JP2013500388A - カチオン性レオロジー剤を含有する除去可能な抗菌コーティング組成物およびその使用方法 - Google Patents
カチオン性レオロジー剤を含有する除去可能な抗菌コーティング組成物およびその使用方法 Download PDFInfo
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Classifications
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Abstract
Description
本出願は、すべて2009年7月27日出願の4つの米国特許仮出願第61/228707号、61/228711号、61/228715号および61/228723号の利益を請求する。
i.水可溶性または水分散性皮膜形成剤;
ii.少なくとも1種類のカチオン性または非イオン性抗菌剤;
iii.水性溶媒;
iv.カチオン性レオロジー剤
を含む、残留自己消毒特性を提供する、除去可能な抗菌コーティング組成物を含む。
a)i)水可溶性または水分散性皮膜形成剤;
ii)少なくとも1種類の抗菌剤;
iii)水性溶媒;
iv)カチオン性レオロジー剤;
を合わせて、剪断減粘性の除去可能なコーティング組成物を得る工程;
b)前記コーティング組成物を前記位置に塗布する工程;
を含み、
前記コーティング組成物が、前記位置に塗布された後に乾燥コーティングを形成するように放置される、方法を含む。
a.(i)電気伝導率0〜10mS/cmの水性溶媒と(ii)水可溶性または水分散性皮膜形成剤とを合わせることによって、懸濁液を形成する工程;
b.前記懸濁液を少なくとも10分間、30℃〜95℃に加熱する工程;
c.任意の順序で(i)抗菌剤;(ii)カチオン性レオロジー剤;(iii)場合により、追加の成分;を添加する工程;
d.組成物を混合する工程;
を含む、除去可能な抗菌コーティング組成物を製造する方法を含む。
の第四級アンモニウムカチオンの塩を意味する。
明確にするために、本明細書で使用される用語は、本明細書に記載のとおり、またはかかる用語が、本発明の当業者によって理解されるであろうように理解されるものとする。本明細書で使用される特定の用語の更なる説明は以下に示す:
本明細書に記載の組成物の成分の詳細な説明を以下に示す。
の第四級アンモニウムカチオンである。このカチオン性官能基に対して対応するアニオンは任意のアニオンであることができる。
本発明の実施において有用な、適切な抗菌剤は、所有者共通の、かつ同時係属の米国特許出願第2008/0026026号明細書および2007/0275101号明細書に記述されている。抗菌剤を含むコーティング組成物は、多種多様な微生物に対する保護を提供する。
「ATCC」はアメリカ培養細胞系統保存機関(American Type Culture Collection)を意味し;「℃」は摂氏温度を意味し;「CFU」はコロニー形成単位を意味し;「rpm」は毎分回転数を意味し;「モル/L」は1リットル当たりのモル数を意味し;「PFU/mL」は1ミリリットル当たりのプラーク形成単位を意味し;「kg」はキログラムを意味し、「DI」は脱イオン化を意味し;「FBS」はウシ胎児血清を意味し;「cm」はセンチメートルを意味し;「m」はメートルを意味し;「μm」はマイクロメートル;「m2/分」は平方メートル/分を意味し;「g/m2」はグラム/平方メートルを意味し;「g」は地心重力定数を意味し;「L」はリットルを意味し;「log CFU」は、CFU数の10を底とする対数であり;「log CFU」は、未処理試料のlog CFUとコーティング組成物で処理された試料のlog CFUの差であり;「mL」はミリリットルを意味し;「MPa」はメガパスカルを意味し;「mS/cm」はミリジーメンス/センチメートルを意味し;「NFC」は、非食品接触清浄薬試験を意味し;「Pa」はパスカルを意味し;「Pa・s」はパスカル秒を意味し;「PEG」はポリエチレングリコールを意味し;「rpm」は毎分回転数を意味し;RSSは残留自己消毒活性を意味し;「s-1」は秒のマイナス1乗を意味し;「SS316」は、ステンレス鋼、316型(ASTM標準)を意味し;「wt%」は重量%を意味する。
別段の指定がない限り、すべての化学物質をSigma−Aldrich(St.Louis,MO,USA)から入手した。Alco Chemical(登録商標)(Chattanooga,TN,USA)からAlcogum(登録商標)L−520を入手した。Rheovis(登録商標)FRCは、Ciba(登録商標)(Basel,Switzerland)から入手した。Elvanol(登録商標)51−04および1,1,1,2−テトラフルオロエタンをDuPont(Wilmington,DE,USA)から入手した。ポリエチレングリコール(PEG−300)をDow(Midland,MI,USA)から入手した。FD&C Blue No.1染料をPylam Products(Tempe,AZ,USA)から入手した。BTC(登録商標)885およびBiosoft(登録商標)N25−7をStepan(Northfield,IL,USA)から入手した。Surfynol(登録商標)MD−20およびEnviroGem(登録商標)360をAirProducts(Allentown,PA,USA)から入手した。Bacto(商標)D/E中和ブロスをDifco(カタログ番号281910,Difco−Laboratories,Detroit,MI,USA)から入手した。Liquitint(登録商標)Patent BlueをMilliken(Spartanburg,SC,USA)から入手した。
硬質表面上の抗菌有効性の試験方法
以下に記載の試験方法を用いて、本発明の開示によるコーティング組成物の殺菌性または抗菌有効性を測定した。
抗菌コーティング組成物を塗布した時点で標的表面上に微生物汚染が既に存在する状況に関して、本発明の開示内容によるコーティング組成物の抗菌活性を評価するために、ASTM標準E1153−03準拠した「Standard Test Method for Efficacy of Sanitizers Recommended for Inanimate Non−Food Contact Surfaces」を用いた。この試験方法は、非食品接触清浄薬試験またはNFC試験と呼ばれる。その結果は、接種された未処理対照クーポンのlog CFUと、本明細書に示される方法に従ってコーティング組成物で処理されたクーポンのlog CFUの差を意味するlog CFUとして報告される。対照と処理クーポン両方のlog CFU数を計算した。反復試験クーポン上に生存する微生物の数の幾何平均として計算した。すべてのlog数は10を底とする対数である。
微生物の汚染が既に乾燥しているコーティングと接触している状況について、この方法に従ってコーティング組成物の抗菌活性を評価するために、以下の残留自己消毒試験法を用いた。この試験法は、残留自己消毒試験またはRSS試験と呼ばれる。25.4mm×25.4mm、非多孔質、予め浄化されたステンレス鋼(SS316型)クーポンを試験に用いた。試験微生物を凍結保存培養から培地のチューブへと移した。良好な成長が得られる期間および時間、そのチューブをインキュベートした。新たな培地に継続的に移すことによって、接種材料を維持した。およそ48時間経過した接種懸濁液を約3秒間混合し、15分間静置しておいた。接種材料懸濁液は一般に、約1×108CFU/mLを含有した。接種材料全容積の上部3分の2をデカントし、ピペットで取り、新たな滅菌チューブに移した。一定容積の滅菌FBSを添加し、有機土壌添加率5重量%を得た。接種材料を室温で約15分間放置した。
微生物の汚染が既に乾燥しているコーティングと接触している状況について、本発明の開示に従ってコーティング組成物の抗菌活性を評価するために、以下の残留自己消毒試験法を用いた。この試験法は、残留自己消毒試験またはRSS試験と呼ばれる。25.4mm×25.4mm、非多孔質、予め浄化されたステンレス鋼(SS316型)クーポンを試験に用いた。この研究に使用された試験微生物は毛瘡白癬菌(Trichophyton mentagrophytes)ATCC9533であった。ジャガイモブドウ糖寒天(Potato Dextrose Agar(PDA))を用いた。20枚のプレートを培養物のうちの1つで画線し、室温で2週間インキュベートした。次いで、Tween(登録商標)80 0.01重量%を含有する滅菌脱イオン水でプレートを2回洗浄し、滅菌延展器でこすった。ガラスビーズを有する滅菌フラスコ内で洗浄物を合わせ、wrist action振盪機上で1時間振盪した。次いで、滅菌ガーゼを通して、フラスコ内容物を濾過し、新たな滅菌フラスコに入れ、4℃で保存した。標準平板菌数方法論によって、滅菌リン酸緩衝液での段階希釈を用い、PDAプレート上に広げて、生存真菌胞子の濃度を決定した。コロニーをカウントする前に、PDAプレートを4日間インキュベートした。試験を開始する前、胞子試料24mLを5,000×gにて10分間遠心した。上清を除去し、Tween(登録商標)80 0.01%を含有する滅菌脱イオン水8mLにペレットを再懸濁した。濃縮胞子試料のアリコート(4.75mL)を取り出し、ウシ胎児血清(最終濃度5重量%)0.25mLと混合し、接種材料を得た。
カチオン性レオロジー剤を含むコーティング組成物
表1のコーティング組成物を次の実施例で調製し、使用した。
酸活性化レオロジー剤を含む比較用コーティング組成物
酸活性化レオロジー剤を含み、かつ本発明の組成物(次の実施例で開示される)との比較として使用されるコーティング組成物を以下のとおり調製した。
酸活性化レオロジー剤とカチオン性レオロジー剤の両方を含むコーティング組成物を除去した後の、表面の外観
水道水ですすいでコーティングを除去した後に、酸活性化レオロジー剤とカチオン性レオロジー剤でコーティングされた表面の外観を調べた。アルミニウムとポリカーボネート(Lexan(登録商標)141R−701−BLK型,寸法305mm×102mm×3.2mm,General Electric Co.,(Fairfield,CT,USA))の両方をコーティングする表面として使用した。湿潤フィルムアプリケーター(フィルム厚203μm,AP−15SS型,Paul N.Gardner Co.Inc.,(Pompano Beach,FL,USA))を用いて、パネルを最初に液体コーティング組成物でコーティングした。次いで、コーティングを少なくとも24時間、空気中で乾燥させた。約25℃の水道水ですすぐことによって、乾燥したコーティングを洗い流した。パネルを再び、空気中で乾燥させ、残留物について目視でパネルの外観を分析し、その結果を表3にまとめる。コーティング組成物#248は、すすぎの後、試験された両方の表面材料上にはっきりと目に見える濁った残留物を残したのに対して、コーティング組成物#271は、低減された(reduced)依然として目立つ残留物によるを生成した。それと対照的に、本発明の組成物#286および#290は、試験された表面上に目立つ残留物を残さなかった。
バックパック・スプレーシステムを用いた噴霧塗布
AG03型噴霧ノズルを備えたバックパック・スプレーシステム(SP Professional Backpack Sprayer,Model SP0,SP Systems LLC,(Santa Monica,CA,USA))に実施例1のコーティング組成物#701を充填した。一体型ポンプレバーを用いて、バックパック噴霧器を0.7〜1.0MPaに加圧した。ファン開口角度約80度の三角形ファンが達成された。これによって、噴霧ノズルと標的表面の噴霧距離約0.3mを用いて、幅約0.5mの噴霧領域を効率的かつ迅速にカバーすることが可能となる。目に見えるコーティングの欠陥なく、優れた被覆率(99〜100%)が達成された。
エアロゾルスプレー缶を使用した噴霧塗布
実施例1の配合物#319(204g)を容積約0.21Lのエアロゾルスプレー缶に噴射剤(8.1g)と共に充填した。噴射剤は、質量比67:1の1,1,1,2−テトラフルオロエタンと窒素ガスの混合物であった。充填後の圧力は約0.97MPaであった。
エアレススプレー装置を用いた、コーティング組成物の噴霧塗布
エアレススプレーシステム(President 46/1 SSTモデル,Graco Inc.,(Minneapolis,MN,USA))を用いて噴霧することによって、コーティング組成物#286および#290を表面に塗布した。圧力調整器を用いて、供給空気圧を0.55〜0.65MPaに設定し、噴霧圧力約25〜30MPaが得られた。0.9メートル延長(モデル#287023,Graco)を有し、かつ広角スプレーチップ(モデル711,Graco)を備えたポールスプレーガン(モデルXTR 502,Graco)を使用した。コーティング組成物を温度約10℃〜25℃でスプレーした。選択条件下にて、有利な噴霧開口角度75〜90度に相当する、噴霧距離約0.35mでのファン幅55〜70cmが提供された。効率的な霧化、完全な被覆、および垂直面もしくは傾斜面から垂れる、または滴り落ちる傾向が低いことなど、優れた噴霧適性が達成された。垂れポイントは、垂直面上にスプレーし、乾燥させた後に、コーティングが目に見える垂れ、または滴りを示し始めるそのポイントでのコーティングの厚さとして定義される。垂れポイントは、コーティング組成物#286および#290については20℃で約7.0μm、10℃で7.5μmと測定され、垂れおよび滴りに対して高い抵抗性を示した。
凍結融解条件下でのコーティング組成物#286の安定性
コーティング組成物#286を凍結融解安定性試験にかけて、温度変化に対する長期間の安定性を評価し、保管中または輸送中に意図せず凍結された場合の組成物の挙動を予想した。組成物を3回の凍結融解サイクルにかけ、各凍結融解サイクルは、組成物を−20〜−16℃で24時間保管し、続いて組成物を+20〜+25℃で24時間保管することを特徴とした。凍結融解処理あり、および凍結融解処理なしで、コーティング組成物#286の垂れポイントを測定し、同一(7.0μm)であることが判明し、コーティング組成物#286の良好な凍結融解安定性が強調された。
短期間の抗菌特性
上述のNFC法を用いて、実施例1のコーティング組成物#286および#290を短期間の抗菌活性について試験した。コーティング組成物がまだ液状である間に、NFC法によって、コーティング組成物の抗菌活性を評価した。使用した微生物は大腸菌(Escherichia coli)O157:H7、サルモネラ・エンテリカ(Salmonella enterica)ATCC 10708、黄色ブドウ球菌(Staphylococcus aureus)ATCC 6358および肺炎杆菌(Klebsiella pneumoniae)ATCC 4352であった。表4に示すように、どちらのコーティング組成物も、試験されたすべての微生物に対して、少なくとも99.998%のCFU数の減少に相当する、少なくとも4.8log CFUの減少を示した。
残留抗菌活性
上述の残留自己消毒(RSS)試験法を用いて、実施例1のコーティング組成物#286および#290を試験した。コーティング組成物が表面上で乾燥した後に、RSS法でコーティング組成物の抗菌活性を評価する。使用した試験微生物は、黄色ブドウ球菌(Staphylococcus aureus)ATCC 6358および肺炎杆菌(Klebsiella pneumoniae)ATCC 4352であった。表5に示すように、試験された微生物に関して接触時間5分以内に、両方のコーティング組成物によって、5.3log CFUを超える減少が達成された。
カチオン性レオロジー剤を含むコーティング組成物の流動学的特性
Bohlin Gemini制御応力レオメーター(Malvern Instruments Ltd.,(Worcestershire,UK))を使用して、液体抗菌配合物の流動学的特性を評価した。この装置は、ペルチェ加熱システムおよび滑らかな表面を有する40mm平行プレートを備えた。「ギャップ」と呼ばれるプレート間の距離を0.150mmに調節した。このシステムを所望の試験温度に設定した。試料1ml未満をペルチェプレートに添加した。上部の平行プレートを所望のギャップに下げた。最初に余分な材料をピペットで除去し、次いで1片のプラスチックの直定規を用いて、平行なプレートの周りの試料をきれいに取り除いた。剪断速度2000s-1にて試料を30秒間予備剪断し、次いで、装置が温度設定ポイントに達すると同時に回復させた。400秒間の過程にわたって、0.03s-1〜30,000s-1の剪断速度スイープを行った。
カチオン性レオロジー剤を含むコーティング組成物の剪断減粘指数
「偽塑性指数」または「剪断減粘指数」(STI)は、垂れおよび滴りに対する組成物の抵抗性の指標を提供する。一般的な測定では、1s-1および10s-1などの2つの異なる剪断速度で粘度が決定される。低い剪断速度で記録された値は、高い剪断速度での値で割られ、STIが得られる。一般に、STIが高いほど、コーティング材料が有する、垂れおよび滴りに対する抵抗性が高くなる。
コーティングを除去した後の表面残留物の研究
除去可能な抗菌コーティングを意図的に除去した後、目に見える表面残留物の存在および程度を調べるために、以下の実験を行った。湿潤フィルムアプリケーター(フィルム厚203μm,AP−15SSモデル,Paul N.Gardner Co.Inc.,(Pompano Beach,FL,USA))を用いて、液体コーティング組成物#271(比較)および#286(本発明)をアルミニウムパネルに塗布した。次いで、湿潤フィルムを空気中で少なくとも12時間乾燥させた。スプレーボトル(型番号23609−182,VWR International,(West Chester,PA,USA))を使用して、表8に示す液体を均一にスプレーするか、または対照としてスプレーしないままにしておいた。スプレーされたコーティングを少なくとも3時間、再び乾燥させた。次いで、乾燥したコーティングを約25℃の水道水ですすいで洗い流した。水で濡れたパネルを再び、空気中で少なくとも3時間乾燥させ、残留物について目視でパネルの外観を分析した。その結果を表8にまとめる。
Claims (11)
- i.水可溶性または水分散性皮膜形成剤;
ii.少なくとも1種類のカチオン性または非イオン性抗菌剤;
iii.水性溶媒;
iv.カチオン性レオロジー剤;
を含む、残留自己消毒特性を提供する除去可能な抗菌コーティング組成物。 - 前記皮膜形成剤が、ポリ(ビニルアルコール)またはそのコポリマーを含む、請求項1に記載の組成物。
- 前記抗菌剤が、第四級アンモニウム化合物を含む、請求項1〜2のいずれか一項に記載の組成物。
- 前記抗菌コーティング組成物がさらに:前記抗菌コーティング組成物に対して濃度0.01〜2重量%で第1界面活性剤と、前記抗菌コーティング組成物に対して濃度0.001〜0.2重量%で第2界面活性剤とを含み;
前記第1界面活性剤が非イオン性であり、かつ前記第2界面活性剤がアルコールエトキシレートを含む、請求項1〜3のいずれか一項に記載の組成物。 - 前記抗菌コーティング組成物が、2〜6または2.5〜4の剪断減粘指数を有する、請求項3に記載の組成物。
- 10℃および剪断速度1s-1で測定される前記抗菌コーティング組成物の粘度が、0.5〜100Pa・sまたは2〜50Pa・sである、請求項1に記載の組成物。
- ある位置での微生物の制御を提供する方法であって、
a)i)水可溶性または水分散性皮膜形成剤;
ii)少なくとも1種類の抗菌剤;
iii)水性溶媒;
iv)カチオン性レオロジー剤;を合わせて、剪断減粘性の除去可能なコーティング組成物を得る工程と、
b)前記コーティング組成物を前記位置に塗布する工程と、
を含み、
前記位置に塗布した後に、乾燥コーティングを形成するように、前記コーティング組成物が放置される、方法。 - 前記位置が、金属、鉱物、天然および合成ポリマー、プラスチック、れんが、タイル、セラミック、磁器、ビニル、ガラス、リノリウムおよび木材からなる群から選択される材料を含む物品の少なくとも1つの表面を含む、請求項8に記載の方法。
- 前記乾燥コーティング上に水溶液を塗布することによって、前記乾燥コーティングを除去することをさらに含む、請求項8に記載の方法。
- a.(i)電気伝導率0〜10mS/cmまたは0および1mS/cmの水性溶媒;ならびに(ii)水可溶性または水分散性皮膜形成剤を合わせることによって、懸濁液を形成する工程と、
b.前記懸濁液を少なくとも10分間、30℃〜95℃に加熱する工程と、
任意の順序で(i)抗菌剤;(ii)カチオン性レオロジー剤;(iii)場合により、消泡剤、第1界面活性剤、第2界面活性剤、着色剤、可塑剤および腐食防止剤のうちの1種または複数種を含む追加の成分;を添加する工程と、
c.前記組成物を混合する工程と、
を含む、除去可能な抗菌コーティング組成物を製造する方法。
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US61/228,715 | 2009-07-27 | ||
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US61/228,723 | 2009-07-27 | ||
US12/843,120 US20110177146A1 (en) | 2009-07-27 | 2010-07-26 | Removable antimicrobial coating compositions containing cationic rheology agent and methods of use |
US12/843,120 | 2010-07-26 | ||
PCT/US2010/043382 WO2011017097A1 (en) | 2009-07-27 | 2010-07-27 | Removable antimicrobial coating compositions containing cationic rheology agent and methods of use |
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EP (1) | EP2459659B1 (ja) |
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CN (1) | CN102597132B (ja) |
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CN102597132B (zh) | 2015-04-15 |
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JP6051270B2 (ja) | 2016-12-27 |
AU2010281411A1 (en) | 2011-12-08 |
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