置いて、朝、夕2回10分間引き戸を開放した。他の条件は評価試験１と同様にして、防菌防黴効果評価試験を行った。結果を表１に示す。
【００３２】
評価試験３（防菌防黴効果評価試験Ｃ：流し台下収納庫想定）
評価試験１で調整したサンプル１〜１１を、巾７００ｍｍ×高さ５００ｍｍ×奥行き５００ｍｍの樹脂張り、開き戸式、２段棚の箱の最上階天井に評価試験１と同一の方法で設置し、評価シャーレを各段に2個ずつ設置して、朝、夕2回10分間引き戸を開放した。他の条件は評価試験１と同様にして防菌防黴効果評価試験を行った。結果を表１に示す。
【００３３】
【発明の効果】
本発明の閉鎖空間用防菌防黴剤、また、閉鎖空間内の防菌防黴方法によれば、無臭又は微臭性気化性防菌防黴成分が気化して細菌や黴の繁殖を防止するため、洗濯機の洗濯槽の裏側や収納物が多く、かつ収納物の形状が複雑であり通常の殺菌剤や防菌防黴剤では細菌や黴の除去や繁殖防止が困難な下駄箱や流し台下収納庫等の防菌防黴を効果的に達成することができる。また、無臭又は微臭性の気化性防菌防黴剤を使用し、かつ気化性防菌防黴剤の特性に合わせて気化性防菌防黴剤を多分子包接化合物としたり包装フィルムを選択して、気化性防菌防黴剤の気化速度を制御することにより、気化性防菌防黴剤の臭気を抑制し、防菌防黴剤の使用による洗濯衣類や収納物等の異臭を嫌うものへの臭気付着を防止するとともに、使用者に不快感を与えなくすることができる。また、防菌防黴剤の気化速度が制御できるため、長期にわたり防菌防黴効果を維持できるとともに、余分な成分の気散による人体や環境への影響も抑制することができる。
【図面の簡単な説明】
【図１】本発明の洗濯機用防菌防黴剤を示す斜視図である。
【図２】本発明の洗濯機用防菌防黴剤を示す斜視図である。
【図３】本発明の洗濯機用防菌防黴剤を示す断面図である。
【図４】本発明の洗濯機用防菌防黴剤を示す斜視図である。
【図５】本発明の洗濯機用防菌防黴剤を示す断面図である。
【図６】本発明の洗濯機用防菌防黴剤を示す斜視図である。
【符号の説明】
１・・・・・・洗濯機
１ａ・・・・・・蓋
２・・・・・・袋
２ａ・・・・・・通気性、非通水生フィルム
２ｂ・・・・・・非通気性フィルム
３・・・・・・シート
３ａ・・・・・・不織布
３ｂ・・・・・・格子状の接着部
４・・・・・・通気性収納容器
４ａ・・・・・・収納部
４ｂ・・・・・・２枚の通気板
４ｃ・・・・・・固定部
４ｄ・・・・・・スリット状の外側開口部
４ｅ・・・・・・スリット状の内側開口部
Ｍ・・・・・・防菌防黴薬剤
Ｓ・・・・・・接着剤[0001]
BACKGROUND OF THE INVENTION
The present invention is a place where there is a lot of moisture and microorganisms such as bacteria and wrinkles easily propagate in closed spaces with poor ventilation, such as a washing tub of a washing machine, a shoebox, a storage under a sink, and clothes, shoes , Odorless or slightly odorous antibacterial and antifungal agents for closed spaces used in places where strong odorous chemicals cannot be used due to dislike of odor transfer to cooking utensils, etc.黴 About the method.
[0002]
[Prior art]
Washing tubs, especially fully automatic washing tubs, have a lot of unreachable space, and the problem is that cocoon breeds using washing sewage and detergent waste as a nutrient source. Chlorine detergents and percarbonates Although the wrinkle removal agent which consists of etc. is marketed, the structure of a washing tub is complicated and it is difficult to apply | coat a concentrated liquid directly to the wrinkle which generate | occur | produced on the back surface. For this reason, a method of filling the washing tub with water, dissolving a chemical such as a disinfectant and leaving it for a certain period of time has been adopted, but with such a method, the capacity of the washing tub is large and it is difficult to increase the concentration of the drug. In addition, it was necessary to leave for a long time, and the work was time consuming and troublesome. Moreover, there also existed a problem that the top of the washing tub which cannot store water could not be removed.
[0003]
In addition, shoes and boots are stored in the clog box, but because of moisture from sweat and wet shoes, the bacteria propagate and produce an unpleasant odor. There was a problem that the bag shortened the life of the shoes. In addition, cooking utensils such as pans and frying pans are often stored in the storage section under the sink, but it is unpleasant and sanitary because it is in a humid state where bacteria and straws have propagated. It was. As antibacterial and antifungal methods in these places, desiccants are generally used, but the effect is insufficient and the propagation of bacteria and moths cannot be prevented.
[0004]
Containers filled with sublimable or vaporizable antibacterial and antifungal agents are permeable to microporous membranes with micropores of several microns or less of fluororesin and polyurethane, and gases such as silicone resin and polyaminourethane resin There is known a refrigerator which is formed of a non-porous membrane having a molecular gap to be made and a container in which gas permeation is ensured is disposed in the refrigerator so as to suppress the growth of spoilage bacteria in the refrigerator ( Japanese Patent Laid-Open No. 3-164681). Further, a deodorizing, antibacterial, insect repellent foam (Japanese Patent Laid-Open No. 8-24321) in which a compound in which an essential oil component is included in a host compound is supported on a foam such as polyethylene, or cyclodextrin inclusion including hinokitiols An antibacterial stretch film for food packaging having a layer containing a compound in polypropylene or the like (JP-A-4-359029) is also known.
[0005]
However, such antibacterial and antifungal agents are effective in places where the temperature is low and microorganisms have a low fertility, such as in refrigerators, and in food packaging films where the antibacterial agent is vaporized and completely sealed from the entire surface of the packaging film. Demonstrated, but it was vaporized because it was hot and humid, and the ability of microorganisms to grow was strong, such as a washing tub in a washing machine, a shoebox, and a sink under a sink It was difficult to prevent the growth of microorganisms in a place where the antibacterial and fungicidal agents were outside the system.
[0006]
On the other hand, the present inventors have proposed a fungicide and fungicide for a washing machine (Japanese Patent Application No. 2001-369082) containing a vaporizable fungicide and fungicide such as a natural essential oil component as an active ingredient. In addition, an antibacterial agent for closed spaces such as a storage under a washstand containing aromatic isothiocyanate as an active ingredient (Japanese Patent Laid-Open No. 2001-220304), dimethyl fumarate, monomethyl fumarate, or diethyl fumarate is ventilated. Also known is a method for preventing germs and deodorizing septic waste stored in an adhesive packaging material (Japanese Patent Laid-Open No. 11-21202). However, these drugs are effective as antibacterial and antifungal agents, but they all have a strong odor peculiar to the drugs, and when used in washing machines, they are used for odor adherence to clothing and used as a clog box. In some cases, odor adheres to shoes, and when used in a sink under storage, not only odor adheres to stored items, but also the user feels a strong odor when opening the lid or door. It was difficult to put to practical use.
[0007]
[Problems to be solved by the invention]
The problem of the present invention is that by using a vaporizable antibacterial and fungicidal agent, the back side of a washing tub in a washing machine, the inside of a shoe in a shoe box, a storage under a sink, etc. It is possible to suppress the occurrence of fungi and fungi even in places where it is difficult to use, and by using a slightly odorous vaporizable antibacterial and fungicidal agent as an active ingredient, laundry clothes, shoe shoes and sinks An object of the present invention is to provide a closed space antibacterial / antifungal agent and a closed space antibacterial / antibacterial method that does not cause odors to adhere to items stored in a lower storage, and does not cause these users to feel unpleasant odors.
[0008]
[Means for Solving the Problems]
In order to efficiently perform antibacterial and antifungal activities, such as inside a washing machine having a complicated shape, a clog box storing shoes and boots, and a sink under storage storing cooking utensils and foods, etc. Is suitable for vaporizing antibacterial and antifungal agents that diffuse and penetrate into the corners of complex shaped spaces, and that are effective at low concentrations, especially for laundry clothes and stored items. We paid attention to the fact that odorless or slightly odorable vaporizable antibacterial and antifungal agents that do not allow the odor of the agent to adhere are suitable. Therefore, (1) by using a vaporizable antibacterial and fungicidal compound as an active ingredient and controlling the vaporization rate of the vaporizable substance, the antibacterial and antifungal effect can be obtained over a long period of time. (2) The usage time is about 1 to 2 hours a day, and the clog box and sink storage are opened and closed several times a day. Even if the closed space condition continues for a long time, such as at night or during the day, antibacterial protection It should be used effectively without waste and has no effect on the human body or surroundings. (3) Can be easily mounted on the back of a washing machine, a shoebox, the ceiling or wall of a sink under the sink. , (4) The concept was that the odors of the vaporizing antibacterial and antifungal agent would not adhere to the items stored in the laundry, clogs, and sinks under the sink, and that no unpleasant odor would be felt when the lid or door was opened. As a result, it is vaporizable and has an odorless or slightly odorous antifungal agent, preferably The antibacterial and fungicidal agent containing the component as a polymolecular inclusion compound is fixed and used with an adhesive or an adhesive on the back side of the lid of the washing machine, on the ceiling or wall of the clog box or the sink under the sink. As a result, a remarkable antibacterial / antifungal effect can be obtained in the washing tub of the washing machine, the clog box, and the sink under the sink, and the odor of the antibacterial / antifungal agent does not adhere to stored items such as laundry and shoes. I found out. Furthermore, the present inventors store the antibacterial / antifungal agent in a bag having a breathable film or a film that allows the antibacterial / antifungal component to permeate, sandwich the film into a sheet, or mix it with fibers. By forming into a sheet or plate shape or storing in a breathable container, the antibacterial and antifungal action can be obtained over a long period of time, the odor of the antibacterial and antifungal agent can be further reduced, It is easy to fix on the back of the lid of the washing machine, the ceiling or wall of the clog box or sink under storage, and even when used in situations where it gets wet, such as splashes of washing water, it is adequate to prevent germs It has been found that a wrinkle effect can be obtained, and the present invention has been completed.
[0009]
That is, the present invention (1) Presence in uniform mixed state with silica gel fine powder or diatomaceous earth An antibacterial / antifungal agent for closed spaces, characterized by containing an odorless or slightly odorizable vaporizing antibacterial / antifungal component (2) Formula [I]
[0010]
[Chemical formula 2]

[0011]
(Where X is (CH ₂ ) _n N is 0, 1, 2 or 3, and R ¹ ~ R ⁸ May be the same or different, and a hydrogen atom, C1-C6 An alkyl group, an optionally substituted phenyl group, a halogen atom or C1-C6 An alkoxy group is shown. ) Tetrakisphenol as a host compound It is a polymolecular inclusion compound An antibacterial and antifungal agent for closed spaces, characterized by containing an odorless or slightly odorizable vaporizing antibacterial and antifungal component Agents and , (3) The host compound is 1,1,2,2-tetrakis (hydroxyphenyl) ethane or 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ) Eta In It is characterized by being (2) Antibacterial and fungus for enclosed space as described Agents and , (4) The odorless or slightly odorizing vaporizing antibacterial and antifungal component is one or more components selected from dialkyl fumarate, higher alcohols having 6 to 20 carbon atoms, and salicylic acid. (1) ~ (3) Antibacterial and fungus for closed space according to any one of Agents and , (5) The dialkyl fumarate is one or more components selected from dimethyl fumarate, dinormal butyl fumarate, diheptyl fumarate, dihexyl fumarate and dioctyl fumarate, (4) Antibacterial and fungus for enclosed space as described Agents and , (6) It is characterized in that at least a part is stored in a bag formed of a film that allows the passage of the odorless or slightly odorizable vaporizing antibacterial and antifungal component. (1) ~ (5) An antibacterial and antifungal agent for closed spaces according to any one of (7) The odorless or slightly odorizing antibacterial and antifungal ingredient is dimethyl fumarate (6) Antibacterial and fungus for enclosed spaces as described in Agents and , (8) At least partly odorless or Strong enough not to feel unpleasant odor It is housed in a bag formed of a breathable film that allows the vapor of a slightly odorizing vaporizing antibacterial and fungicidal component to pass through. (1) ~ (7) Antibacterial and fungus for closed space according to any one of Agents and , (9) The breathable film is a breathable / non-water-permeable film (8) Antibacterial and fungus for enclosed space as described Agents and , (10) It is stored in a breathable storage container (1) ~ (9) Antibacterial and fungus for closed space according to any one of Agents and , (11) A warming body is installed in the breathable storage container to promote evaporation of the slightly odorous, vaporizable antibacterial and fungicidal agent. (10) Antibacterial and fungus for enclosed spaces as described in To the agent Related.
[0012]
The present invention also provides: (12) It is characterized by being fixed with an adhesive or adhesive. (1) ~ (11) Antibacterial and fungus for closed space according to any one of Agents and , (13) It is characterized in that the surface of the antibacterial / antifungal surface fixed with an adhesive or an adhesive is odorless or slightly odorous and does not allow vapor to pass through the antibacterial / antifungal component. (12) Antibacterial and fungus for enclosed spaces as described in Agents and , (14) The closed space is a space inside the washing machine (1) ~ (13) Antibacterial and fungus for closed space according to any one of Agents and , (15) The enclosed space is a space inside a shoe rack (1) ~ (13) Antibacterial and fungus for closed space according to any one of Agents and , (16) The closed space is a storage space under the sink (1) ~ (13) Antibacterial and fungus for closed space according to any one of Agents and , (17) (1) ~ (16) The present invention relates to an antibacterial / antifungal method for closed spaces, characterized in that the antibacterial / antifungal agent for closed spaces according to any one of the above is used.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
As the antibacterial / antifungal agent for closed spaces of the present invention, it contains an odorless or slightly odorous and vaporizable antibacterial / antifungal component, the back side of the lid of the washing machine, the ceiling or the wall surface of the storage box or under the sink Any one may be used as long as it is configured so that it can be used in a fixed state, etc., but the vaporizable antibacterial and fungicidal component is contained as a solid form multi-molecular inclusion compound. preferable.
[0014]
As the odorless or slightly odorizable antibacterial / antifungal component of the present invention, the vaporized vapor has an antibacterial / antifungal action, and the odor is strong enough not to feel an odorless or unpleasant odor. Natural extracts and synthetic compounds may be used as long as they are natural. Specific examples include dialkyl fumarate, higher alcohols having 6 to 20 carbon atoms, salicylic acid and the like, and particularly preferred are normal butyl fumarate, dipentyl fumarate, dihexyl fumarate, diheptyl fumarate, dioctyl fumarate, and the like. It can be illustrated. Since dimethyl fumarate has a slightly strong odor compared to the above drugs, it produces an unpleasant odor when used as it is, but has a strong antibacterial and antifungal effect and is solid so that the remaining amount of the drug can be visually determined. Because there are advantages, it is preferable to take measures such as controlling the vapor concentration by selecting the thickness of the permeable film or reducing the saturated vapor concentration of dimethyl fumarate in a closed space as a polymolecular inclusion compound. Can be used for Examples of the higher alcohol having 6 to 20 carbon atoms include hexyl alcohol, octyl alcohol, dodecyl alcohol (lauryl alcohol) octadecyl alcohol (stearyl alcohol), and the like.
[0015]
The vaporizable antibacterial / antifungal component described above is preferably contained as a polymolecular inclusion compound because an antibacterial / antifungal action can be obtained over a long period of time. The vaporization rate of the vaporizable antibacterial and fungicidal component can be adjusted by the configuration of the packaging material, the opening area of the container, etc., and can be dissolved in a solvent or gel to delay the vaporization rate or kneaded with the resin. By molding or microencapsulating antibacterial and antifungal ingredients, the vaporization rate can be delayed and the antibacterial and antifungal effect can be sustained. Since the surplus vaporizable antibacterial and fungicidal component is included in the host compound again and maintains a saturated equilibrium state, the saturated vapor pressure of the guest compound is 1 to It is reduced to several tenths. For this reason, in places such as a washing machine, a shoebox, and a sink under storage that have been closed for a long time, an excellent characteristic that the effective period of the antibacterial / antifungal agent can be greatly extended is exhibited. For example, in a washing machine that is used only once a day in a normal home, only once every 2-7 days in a small family, and is left with the lid closed for a long time, most of the time zone is Since the vaporized antibacterial and fungicidal component has a saturated vapor pressure, the saturated concentration of the gas of the vaporizable antibacterial and fungicidal component itself can be reduced by making the vaporized antibacterial and fungicidal component a polymolecular inclusion compound. The vaporizing antibacterial and antifungal effect time can be extended several times to several tens of times. In particular, by selecting a multi-molecular inclusion compound consisting of a combination of a host compound and a guest compound, the vaporizable antibacterial / antifungal effect can be maintained over a long period of time while preventing the loss of the vaporizable antifungal / antifungal component. can do. Furthermore, since the amount of the vaporizable antibacterial and antifungal component that leaks out of the washing machine is reduced with the reduction of the disappearance amount of the vaporizable antibacterial and antifungal component, the influence on the human body and the like can be avoided.
[0016]
As described above, the host compound for inclusion of the guest compound when the vaporizable antibacterial / antifungal component is a multimolecular inclusion compound is not particularly limited as long as it is a known host compound capable of forming a multimolecular inclusion compound. However, tetrakisphenol represented by the general formula [I] is preferable. In the formula [I], X represents (CH ₂ ) _n N is 0, 1, 2 or 3, and R ¹ ~ R ⁸ May be the same or different from each other, and each represents a hydrogen atom, a lower alkyl group, a phenyl group optionally having a substituent, a halogen atom or a lower alkoxy group. Examples of the lower alkyl group include C1-C6 alkyl groups such as methyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, and cyclohexyl group. In addition, examples of the substituent of the phenyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a C1-C6 lower alkyl group. The halogen atom includes a fluorine atom and a chlorine atom. , A bromine atom, an iodine atom, and the like. Examples of the lower alkoxy group include C1-C6 lower alkoxy groups such as a methoxy group, an ethoxy group, and a t-butoxy group.
[0017]
Specific examples of the compound represented by the general formula [I] include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4). -Hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-4-hydroxyphenyl) ethane, 1,1,2, 2-tetrakis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-tert-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis ( , 5-Di-t-butyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-fluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5 -Difluoro-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3,5-dimethoxy-4-hydroxy) Phenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-bromo-5-methyl-4-hydroxy) Phenyl) ethane, 1,1,2,2-tetrakis (3-methoxy-5-methyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-t-butyl-5- Til-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5-bromo-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-chloro-5- Phenyl-4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis [(4-hydroxy-3-phenyl) phenyl] ethane, 1,1,3,3-tetrakis (4-hydroxyphenyl) propane, , 1,3,3-tetrakis (3-methyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1,3,3 -Tetrakis (3-chloro-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dichloro-4-hydroxyphenyl) propane, 1,1,3 , 3-tetrakis (3-bromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3 -Phenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-diphenyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-methoxy-4-hydroxy) Phenyl) propane, 1,1,3,3-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3-t-butyl-4-hydroxyphenyl) propane, 1,1,3,3-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 1,1,4,4-tetrakis (4-hydroxy) Enyl) butane, 1,1,4,4-tetrakis (3-methyl-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimethyl-4-hydroxyphenyl) butane, 1,4,4-tetrakis (3-chloro-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dichloro-4-hydroxyphenyl) butane, 1,1,4,4- Tetrakis (3-methoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dimethoxy-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-bromo- 4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-dibromo-4-hydroxyphenyl) butane, 1,1,4,4-tetrakis (3-t-butyl- -Hydroxyphenyl) butane, 1,1,4,4-tetrakis (3,5-di-t-butyl-4-hydroxyphenyl) butane, among others, 1,1,2,2-tetrakis (Hydroxyphenyl) ethane and 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenylethane) are preferred. These tetrakisphenol compounds may be used alone or in combination of two or more.
[0018]
The odorless or slightly odorizable antibacterial / antifungal component of the present invention can be mixed with other shaping agents, fragrances, etc., and formed into tablets or powdered antifungal / antifungal agents. In addition, the vaporizable antibacterial and fungicidal agent may be formed into a paper shape together with pulverized pulp and fibers, or the vaporizable antibacterial and antifungal component may be mixed with fibers to form a thick nonwoven fabric or the like. it can.
[0019]
The antibacterial / antifungal agent containing the odorless or slightly odorizable vaporizing antibacterial / antifungal component of the present invention may be used by being fixed to the back side of the lid of the washing machine, the ceiling or the wall of the storage box or sink under storage. Any method can be used as long as it can be installed / placed at a target location, and the antibacterial / antifungal agent is directly sandwiched and fixed with a clip or attached with an adhesive tape. However, if it is installed on the back side of the lid of the washing machine, at least a part of it, such as one side or both sides, is prevented so that the washing water is scattered and the vaporization of the vaporizable antibacterial and antifungal agent is not inhibited. The antibacterial / antifungal agent formed into a sheet by sandwiching it between a film through which the component permeates or a breathable film is used by fixing it with an adhesive or an adhesive, or at least a part of such as one side or both sides Molded with a transparent film or breathable film The antibacterial / antifungal agent contained in the bag may be fixed with an adhesive or an adhesive, and the air permeable film may be a breathable / non-water permeable film. It is preferable because water droplets can be prevented from coming into contact with the antibacterial / antifungal agent, and inhibition of vaporization of the vaporizable antifungal / antifungal component can be avoided. In addition, a method in which a vaporizable antibacterial / antifungal component is uniformly mixed with fibers and formed into a breathable sheet or plate and fixed with an adhesive, an adhesive, etc. A glaze component, a bag containing the glaze component, or a sheet or plate containing a vaporizable antibacterial / antifungal component, is stored in a breathable storage container, and is used with an adhesive or adhesive. It is also possible to use a fixed method.
[0020]
In addition, in this invention, when fixing the bag or sheet | seat of an antibacterial and antifungal component with an adhesive or an adhesive, or the bag or sheet | seat of a breathable film, the side which uses an adhesive or an adhesive is used. The surface of the bag or sheet is preferably formed of a film or plate made of a material that does not allow the antibacterial and antifungal component to permeate or vapor passes therethrough. In general, since many antibacterial and antifungal components have a function as a solvent for dissolving an adhesive and an adhesive, a film that permeates the antifungal and antifungal component or allows vapor to pass through is used. If it is used on the side, the trouble of peeling off from the place where the antibacterial and fungicidal agent of the present invention is fixed will occur. In addition, when the antibacterial / antifungal component is stored in a bag or sheet of a film and used, the antibacterial / antifungal component is liquid so that the antibacterial / antifungal component can be constantly vaporized regardless of the passage of time. In this case, it is preferable to use the product by uniformly impregnating fine silica gel powder or fine clay mineral powder, and even when the antibacterial / antifungal component is a solid, it is used in the case of a compound having a low vaporization rate or a compound having a low melting point. Fine particles by mixing uniformly with silica gel fine powder or clay mineral fine powder at a temperature higher than the melting point of the fungicide antibacterial ingredient, or by mixing the antibacterial fungus ingredient with silica gel fine powder or clay mineral fine powder and then air pulverizing the mixture If the is stabilized, vaporization of the antibacterial / antifungal component can be performed constantly regardless of the passage of time.
[0021]
The closed space antibacterial / antifungal method of the present invention is not particularly limited as long as it is a method using the above-described closed space antifungal / antifungal agent. Use a multi-molecular inclusion compound consisting of a combination of a host compound and a guest compound so that the concentration of the vaporizable antibacterial and fungicidal component when the equilibrium is reached in the closed space by contact will be the effective concentration of the antibacterial and antifungal component The method is preferred.
[0022]
According to the antibacterial / antifungal method for closed spaces of the present invention using the antibacterial / antifungal agent for closed spaces of the present invention, since the antibacterial / antifungal component is heavier than air, the reverse side of the lid of the washing machine, Vaporizing antibacterial and fungicidal components fixed on the ceiling and wall of the sink under the sink evaporate and move to the lower part of the closed space while mixing with the air in the closed space, and in every corner of the complex shaped space Diffusion and permeation until antibacterial and antifungal effects are obtained. In addition, when the vaporizable antibacterial / antifungal component is used as a multimolecular inclusion compound, the vaporization rate of the vaporizable antifungal / antifungal component can be controlled, and the vaporizable antibacterial / antifungal component, which is a guest compound, can be controlled. Once the soot component is released, it is included in the host compound again to maintain a saturated equilibrium state, so that the saturated vapor pressure of the gas is reduced, that is, the saturated concentration of the vaporizable antibacterial and antifungal component without a closed space is reduced. It can be reduced, and the amount of disappearance of the vaporizable antibacterial and antifungal component can be reduced. In particular, since washing machines are used for a short time and are often left with the lid closed for a long time, the vaporizable antibacterial / antifungal agent is kept saturated at a low concentration, and the antibacterial / antifungal effect is prolonged. In addition to being able to be obtained over a period of time, the amount of the vaporizable antibacterial and fungicidal agent leaking from the washing machine is also reduced, the influence on the human body and the like can be suppressed, and the maximum effect can be obtained with a small amount. In addition, even when used in situations where the product gets wet, using aeration / non-water-permeable film can prevent the splash of washing water from coming into contact with it, preventing the vaporization of the vaporizable antibacterial and antifungal component. Therefore, when using the washing machine, it is possible to avoid the repetition of the operation of taking out the antibacterial / antifungal agent and fixing it again at the end of washing.
[0023]
Hereinafter, the case where the antibacterial / antifungal agent for closed spaces of the present invention is used in a washing machine will be described with reference to the drawings. However, the scope of the present invention is not limited to these examples.
As shown in FIG. 1, the antibacterial / antifungal agent for a washing machine according to the present invention comprises an antibacterial / antifungal agent M containing, as a solid, a vaporizable antibacterial / antifungal component that is heavier than air when vaporized. 1 is installed on the back side of the lid 1a.
[0024]
The antibacterial and antifungal agent M is in a solid or powder form, and as shown in FIGS. 2 and 3, the surface facing the inside of the washing machine 1 is a breathable / water-impermeable film 2a and faces the lid 1a. The surface is accommodated in a bag 2 formed of a non-breathable film 2b. The air / non-water-permeable film 2a is formed with fine pores of 1 to 5 μm formed in a hydrophobic film, and gas particles can permeate through the pores but water particles cannot permeate. This prevents the stored antibacterial / antifungal agent M from coming into contact with water even if the droplets are attached. Examples of the breathable / non-water-permeable film 2a include a Tyvek film (trade name: manufactured by DuPont) and an NF sheet (trade name: manufactured by Tokuyama Corporation). The bag 2 is fixed to the lid 1a of the washing machine 1 with an adhesive S.
[0025]
Moreover, as shown in FIG. 4, the antibacterial / antifungal agent for washing machines, the vaporizable antibacterial / antifungal component as it is, or the antibacterial / antifungal agent M is sandwiched between the nonwoven fabrics 3a, and the lattice-shaped adhesive portions 3b You may comprise with the sheet | seat 3 formed by adhere | attaching. In addition, as antibacterial and antifungal agents for washing machines, powdered antibacterial and antifungal agents M and vaporizing antibacterial and antifungal ingredients are added to pulverized pulp, mixed and dried on paper, raw fiber and vaporizable A non-woven fabric formed by mixing antibacterial and antifungal components thickly, a thick non-woven fabric impregnated with a solvent in which antibacterial and antifungal components are dissolved in paperboard, or those stored in a bag 2 can also be used. .
[0026]
FIG. 5 shows an example of a breathable storage container 4 for storing the antibacterial / antifungal agent M, and the breathable storage container 4 is fixed to the lid 1a of the washing machine by the adhesive S. It has a fixed portion 4c and a storage portion 4a detachably provided on the fixed portion 4c. The bottom surface of the storage portion 4a has a plurality of slit-like outer openings 4d and inner openings 4e alternately. The two ventilation plates 4b are provided so as to be positioned, and as shown in FIG. 6, the two ventilation plates 4b are installed so that the positions of the slit-shaped openings 4d and 4e do not coincide with each other. In addition, it is mounted in parallel to the storage portion 4a. Through the openings 4d and 4e provided in the ventilation plate 4b, the vaporized antibacterial and fungicidal component can be diffused into the washing machine 1, and splashes of washing water are stored in the storage container 4. It does not come into direct contact with the antibacterial / antifungal agent M or the like. When the antibacterial / antifungal agent stored in the storage container 4 is consumed, the storage portion 4a can be removed from the fixing portion 4c, and the antibacterial / antifungal agent M or the like can be replaced with a new one.
[0027]
Furthermore, in the visible part of the bag 2, the sheet 3, the storage container 4, and the antibacterial / antifungal agent formed in a plate shape in which the antibacterial / antifungal agent M is stored, it reacts with the vaporizable antibacterial / antifungal agent. It is also possible to provide a signal marker made of a substance that can recognize changes such as coloring and discoloration, and to detect consumption of the vaporizing antibacterial and antifungal component by visually observing the changes. In addition, the method of fixing the bag 2, the sheet 3, and the storage container 4 containing the antibacterial / antifungal agent M to the lid of the washing machine is not limited to the adhesive, and an adhesive tape is used or attached to the adhesive surface. You may make it adhere | attach to the lid | cover of a washing machine except a release paper.
[0028]
【Example】
<Preparation of antibacterial / antifungal agent>
An antibacterial / antifungal agent having the composition shown in Table 1 containing the odorless or slightly odorizable antibacterial / antifungal component of the present invention and a comparative control vaporizable antibacterial / antifungal component was prepared. The antibacterial / antifungal agent was prepared by mixing a vaporizable antibacterial / antifungal component with silica gel fine powder and / or diatomaceous earth to form a powder. When using a vaporizable antibacterial and fungicidal component as a multimolecular inclusion compound, add 50 g of 1,1,2,2-tetrakis (hydroxyphenyl) ethane (TEP) as a host compound to 500 mL of methanol, and The mixture was heated and dissolved, 100 g of the guest compound described in Table 1 was gradually added thereto, and the mixture was stirred at 60 ° C. for 30 minutes to react, and insoluble matters were removed by filtration. The filtrate was allowed to stand overnight at room temperature, and the resulting crystals were filtered, washed with methanol, and then vacuum dried at 40 ° C. for 1 hour to obtain a polymolecular inclusion compound. In Table 1, TEP-dimethyl fumarate was TEP: dimethyl fumarate = 1: 2 (mol).
[0029]
[Table 1]

[0030]
Evaluation test 1 (antibacterial / antifungal effect evaluation test A: assumption of washing tub)
A predetermined amount of each of the 11 antibacterial / antifungal agents obtained in Example 1 (corresponding to 5 g of the vaporizable antibacterial / antifungal agent, described in Table 1), one side of which is a breathable / non-water-permeable film (NF sheet: (stock) ) Film A made by Tokuyama Corp .; air permeability 50 seconds / 100 m) or film B made permeable film (low density polyethylene film, thickness 0.05 mm), the other side is 0.06 mm nylon and low density polyethylene 0 Was stored in a 100 mm × 120 mm bag made of .05 laminate film, and the surroundings were heat-sealed to prepare drug storage samples 1 to 11. Next, place a petri dish of potato dextrol agar medium inoculated with 0.1 mL of black spore (Aspergillus niger IFO No442) spore suspension at the top, middle, and bottom in a 70-L plastic bucket. The above-mentioned drug storage samples 1 to 11 were fixed with an adhesive tape with a ventilation / non-water-permeable film (film A) or a permeable film (film B) facing downward. A large petri dish filled with water was placed on the bottom of the plastic bucket, and the lid was left standing in a wet state. Once a day for 1 hour (saturated for 2 weeks or more, leave with the lid closed) Leave the lid in a constant temperature room (20-27 ° C) with the lid removed, and leave the wrinkle for 2 days until 2 weeks. Observation was performed at intervals of 1 week for intervals of 2 weeks or more. Two petri dishes were installed and replaced with new ones every week to prevent the culture medium from drying. The results are shown in Table 1. In the table, the period in which no wrinkles occurred in any of the top, middle and bottom petri dishes was displayed as the effective period. The case where no antibacterial / antifungal agent was used was used as a control. Table 1 also shows the results of the following four-level evaluation of the odor immediately after opening the lid by a sensory test at intervals of two weeks.
A: No odor of antibacterial and antifungal agent
○: Slight odor of antibacterial / antifungal agent but not unpleasant
Δ: The odor of the antibacterial and antifungal agent is clearly felt and is slightly uncomfortable.
X: The odor of the antibacterial / antifungal agent is strongly felt and uncomfortable.
[0031]
Evaluation test 2 (antibacterial and antifungal effect evaluation test B: assumed to be a clog box)
Samples 1 to 11 prepared in Evaluation Test 1 are installed in the same manner as in Evaluation Test 1 on the top floor ceiling of a wooden, sliding door type, 4-tier shelf clog box with a width of 700 mm, a height of 750 mm, and a depth of 400 mm. Two petri dishes were placed on each stage, and the sliding doors were opened twice a morning and evening for 10 minutes. Other conditions were the same as those in Evaluation Test 1, and an antibacterial and antifungal effect evaluation test was conducted. The results are shown in Table 1.
[0032]
Evaluation test 3 (antibacterial / antifungal effect evaluation test C: assuming sink under sink)
Samples 1 to 11 prepared in Evaluation Test 1 are installed in the same manner as Evaluation Test 1 on the top floor ceiling of a resin-coated, hinged door type, two-tier shelf box with a width of 700 mm, a height of 500 mm, and a depth of 500 mm. Two petri dishes were installed on each stage, and the sliding doors were opened twice a morning and evening for 10 minutes. The other conditions were the same as in the evaluation test 1, and the antibacterial and antifungal effect evaluation test was conducted. The results are shown in Table 1.
[0033]
【The invention's effect】
According to the antibacterial / antifungal agent for closed spaces of the present invention and the antibacterial / antifungal method for closed spaces, the odorless or slightly odorizable vaporizable antibacterial / antifungal component is vaporized to prevent the growth of bacteria and sputum Therefore, there are many backsides and items stored in the washing tub of the washing machine, and the shape of the items is complicated, and it is difficult to remove bacteria and wrinkles and prevent breeding with normal fungicides and fungicides. It is possible to effectively achieve antibacterial and fungicidal measures such as storage under the sink. In addition, use a odorless or slightly odorizable vaporizable antibacterial / antifungal agent, and make the vaporizable antibacterial / antifungal agent a multimolecular inclusion compound or a packaging film in accordance with the characteristics of the vaporizable antibacterial / antifungal agent. By selecting and controlling the vaporization rate of the vaporizable antibacterial / antifungal agent, the odor of the vaporizable antibacterial / antifungal agent can be suppressed, and the use of the antibacterial / antifungal agent can reduce the odor of washing clothes and stored items. It is possible to prevent the odor from adhering to the object to be disliked and to make the user uncomfortable. In addition, since the vaporization rate of the antibacterial / antifungal agent can be controlled, the antibacterial / antifungal effect can be maintained over a long period of time, and the influence on the human body and the environment due to the diffusion of excess components can also be suppressed.
[Brief description of the drawings]
FIG. 1 is a perspective view showing an antibacterial / antifungal agent for a washing machine according to the present invention.
FIG. 2 is a perspective view showing an antibacterial / antifungal agent for a washing machine according to the present invention.
FIG. 3 is a cross-sectional view showing the antibacterial / antifungal agent for washing machines of the present invention.
FIG. 4 is a perspective view showing an antibacterial / antifungal agent for a washing machine according to the present invention.
FIG. 5 is a cross-sectional view showing the antibacterial and antifungal agent for washing machines of the present invention.
FIG. 6 is a perspective view showing an antibacterial / antifungal agent for a washing machine according to the present invention.
[Explanation of symbols]
1. Washing machine
1a ... Lid
2 ... bag
2a ... Breathable, non-water-permeable raw film
2b ... Non-breathable film
3. Sheet
3a ... Nonwoven fabric
3b ・・・・・・ Lattice-like adhesive
4 ・・・・・・ Breathable storage container
4a ··· Storage section
4b ... ・ Two ventilation plates
4c ･･･ fixed part
4d ... Slit outer opening
4e ・・・・・・ Slit inner opening
M ・・・・・・ Antibacterial and antifungal agents
S ・・・・・・ Adhesive

Claims

An antibacterial / antifungal agent for closed spaces, which contains an odorless or slightly odorizable vaporizable antibacterial / antifungal component that is present in a uniform mixed state with silica gel fine powder or diatomaceous earth .

One general formula [I]

(Wherein, X represents (CH ₂₎ _n, n is 0, 1, 2 or 3, R ¹ to R ⁸ may be Some same or different, a hydrogen atom, C1 to C6 alkyl group, an optionally substituted phenyl group, odorless or fine a halogen atom or a possibly terminal clathrate compound that the tetrakisphenol the host compound represented by.) of an alkoxy group C1~C6 An antibacterial / antifungal agent for closed spaces, which contains an odorizable vaporizable antibacterial / antifungal component .

Host compound, 1,1,2,2-tetrakis claim 2, wherein the (hydroxyphenyl) ethane or 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane Antibacterial and antifungal agent for closed spaces.

The odorless or slightly odorizing vaporizing antibacterial and antifungal component is one or more components selected from dialkyl fumarate, higher alcohols having 6 to 20 carbon atoms, and salicylic acid. The antibacterial / antifungal agent for closed spaces according to any one of 3 above.

5. The closed space according to claim 4 , wherein the dialkyl fumarate is one or more components selected from dimethyl fumarate, dinormal butyl fumarate, diheptyl fumarate, dihexyl fumarate, and dioctyl fumarate. Antibacterial and antifungal agent.

The enclosed space prevention according to any one of claims 1 to 5 , wherein at least a part thereof is housed in a bag formed of a film that allows passage of an odorless or slightly odorizing vaporizing antibacterial and antifungal component. Antifungal agent.

The antibacterial / antifungal agent for closed spaces according to claim 6, wherein the odorless or slightly odorizing antibacterial / antifungal component is dimethyl fumarate.

At least partially according to any one of claims 1 to 7, characterized in that it is housed in a bag formed of a breathable film for passing steam odorless or faint odor of volatile Antibacterial and Antifungal component Antibacterial and antifungal agent for closed spaces.

The antibacterial and antifungal agent for closed spaces according to claim 8, wherein the air permeable film is an air permeable / non-water permeable film.

Antibacterial and Antifungal Agents for closed space according to any one of claims 1 to 9, characterized in that housed in the ventilation container.

The antibacterial / antifungal agent for closed spaces according to claim 10 , wherein a warming body that promotes evaporation of the slightly odorous vaporizable antibacterial / antifungal agent is installed in the breathable storage container.

The antibacterial and antifungal agent for closed spaces according to any one of claims 1 to 11 , wherein the antibacterial and antifungal agent for closed spaces is used by being fixed with an adhesive or an adhesive.

The closure according to claim 12 , wherein the material of the surface of the antibacterial / antifungal agent fixed with an adhesive or an adhesive is odorless or slightly odorous and does not allow vapor to pass through the antibacterial / antifungal component. Antibacterial and antifungal agent for space.

The antibacterial and antifungal agent for closed spaces according to any one of claims 1 to 13 , wherein the closed space is a space in a washing machine.

The antibacterial and antifungal agent for closed spaces according to any one of claims 1 to 13 , wherein the closed space is a space in a shoe rack.

The antibacterial / antifungal agent for closed spaces according to any one of claims 1 to 13 , wherein the closed space is a storage space under the sink.

An antibacterial / antifungal method for closed spaces, wherein the antibacterial / antifungal agent for closed spaces according to any one of claims 1 to 16 is used.