JP4035009B2 - A simple method for producing an iodine-containing article, an iodine gas sustained-release device having water resistance, and a disinfection system using them. - Google Patents
A simple method for producing an iodine-containing article, an iodine gas sustained-release device having water resistance, and a disinfection system using them. Download PDFInfo
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- JP4035009B2 JP4035009B2 JP2002202860A JP2002202860A JP4035009B2 JP 4035009 B2 JP4035009 B2 JP 4035009B2 JP 2002202860 A JP2002202860 A JP 2002202860A JP 2002202860 A JP2002202860 A JP 2002202860A JP 4035009 B2 JP4035009 B2 JP 4035009B2
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Description
【0001】
【発明の属する技術分野】
本発明は、ヨウ素を吸着したヨウ素徐放性高分子化合物をヨウ素ガス発生源とするヨウ素含有物品の簡易製造法に関するものである。
【0002】
【従来の技術】
従来から繊維シート状物にヨウ素を吸着させ、殺菌効果を発現せしめる試みがなされている。例えば特開平1−124688号公報には、ヨード錯体付加物を含有した殺菌性布地が開示され、かかる布地としてナイロン、アクリル等の繊維が記載されている。また特開平11−50376号公報にはヨウ素化合物を担持したビニロン不織布が開示されている。これらは何れもヨウ素化合物溶液に繊維シート状物を浸漬または塗布して、繊維にヨウ素を吸着せしめている。しかしながらヨウ素溶液を用いて繊維シート状物を処理するのは操作が煩雑な上ヨウ素を含む廃液の処理が必要となる問題がある。
【0003】
一方、病院等においては微生物による感染を防止するため手指や器物の消毒が極めて重要となっているが、普通用いられるビグアニド系殺菌剤、4級アンモニウム塩系殺菌剤、ポリビニルピロリドンとヨウ素の錯体、アルコール等は手荒れの問題、抗菌スペクトルの問題や使い勝手の問題等があり、すべての面で満足とは言えないため、さらに優れた消毒剤あるいは消毒システムの開発が望まれている。
【0004】
また病院手術室等で用いられる手洗い用の無菌水の蛇口を微生物逆汚染から守るため,蛇口内にヨウ素を吸着したプラスチックビーズを挿入し、ビーズから溶出するヨウ素を利用する方法が行われている。この方法は蛇口内に滞留する水を消毒することにより蛇口からの汚染を防止することを目的とするが、装置使用中は流出する水のために微生物汚染の心配はないので、その間水中にヨウ素が放出される必要がない。したがって使用中のヨウ素の放出を制限することはビーズの使用期間を長くもたせることになる。しかし従来法においてはビーズが直接水に接触するため装置使用時は加温された水によりヨウ素が無駄に消費される欠点があった。
【0005】
また従来、病院等において、器物を消毒するためには紫外線やホルムアルデヒドガスなどがよく用いられるが、高価な装置を必要としたり、人体に危険があったりして問題があった。
【0006】
さらに、病室内や床等の消毒についても充分に簡便で確実な方法があるとは言えず、また器物を液剤に浸漬する消毒において、コンタクトレンズのように一般ユーザーが実施する消毒は安全、確実さと簡便さが要求されるが、未だ理想的なものは出現していない状況である。
【0007】
【発明が解決しようとする課題】
本発明は、上述のごとき事情を背景としてなされたもので、本発明の目的は消毒用として病院や家庭で簡単に且つ安全に製造出来るヨウ素含有物品、特にヨウ素を含有する繊維シート状物の製造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】
本発明者らは上記目的を達成するため種々検討した結果、ヨウ素を吸着した高分子化合物をヨウ素ガス発生源として利用することにより、前記目的を達成することに成功し本発明に到達した。
【0009】
すなわち本発明はヨウ素を吸着した高分子化合物ををヨウ素ガス発生源として物品にヨウ素を吸着せしめることを特徴とするヨウ素含有物品の製造方法をその要旨とする。ヨウ素を吸着した高分子化合物として、ABS樹脂、AS樹脂、エチレン・ビニルアルコール共重合体、ポリアミド、ポリビニルアルコール、ホルマール化ポリビニルアルコール等からなる群から選ばれたビーズ、粉末、線維、フィルム、織物、不織布あるいはゲルなどが用いられる。
【0010】
そして前記ヨウ素を吸着した高分子化合物からヨウ素ガスを吸着せしめる物品としてポリアミドエピクロルヒドリン系樹脂またはポリアミン・ポリアミドエピクロルヒドリン系樹脂を含む繊維シート状物が好ましく用いられ、該ヨウ素含有繊維シート状物は水で濡らして用いることにより有力な消毒方法を提供することが出来る。
【0015】
なお。特開平9-67217号、特開平9-122655号、特開平10-165960号には、プラスチックにヨウ素を吸着せしめ、これと水を接触させることにより、水中にヨウ素を徐放する抗菌性組成物が開示されているが、本発明はプラスチックにヨウ素を吸着せしめ、これを水と接触させることなく、ヨウ素ガス徐放剤として用いる新規な方法を開発したものである。
【0016】
【発明の実施の形態】
本発明において、ヨウ素ガス発生源として用いるヨウ素を吸着した高分子化合物としては、ヨウ素吸着性を有する高分子化合物にヨウ素を吸着せしめたものを用いる。ヨウ素吸着性を有するプラスチックとしては、ABS樹脂、AS樹脂、エチレン・ビニルアルコール共重合体(EVOH)、エチレン・酢酸ビニル共重合体、ポリアミド、ポリアクリロニトリル、アクリロニトリル・塩化ビニル共重合樹脂、ポリウレタン樹脂、酢酸セルロース樹脂、ポリビニルアルコール、ホルマール化ポリビニルアルコール、ポリエステル、ポリエチレンオキサイド樹脂、デンプン、ポリビニルピロリドン共重合体(例えばビニルピロリドン・メタクリル酸メチル共重合体)等が用いられる。またヨウ素吸着性の乏しい樹脂であっても、上記のヨウ素吸着性樹脂を混合して成形することにより使用可能となる。
【0017】
上記プラスチックの中で特に望ましいのは、ヨウ素吸着性に優れている点でABS樹脂、AS樹脂、エチレン・ビニルアルコール共重合体(EVOH)である。一般にABS樹脂として市販されているものは、アクリロニトリル成分が20〜30重量%、スチレン成分が40〜70重量%、ブタジエン成分が10〜30重量%程度であるが、本発明においては何れも使用可能である。EVOH系樹脂としては、その共重合体中のエチレンの含有量が20〜50モル%のものを用いるのが好ましい。市販品としては日本合成化学工業(株)製のソアノール各種と(株)クラレ製のエバール各種の中でいずれの品種も使用することが出来る。
【0018】
ヨウ素を吸着した高分子化合物の形態としてはビーズ、粉末、繊維、織物又は不織布、フィルムまたはゲル等種々の形態で使用出来る。また射出成形、押し出し成形、圧縮成型等の熱成形による成形品も使用可能である。好ましい形態は使用方法、用途などによって異なるが、ヨウ素吸着工程の容易さの点ではビーズ状または粉末状が好ましい。ビーズ状の形態としてはプラスチック材料の射出成形用ペレットが、市販品をそのまま利用出来るので有利である。射出成形用ペレットを粉砕して細かくしたものを用いることもできる。
【0019】
ヨウ素吸着性高分子化合物材料(以下高分子材料と略記する)からヨウ素を吸着した高分子化合物を得るには高分子材料にヨウ素を吸着せしめる必要がある。ヨウ素の吸着には高分子材料をヨウ素溶液に浸漬する液相法でもよいが、気相法で行う方が操作性がよく、吸着量を高くすることが容易であり、また廃液が出ることもないので有利である。高分子材料へのヨウ素の吸着方法については、特開平10−165960号等に詳細に記述されている。すなわちヨウ素の気相吸着は、高分子材料と固体ヨウ素を密閉容器に入れ、50℃〜110℃に加熱することにより行われる。加熱は固体ヨウ素が全て高分子材料に吸着される迄行うがその時間は高分子材料の種類、形態及び吸着させるヨウ素量により異なる。
【0020】
上記高分子材料に対するヨウ素の吸着量は5〜200重量%が好ましい。粉末のように表面積の大きい材料ではヨウ素吸着量は比較的少なくてよく、表面積の小さい材料の場合は比較的多量を要する。望ましい吸着量はビーズ状の形態の場合10〜200重量%、特に好ましくは30〜150重量%(対プラスチック重量)である。粉末の場合はヨウ素吸着量は10〜100重量%(対プラスチック重量)程度が適当である。
【0021】
例えばABS樹脂成形用ペレットに対して100重量%のヨウ素を吸着せしめる場合、密閉容器中で樹脂ペレットと等量の固体ヨウ素と混合し、50〜100℃で1〜10時間加熱することによりヨウ素を完全に吸着させることが出来る。
【0022】
ヨウ素を高分子材料に吸着せしめて後、吸着時の温度より高い温度で熱処理を行うとヨウ素は高分子材料のより内部まで侵入する。この場合ヨウ素を吸着した高分子化合物からのヨウ素徐放速度は減少するが、より長時間ヨウ素を徐放することができる。ヨウ素の徐放速度はヨウ素吸着量及び熱処理条件によって、調節することが出来る。高分子材料が微粉末の場合は、熱処理を行わなくても、ヨウ素は内部まで侵入するが、ヨウ素の放出が速いので徐放の時間は短い方向となる。
【0023】
ヨウ素を吸着した高分子化合物としては、上記のように高分子材料にヨウ素を吸着させたものの他、ヨウ素溶液を含浸した親水性高分子化合物のゲルなどを用いることも出来る。
【0024】
本発明においては、上記のヨウ素を吸着した高分子化合物をヨウ素ガス発生源として、ヨウ素吸着性物品にヨウ素を吸着せしめることにより、ヨウ素含有物品を簡単に製造することが出来る。ここでヨウ素吸着性物品とは、ヨウ素を吸着する能力を有する物品を意味する。
【0025】
ヨウ素吸着性物品としては、セルロース、ポリアクリロニトリル系ポリマー、ポリアミド、ポリエステル、エチレン・ビニルアルコール共重合体、ポリビニルアルコール、部分ホルマール化ポリビニルアルコール等の高分子化合物が用いられるが、ポリオレフィン系樹脂、フッ素系樹脂等はヨウ素吸着性に乏しい。ガラス、陶器等は吸着性を有しない。
【0026】
ヨウ素を吸着した高分子化合物をヨウ素ガス発生源として、ヨウ素吸着性物品にヨウ素を吸着せしめることにより、ヨウ素含有物品を製造する方法の具体例の一つとしては、パッキンを備えた着脱自在の蓋を有する密閉容器中に上記ヨウ素を吸着した高分子化合物とヨウ素吸着性物品を入れて放置しておくだけで、ヨウ素吸着性物品はヨウ素を吸着した高分子化合物から徐放されるヨウ素ガスを吸着してヨウ素含有物品が自動的に製造される。
【0027】
上記ヨウ素含有物品の製造は室温でもよいし、加温してもよい。加温するとヨウ素ガス発生量が増加し短時間でヨウ素吸着性物品にヨウ素を吸着せしめることが出来る。加温する場合の温度としては30〜60℃程度が好ましい。ヨウ素吸着性物品にヨウ素ガス徐放剤からヨウ素を吸着せしめる時間は、ヨウ素吸着性物品の形態やヨウ素徐放剤のヨウ素徐放量等により異なるが、通常は室温で1時間から1月である。40〜50℃に加温した場合は時間を数分の1に短縮出来る。
【0028】
上記のヨウ素を吸着した高分子化合物がビーズまたは粉末状の場合は、ポリオレフィン系繊維等の不織布を用いテイーバッグのような袋に入れるなど、耐ヨウ素性を有する材料で被覆して用いることが出来る。
【0029】
本発明のヨウ素含有物品の製造方法によれば、ヨウ素発生源としてヨウ素を吸着した高分子化合物を用い、これとヨウ素吸着性物品を共存せしめることにより、気相でヨウ素含有物品が得られるので、従来の方法と比べ格段に簡単にヨウ素含有物品を製造することが出来る。即ち本発明で用いるヨウ素を吸着させた高分子化合物は、固体ヨウ素のように激しくヨウ素ガスを発生させることがなく、穏やかにヨウ素を徐放するので、扱い易く、開放された普通の部屋で扱うことが出来る。また前記のように、製造条件により、ヨウ素の徐放量を調節することも容易である。また水を用いる必要がないので廃液が出ることもなく、排気の心配もない。このため本発明の方法によれば、病室や家庭内においても簡単に且つ安全に消毒用のヨウ素吸着物品を調製出来る。
【0030】
本発明のヨウ素含有物品の製造法により製造したヨウ素含有物品は、抗菌性物品或いは材料として使用することが出来る。また消毒用途に有用である。
【0031】
本発明の方法によって製造されるヨウ素含有物品の中で、特に有用な形態として繊維シート状物がある。繊維シート状物としては紙、不織布、織物、編み物何れでもよい。ヨウ素含有繊維シート状物を製造するためには、シート状物を構成する繊維がヨウ素を吸着する能力を有すればよい。セルロース系繊維(木綿、再生セルロース繊維、アセテート繊維)、ポリアミド、ポリエステル、アクリル繊維は何れもヨウ素吸着能を有する。ヨウ素含有繊維シート状物の製造には、例えば着脱自在の蓋を有する密閉容器中に上記ヨウ素を吸着した高分子化合物を収納し、容器中にヨウ素吸着性繊維シート状物を入れる。繊維シート状物が以下に述べるような条件により、十分なヨウ素を吸着したら容器から取り出し、ヨウ素含有繊維シート状物として使用することが出来る。この場合ヨウ素を吸着した高分子化合物の量およびヨウ素ガス徐放速度などによって必要な吸着時間を調節する必要がある。
【0032】
消毒を目的とする繊維シート状物としては親水性のセルロース系繊維を使用するのが好ましい。このため木綿ガーゼ、再生セルロース系不織布等を用いることが出来るが、これらはヨウ素吸着能が比較的低いため、吸着に長時間を要する。一方セルロース系繊維シート状物をポリアミン・ポリアミド系又はポリアミドエピクロルヒドリン系樹脂で処理するとヨウ素吸着能が高まり短時間で大量のヨウ素を吸着することが可能となる。繊維シート状物を上記樹脂の水溶液に浸漬して圧搾した後、100〜110℃で乾燥することによりセルロースの水酸基と架橋して、シートの耐水性が高まると同時にヨウ素吸着能の高い繊維シート状物が得られる。これらのエピクロルヒドリン系樹脂は一般に紙の湿潤紙力増強剤として用いられており、例えばハリマ化成(株)より「ハーマイドPY−410」及び「ハーマイドPY−430」として市販されている。
【0033】
現在市販されているティッシュペーパー、紙製ワイパー類には通常上記湿潤紙力増強剤が使用されている。このため市販のテイッシュペーパー、ワイパー類はヨウ素含有繊維シート状物の材料として有利に使用出来る。特に(株)クレシアから市販されているJKワイパー、ケイドライ、キムワイプはヨウ素吸着性が優れているので好ましい。市販テイッシュペーパーも使用可能であるがややヨウ素吸着性が低い。その中で例えばカミ商事(株)のエルモアは比較的ヨウ素吸着性に優れているので使用可能である。
【0034】
ヨウ素吸着性の高い繊維シート状物を用いた場合は、通常ヨウ素吸着所要時間は室温で2、3時間から30時間である。木綿ガーゼ、純粋な再生セルロース不織布のようなセルロース繊維単独の場合は30時間以上を要する。温度を高めた場合は吸着所要時間は大幅に短縮される。繊維シート状物に対するヨウ素の吸着量は通常0.01重量%〜2.5重量%程度である。消毒用繊維シート状物としては0.5重量%以下でも十分な効果を発揮することができる。
【0035】
ヨウ素含有繊維シート状物は種々の用途に使用することが出来るが、特に手指や器物等の消毒に有用である。ヨウ素含有繊維シート状物を消毒目的で使用するには、ヨウ素含有繊維シート状物を水道水等の水で濡らして手指、器物等を拭くことにより目的を達することが出来る。またヨウ素含有繊維シート状物を水に浸漬するとヨウ素が水中に溶出するので、消毒用のヨウ素水を簡単に製造することも出来る。このような消毒方法は病院、診療所、食品工業、食品調理所、介護施設、家庭介護等広い分野で使用出来る。
【0061】
【実施例】
以下本発明をより具体的に明らかにするために、幾つかの実施例を示す。
【0062】
実験例1
ダイヤペットABS(品種PS−505)の成形用ペレット(三菱レイヨン(株)製)200g及びヨウ素フレーク(日本天然ガス(株)製)260gをポリプロピレン製のボトルに入れ、密封して65℃で5時間オーブン中で時々振とうしながら加熱してヨウ素を完全に吸着せしめた。次いで80℃で12時間加熱した後、105℃で24時間熱処理した。ペレットの重量増加からペレットにはABS重量にたいして130重量%のヨウ素が吸着したことがわかった。このペレットをテイーバッグ用の袋に12gずつ詰め、ヒートシールした。
【0063】
実施例1
実験例1で得られたヨウ素を吸着したABS樹脂ペレットの袋6個を18×12×6cmのプラスチック製の角形容器に収め、JKワイパー((株)クレア)20枚を入れてパッキン付の蓋をしクリップで密封した。室温で24時間放置した後にJPワイパーを取り出し、その1枚を水200mlに浸漬すると濃度18ppmのヨウ素水が得られ、消毒用途として十分ななヨウ素を吸着していることがわかった。またこの操作を30回繰り返した後もJPワイパーに吸着するヨウ素量はほとんど変化がなく、多数回使用出来ることが確認された。
【0064】
実施例2および比較例1
本発明の方法で製造されたヨウ素含有物品の手指消毒効果を調べた。先ず消毒前の手のひらの菌を調べるため、直径35mm、深さ10mmの使い捨てシャーレにトリプトソイ寒天培地(パールコア“栄研”lot13102)を入れ、被験者4名の手のひらに押しつけた。次に比較例1としてJPワイパー1枚を滅菌イオン交換水で濡らし、絞った後10秒間被験者4名の手の平を拭いた後上と同様にして培地を手の平に押しつけた。次に実施例2として、実施例1でヨウ素を吸着せしめたJPワイパー1枚を滅菌イオン交換水で濡らし、絞った後10秒間被験者4名の手の平を拭き、上と同様にして培地を手の平に押しつけた。各培地を33℃で48時間培養した後、菌の生育状態を観察した。ワイパーで拭く前の手の平及びヨウ素未吸着のワイパーで拭いた手の平については、何れの被験者についても多数の菌のコロニーが認められたが、ヨウ素を吸着したワイパーで拭いた手の平については何れの被験者についても菌は殆ど消失していた。これにより、本発明のヨウ素含有物品の優れた消毒効果が確認された。
【0065】
実施例3および比較例2
本発明の方法で製造されたヨウ素含有物品を用いた器物の消毒効果を調べた。表面の粗いテーブル等のモデルとして、プラスチックシャーレの内面3.5cm四方に0.5cm間隔で碁盤の目状にカッターでキズを付けた。黄色ブドウ球菌(S.aureus ATCC6538)5.0×106cfu/mlの菌液を調製し、その100μlを上記シャーレに添加し、全体に拡げた。比較例2としてJPワイパー1枚を滅菌イオン交換水で濡らし、絞った後10秒間シャーレの内面を拭き、次いで不活化剤含有希釈液(DPBST液)2mlを添加してシャーレごとボルテックスにかけ、この液を回収して適宜希釈し、不活化剤含有ソイビーンカゼイン培地(SCDLP培地)を用いて33℃で48時間培養し、生菌数を求めたところ、生菌数は1.1×105であった。また実施例3として、実施例1でヨウ素を吸着せしめたJPワイパー1枚を滅菌イオン交換水で濡らし、絞った後比較例2と同様にして10秒間シャーレの内面を拭き、比較例2と同様に処理して生菌数を測定したところ、生菌数は0であった。次に大腸菌(E.coli ATCC8739)5.2×106cfu/mlの菌液を調製し、上と同様の試験を行ったところ、ヨウ素を吸着していないワイパーについては、6.0×104cfu/mlの生菌が検出された。一方実施例2でヨウ素を吸着せしめたワイパーについては、生菌数0であった。これにより本発明のヨウ素含有物品が器物の消毒に有効であることが確認された。
【0077】
【発明の効果】
本発明に従えば、ヨウ素ガス徐放剤をヨウ素ガス発生源とすることにより、実施例1に示したように安全にヨウ素含有繊維シート状物等のヨウ素含有物品が調製出来る。その調製は極めて簡単で且つ安価である。またヨウ素ガス発生源のヨウ素ガス徐放剤は繰り返し何回でも使用可能である。
【0078】
得られた繊維シート状物は水道水等に浸すだけで強力な消毒用シートとなり、実施例2および3に示したように手指の消毒、器物の消毒等に使用出来る。これは従来の方法と比べて簡単で且つ効果的である。本発明の消毒システムはヨウ素ガス徐放剤の周辺の消毒やガーゼ、布巾等の消毒にも使用可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a simple method for producing an iodine-containing article using an iodine sustained-release polymer compound adsorbed with iodine as an iodine gas generation source.
[0002]
[Prior art]
Attempts have been made to adsorb iodine to a fiber sheet to develop a bactericidal effect. For example, JP-A-1-124688 discloses a bactericidal fabric containing an iodo complex adduct and describes fibers such as nylon and acrylic as the fabric. JP-A-11-50376 discloses a vinylon nonwoven fabric carrying an iodine compound. In any of these, a fiber sheet is immersed or applied in an iodine compound solution to adsorb iodine to the fiber. However, the treatment of the fiber sheet using the iodine solution has a problem that the operation is complicated and the treatment of the waste liquid containing iodine is necessary.
[0003]
On the other hand, disinfection of hands and instruments is extremely important in hospitals to prevent infection by microorganisms, but commonly used biguanide fungicides, quaternary ammonium salt fungicides, polyvinylpyrrolidone and iodine complexes, Alcohol has problems such as rough hand, antibacterial spectrum and usability, and is not satisfactory in all aspects. Therefore, development of a more excellent disinfectant or disinfection system is desired.
[0004]
In addition, in order to protect the sterile water faucet for hand washing used in hospital operating rooms from microbial back-contamination, plastic beads that have adsorbed iodine are inserted into the faucet, and iodine eluted from the beads is used. . The purpose of this method is to prevent contamination from the faucet by disinfecting the water remaining in the faucet. Need not be released. Therefore, limiting the release of iodine during use increases the period of use of the beads. However, in the conventional method, since the beads are in direct contact with water, there is a disadvantage that iodine is wasted due to the heated water when the apparatus is used.
[0005]
Conventionally, in hospitals and the like, ultraviolet rays, formaldehyde gas, and the like are often used to disinfect instruments, but there are problems in that expensive equipment is required and there is danger to the human body.
[0006]
Furthermore, it cannot be said that there is a sufficiently simple and reliable method for disinfection of hospital rooms and floors. In addition, disinfection performed by general users like contact lenses is safe and reliable for disinfection in which equipment is immersed in a liquid. However, the ideal situation has not yet emerged.
[0007]
[Problems to be solved by the invention]
The present invention has been made in the background as described above, and the object of the present invention is to manufacture iodine-containing articles that can be easily and safely manufactured at hospitals and homes for disinfection, particularly the production of fiber sheets containing iodine. It is to provide a method.
[0008]
[Means for Solving the Problems]
As a result of various studies to achieve the above object, the present inventors have succeeded in achieving the object by using a polymer compound adsorbed with iodine as an iodine gas generation source, and reached the present invention.
[0009]
That is, the gist of the present invention is a method for producing an iodine-containing article characterized in that iodine is adsorbed on the article using a polymer compound adsorbing iodine as an iodine gas generation source. As a polymer compound adsorbing iodine, beads, powders, fibers, films, fabrics, selected from the group consisting of ABS resin, AS resin, ethylene / vinyl alcohol copolymer, polyamide, polyvinyl alcohol, formalized polyvinyl alcohol, etc. Nonwoven fabric or gel is used.
[0010]
A fiber sheet containing a polyamide epichlorohydrin resin or a polyamine / polyamide epichlorohydrin resin is preferably used as an article for adsorbing iodine gas from the polymer compound adsorbing iodine, and the iodine-containing fiber sheet is wetted with water. Can be used to provide a powerful disinfection method.
[0015]
Note that. In JP-A-9-67217, JP-A-9-122655, and JP-A-10-165960, an antibacterial composition that gradually releases iodine in water by adsorbing iodine to plastic and bringing it into contact with water. However, the present invention has developed a novel method in which iodine is adsorbed on a plastic and used as an iodine gas sustained-release agent without contacting it with water.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention , as the polymer compound adsorbed with iodine used as an iodine gas generation source, a compound obtained by adsorbing iodine to a polymer compound having iodine adsorptivity is used. Plastics having iodine adsorptivity include ABS resin, AS resin, ethylene / vinyl alcohol copolymer (EVOH), ethylene / vinyl acetate copolymer, polyamide, polyacrylonitrile, acrylonitrile / vinyl chloride copolymer resin, polyurethane resin, Cellulose acetate resin, polyvinyl alcohol, formalized polyvinyl alcohol, polyester, polyethylene oxide resin, starch, polyvinylpyrrolidone copolymer (for example, vinylpyrrolidone / methyl methacrylate copolymer) and the like are used. Moreover, even if it is resin with poor iodine adsorptivity, it becomes useable by mixing and shape | molding said iodine adsorptive resin.
[0017]
Among these plastics, ABS resin, AS resin, and ethylene / vinyl alcohol copolymer (EVOH) are particularly desirable because they are excellent in iodine adsorption. In general, those commercially available as ABS resins are 20 to 30% by weight of the acrylonitrile component, 40 to 70% by weight of the styrene component, and 10 to 30% by weight of the butadiene component, but any of them can be used in the present invention. It is. As the EVOH-based resin, one having an ethylene content of 20 to 50 mol% in the copolymer is preferably used. As commercial products, any of the various types of Soarnol manufactured by Nippon Synthetic Chemical Industry Co., Ltd. and various types of Eval manufactured by Kuraray Co., Ltd. can be used.
[0018]
The polymer compound adsorbed with iodine can be used in various forms such as beads, powder, fiber, woven fabric or nonwoven fabric, film or gel. Also, a molded product by thermoforming such as injection molding, extrusion molding, compression molding or the like can be used. The preferred form varies depending on the method of use, application, etc., but from the viewpoint of the ease of the iodine adsorption process, a bead or powder is preferred. As a bead-like form, plastic material injection molding pellets are advantageous because commercially available products can be used as they are. It is also possible to use a finely pulverized injection molding pellet.
[0019]
In order to obtain a polymer compound in which iodine is adsorbed from an iodine adsorbing polymer compound material (hereinafter abbreviated as a polymer material), it is necessary to adsorb iodine in the polymer material. The liquid phase method in which a polymer material is immersed in an iodine solution may be used for adsorption of iodine. However, it is easier to operate by the gas phase method, the adsorption amount can be easily increased, and waste liquid can be produced. It is advantageous because it is not. The method for adsorbing iodine to a polymer material is described in detail in JP-A-10-165960. That is, the vapor phase adsorption of iodine is performed by putting the polymer material and solid iodine in a sealed container and heating to 50 ° C to 110 ° C. The heating is performed until all the solid iodine is adsorbed on the polymer material, but the time varies depending on the kind and form of the polymer material and the amount of iodine to be adsorbed.
[0020]
The amount of iodine adsorbed on the polymer material is preferably 5 to 200% by weight. A material having a large surface area such as a powder may have a relatively small amount of iodine adsorption, and a material having a small surface area requires a relatively large amount. A desirable adsorption amount is 10 to 200% by weight, particularly preferably 30 to 150% by weight (with respect to plastic weight) in the form of beads. In the case of powder, the iodine adsorption amount is suitably about 10 to 100% by weight (vs. plastic weight).
[0021]
For example, when adsorbing 100% by weight of iodine to an ABS resin molding pellet, the iodine is mixed by mixing with solid iodine equivalent to the resin pellet in an airtight container and heating at 50 to 100 ° C. for 1 to 10 hours. Can be completely adsorbed.
[0022]
When iodine is adsorbed on the polymer material and then heat treatment is performed at a temperature higher than the temperature at the time of adsorption, iodine penetrates further into the polymer material. In this case, the iodine sustained release rate from the polymer compound adsorbed with iodine decreases, but iodine can be released gradually for a longer time. The sustained release rate of iodine can be adjusted by the amount of iodine adsorbed and the heat treatment conditions. When the polymer material is a fine powder, iodine penetrates into the inside without performing heat treatment, but since the release of iodine is fast, the time for sustained release becomes shorter.
[0023]
As the polymer compound to which iodine is adsorbed, a gel of a hydrophilic polymer compound impregnated with an iodine solution can be used in addition to the polymer compound in which iodine is adsorbed as described above.
[0024]
In the present invention, an iodine-containing article can be easily produced by adsorbing iodine to an iodine-adsorbing article using the above-described polymer compound adsorbing iodine as an iodine gas generation source. Here, the iodine adsorbing article means an article having an ability to adsorb iodine.
[0025]
As iodine-adsorbing articles, polymer compounds such as cellulose, polyacrylonitrile-based polymer, polyamide, polyester, ethylene / vinyl alcohol copolymer, polyvinyl alcohol, and partially formalized polyvinyl alcohol are used. Resins are poor in iodine adsorption. Glass, earthenware, etc. have no adsorptivity.
[0026]
A specific example of a method for producing an iodine-containing article by adsorbing iodine to an iodine-adsorbing article using a polymer compound that has adsorbed iodine as an iodine gas generation source is a removable lid provided with a packing. The iodine-adsorbing article adsorbs iodine gas that is slowly released from the iodine-adsorbing polymer compound simply by placing the iodine-adsorbing polymer compound and iodine-adsorbing article in a closed container having Thus, iodine-containing articles are automatically manufactured.
[0027]
The iodine-containing article may be produced at room temperature or warmed. When heated, the amount of iodine gas generated increases, and iodine can be adsorbed to the iodine-adsorbing article in a short time. The temperature for heating is preferably about 30 to 60 ° C. The time for adsorbing iodine from the iodine gas sustained-release agent to the iodine-adsorbing article varies depending on the form of the iodine-adsorbing article, the iodine sustained-release amount of the iodine-releasing agent, etc., but is usually 1 hour to 1 month at room temperature. When heated to 40-50 ° C., the time can be shortened to a fraction.
[0028]
When the polymer compound adsorbing iodine is in the form of beads or powder, it can be used by being coated with a material having iodine resistance, such as using a nonwoven fabric such as polyolefin-based fibers and putting it in a bag such as a tee bag.
[0029]
According to the method for producing an iodine-containing article of the present invention, an iodine-containing article can be obtained in the gas phase by using a polymer compound that adsorbs iodine as an iodine generation source and coexisting with the iodine-adsorbing article. Compared with conventional methods, iodine-containing articles can be manufactured much more easily. That is, the polymer compound adsorbed with iodine used in the present invention does not generate intense iodine gas unlike solid iodine, and gently releases iodine, so it is easy to handle and is handled in an open ordinary room. I can do it. Further, as described above, it is easy to adjust the sustained release amount of iodine depending on the production conditions. Moreover, since it is not necessary to use water, there is no waste liquid and there is no concern about exhaust. Therefore, according to the method of the present invention, an iodine-adsorbing article for disinfection can be prepared easily and safely even in a hospital room or at home.
[0030]
The iodine-containing article produced by the method for producing an iodine-containing article of the present invention can be used as an antibacterial article or material. It is also useful for disinfecting applications.
[0031]
Among the iodine-containing articles produced by the method of the present invention, a particularly useful form is a fiber sheet. The fiber sheet may be paper, non-woven fabric, woven fabric, or knitted fabric. In order to produce an iodine-containing fiber sheet material, it is sufficient that the fibers constituting the sheet material have an ability to adsorb iodine. Cellulosic fibers (cotton, regenerated cellulose fibers, acetate fibers), polyamides, polyesters, and acrylic fibers all have iodine adsorption ability. For production of the iodine-containing fiber sheet material, for example, the polymer compound adsorbing iodine is stored in a closed container having a detachable lid, and the iodine-adsorbing fiber sheet material is placed in the container. When the fiber sheet is adsorbed with sufficient iodine under the conditions described below, it can be removed from the container and used as an iodine-containing fiber sheet. In this case, it is necessary to adjust the necessary adsorption time depending on the amount of the polymer compound that has adsorbed iodine and the rate of sustained release of iodine gas.
[0032]
It is preferable to use hydrophilic cellulosic fibers as the fiber sheet for disinfection. For this reason, cotton gauze, regenerated cellulose nonwoven fabric and the like can be used, but these require a long time for adsorption because of their relatively low iodine adsorption capacity. On the other hand, when the cellulose fiber sheet is treated with a polyamine / polyamide-based or polyamide epichlorohydrin-based resin, the iodine adsorbing ability is increased and a large amount of iodine can be adsorbed in a short time. The fiber sheet is immersed in an aqueous solution of the resin and squeezed, and then dried at 100 to 110 ° C. to crosslink with the hydroxyl group of cellulose, thereby increasing the water resistance of the sheet and at the same time a fiber sheet having a high iodine adsorption capacity. Things are obtained. These epichlorohydrin-based resins are generally used as wet paper strength enhancers for paper, and are commercially available, for example, as “Harmide PY-410” and “Harmide PY-430” from Harima Kasei Co., Ltd.
[0033]
The above-mentioned wet paper strength enhancer is usually used for tissue papers and paper wipers currently on the market. For this reason, commercially available tissue papers and wipers can be advantageously used as materials for iodine-containing fiber sheets. In particular, JK wipers, Keidry, and Kimwipes commercially available from Crecia Co., Ltd. are preferred because of their excellent iodine adsorption. Commercially available tissue paper can also be used, but the iodine adsorptivity is somewhat low. Among them, for example, Lmore from Kami Shoji Co., Ltd. can be used because it is relatively excellent in iodine adsorption.
[0034]
When a fiber sheet-like material having high iodine adsorptivity is used, the time required for iodine adsorption is usually 2, 3 to 30 hours at room temperature. In the case of cellulose fibers alone such as cotton gauze and pure regenerated cellulose nonwoven fabric, it takes 30 hours or more. When the temperature is increased, the time required for adsorption is greatly reduced. The amount of iodine adsorbed on the fiber sheet is usually about 0.01% to 2.5% by weight. As a disinfectant fiber sheet, a sufficient effect can be exhibited even at 0.5% by weight or less.
[0035]
The iodine-containing fiber sheet can be used for various purposes, but is particularly useful for disinfecting fingers and instruments. In order to use the iodine-containing fiber sheet for the purpose of disinfection, the objective can be achieved by wiping the fingers, instruments and the like by wetting the iodine-containing fiber sheet with water such as tap water. Moreover, since iodine elutes in water when an iodine-containing fiber sheet is immersed in water, iodine water for disinfection can be easily produced. Such a disinfection method can be used in a wide range of fields such as hospitals, clinics, food industries, food cooking places, nursing homes, home care.
[0061]
【Example】
In order to clarify the present invention more specifically, some examples will be shown below.
[0062]
Experimental example 1
200 g of Diapet ABS (variety PS-505) molding pellets (Mitsubishi Rayon Co., Ltd.) and 260 g of iodine flakes (Nippon Natural Gas Co., Ltd.) were placed in a polypropylene bottle, sealed, and sealed at 65 ° C. The iodine was completely adsorbed by heating with occasional shaking in the oven. Subsequently, after heating at 80 degreeC for 12 hours, it heat-processed at 105 degreeC for 24 hours. From the increase in the weight of the pellet, it was found that 130% by weight of iodine was adsorbed on the pellet with respect to the ABS weight. 12 g of this pellet was packed into a bag for a tee bag and heat sealed.
[0063]
Example 1
Six pieces of ABS resin pellets adsorbed with iodine obtained in Experimental Example 1 are placed in a 18 × 12 × 6 cm plastic square container, and 20 pieces of JK Wiper (Crea Co., Ltd.) are put into a lid with packing. And sealed with a clip. After leaving for 24 hours at room temperature, the JP wiper was taken out and one of them was immersed in 200 ml of water to obtain iodine water with a concentration of 18 ppm. It was found that sufficient iodine was adsorbed for disinfection. Moreover, even after repeating this operation 30 times, the amount of iodine adsorbed on the JP wiper hardly changed, and it was confirmed that it could be used many times.
[0064]
Example 2 and Comparative Example 1
The hand disinfection effect of the iodine-containing article produced by the method of the present invention was examined. First, in order to examine the germs of the palm before disinfection, tryptosoy agar medium (Pearl Core “Eiken” lot 13102) was placed in a disposable petri dish with a diameter of 35 mm and a depth of 10 mm and pressed against the palms of four subjects. Next, as Comparative Example 1, one JP wiper was wetted with sterilized ion-exchanged water, and after squeezing, the palm of four subjects was wiped for 10 seconds, and then the medium was pressed against the palm in the same manner as above. Next, as Example 2, one JP wiper on which iodine was adsorbed in Example 1 was wetted with sterilized ion-exchanged water, and after squeezing, the palms of four subjects were wiped for 10 seconds. Pressed. Each medium was cultured at 33 ° C. for 48 hours, and then the growth state of the bacteria was observed. Regarding the palm before wiping with a wiper and the palm wiped with an iodine non-adsorbed wiper, a large number of bacterial colonies were observed for any subject, but for any subject with a palm wiped with an iodine-adsorbed wiper The fungus was almost gone. Thereby, the outstanding disinfection effect of the iodine containing article of the present invention was confirmed.
[0065]
Example 3 and Comparative Example 2
The disinfection effect of the container using the iodine-containing article produced by the method of the present invention was examined. As a model of a table having a rough surface, the inner surface of a plastic petri dish was scratched with a cutter in the shape of a grid at intervals of 0.5 cm. A bacterial solution of S. aureus ATCC 6538 (5.0 × 10 6 cfu / ml) was prepared, and 100 μl thereof was added to the petri dish and spread over the whole. As Comparative Example 2, one JP wiper was wetted with sterilized ion-exchanged water, and after squeezing, the inner surface of the petri dish was wiped for 10 seconds, then 2 ml of an inactivating agent-containing diluent (DPPBST solution) was added and vortexed with the petri dish. Was collected, diluted appropriately, and cultured at 33 ° C. for 48 hours using a soy bean casein medium (SCDLP medium) containing an inactivating agent. The number of viable bacteria was determined, and the viable cell count was 1.1 × 10 5. It was. In addition, as Example 3, one JP wiper on which iodine was adsorbed in Example 1 was wetted with sterilized ion-exchanged water, and after squeezing, the inner surface of the petri dish was wiped for 10 seconds in the same manner as in Comparative Example 2, and the same as in Comparative Example 2 When the viable cell count was measured after treatment, the viable cell count was 0. Next, a bacterial solution of E. coli ATCC 8739 (5.2 × 10 6 cfu / ml) was prepared and tested in the same manner as above. As for the wiper not adsorbing iodine, 6.0 × 10 6 was obtained. 4 cfu / ml viable bacteria were detected. On the other hand, for the wiper on which iodine was adsorbed in Example 2, the viable cell count was zero. Thereby, it was confirmed that the iodine-containing article of the present invention is effective for disinfection of the container.
[0077]
【The invention's effect】
According to the present invention, an iodine-containing article such as an iodine-containing fiber sheet can be safely prepared as shown in Example 1 by using an iodine gas sustained-release agent as an iodine gas generation source. Its preparation is very simple and inexpensive. Moreover, the iodine gas sustained release agent of an iodine gas generation source can be used repeatedly many times.
[0078]
The obtained fiber sheet-like material becomes a powerful disinfecting sheet simply by immersing in tap water or the like, and can be used for disinfection of fingers, disinfection of equipment, etc. as shown in Examples 2 and 3. This is simple and effective compared to the conventional method. The disinfecting system of the present invention can also be used for disinfecting around the iodine gas sustained-release agent and disinfecting gauze and cloths.
Claims (6)
セルロース系繊維、ポリアミド系繊維、ポリエステル系繊維、アクリル系繊維からなる群より選択された一種以上の繊維シート状物に接触させることにより
ヨウ素を吸着せしめることを特徴とするヨウ素吸着繊維シートの製造方法。Iodine that is sustainedly released from an iodine sustained-release polymer compound that adsorbs 10 to 200% by weight of iodine ,
A method for producing an iodine-adsorbing fiber sheet , wherein iodine is adsorbed by contacting with one or more fiber sheet-like materials selected from the group consisting of cellulosic fibers, polyamide fibers, polyester fibers, and acrylic fibers .
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| JP4680494B2 (en) * | 2003-12-08 | 2011-05-11 | 関東天然瓦斯開発株式会社 | Sterilized solid article, method for sterilizing solid article |
| JP4663977B2 (en) * | 2003-12-08 | 2011-04-06 | 関東天然瓦斯開発株式会社 | Solid article sterilizer, iodine gas generator |
| JP4660641B2 (en) * | 2003-12-08 | 2011-03-30 | 関東天然瓦斯開発株式会社 | Sterilized seedling article, method of sterilizing seedling article |
| JP2008029498A (en) * | 2006-07-27 | 2008-02-14 | Arupiko Kk | Shoe sterilizer |
| JP5448381B2 (en) * | 2007-07-19 | 2014-03-19 | トーメー商事株式会社 | Iodine rapid release material and method for producing the same |
| CN105561950B (en) * | 2015-12-14 | 2018-02-02 | 珠海健帆生物科技股份有限公司 | Macroporous absorbent resin and preparation method thereof |
| CN105954342A (en) * | 2016-04-26 | 2016-09-21 | 兰州蓝星纤维有限公司 | Method for testing density of polyacrylonitrile protofilament fibers |
| CN109575326B (en) * | 2018-12-03 | 2021-05-25 | 中国工程物理研究院材料研究所 | Preparation method of super-crosslinked porous polymer for iodine adsorption enrichment |
| JP7781390B2 (en) * | 2021-08-13 | 2025-12-08 | 国立大学法人山形大学 | Disinfectants, disinfectant films and disinfectant beads |
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| JPS60232288A (en) * | 1984-05-01 | 1985-11-18 | Mitsubishi Rayon Co Ltd | Sterilization material for water treatment |
| JPH0446002A (en) * | 1990-06-13 | 1992-02-17 | Health Kosan:Kk | Production of gel composition for generating gaseous chlorine dioxide |
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| BR9612477A (en) * | 1996-01-22 | 1999-07-13 | Bausch & Lomb | Method for treating a lens and system for disinfecting contact lenses |
| JPH09273062A (en) * | 1996-04-03 | 1997-10-21 | Oji Paper Co Ltd | Antibacterial composite non-woven fabric and method for producing the same |
| JP3999835B2 (en) * | 1996-12-10 | 2007-10-31 | 株式会社トーメー | ANTIBACTERIAL COMPOSITION AND PROCESS FOR PRODUCING THE SAME, ANTIBACTERIAL MIXED PARTICLE USING THE ANTIBACTERIAL COMPOSITION, LIQUID SUPPLIER WITH MICROBODY INTRODUCTION PREVENTION FUNCTION, AND IODINE-CONTAINING SOLUTION MANUFACTURING DEVICE |
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2002
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