JP3983204B2 - Wipe sheet - Google Patents

Description

【００４５】
式（１）中、Ｅ¹で示されるヒドロキシ基又はオキソ基が置換していてもよい炭素数１〜６のアルキレン基としては、直鎖又は分岐鎖のいずれでもよく、特に炭素数２又は３の直鎖のアルキレン基が好ましい。具体的には、例えばエチレン基、プロピレン基、トリメチレン基、２−ヒドロキシトリメチレン基、１−ヒドロキシメチルエチレン基、１−オキソエチレン基、１−オキソトリメチレン基、１−メチル−２−オキソエチレン基等が好ましく、特に２−ヒドロキシトリメチレン基、１−ヒドロキシメチルエチレン基が好ましい。
【００４６】
式（１）中、Ａで示される同一又は異なって炭素数１〜６のアルキレン基としては、直鎖又は分岐鎖のいずれでもよく、特に炭素数２又は３の直鎖のアルキレン基が好ましい。具体的には、例えばエチレン基、プロピレン基及びトリメチレン基等が好ましく、特にエチレン基が好ましい。
【００４７】
ｎで表される（−ＯＡ−）の重合度は、０〜５０であるが、アレルゲン低減化効果の点から０〜４０、更に０〜３０、更に０〜２０、更に１０〜２０が好ましく、特に１０〜１５が好ましい。ｎ個のＡは同一でも異なってもよい。ここでｎは平均付加モル数の意味である。
【００４８】
式（１）中、Ｅ²はエーテル結合又はオキシカルボニル基（−ＯＣＯ−又は−ＣＯＯ−）であるが、エーテル結合が好ましい。
【００４９】
式（１）中、Ｒで示されるヒドロキシ基が置換していてもよい炭素数４〜３０のアルキル基としては、直鎖又は分岐鎖のいずれでもよく、炭素数５〜２５、更に６〜２０のものが好ましく、特に炭素数６〜２０の直鎖アルキル基が好ましい。具体的には、例えばオクチル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、イソステアリル基等が好ましく、特にドデシル基、ヘキサデシル基、オクタデシル基が好ましい。
【００５０】
Ｒで示されるヒドロキシ基が置換していてもよい炭素数１〜５のスルホアルキル基としては、例えば２−スルホエチル基、３−スルホプロピル基、３−スルホ−２−ヒドロキシプロピル基、２−スルホ−１−（ヒドロキシメチル）エチル基等が挙げられ、中でも３−スルホ−２−ヒドロキシプロピル基、２−スルホエチル基が好ましい。
当該スルホアルキル基は、その全てあるいは一部がＮａ、Ｋ、Ｃａ、Ｍｇ等の１族又は２族元素、アミン類、アンモニウム等の有機カチオン等との塩となっていてもよい。
また、スルホアルキル基の置換度は、構成単糖残基当たり０〜１．０、更に０〜０．８、特に０〜０．５の範囲が好ましい。
【００５１】
前記アレルゲン低減化剤としての前記多糖誘導体は、ＷＯ００／７３３５１号公報記載の方法に準じて製造すればよく、例えばセルロースエーテル又はスターチエーテルを、下記一般式（２）
Ｅ³−（ＯＡ）_n−Ｅ²−Ｒ （２）
〔式中、Ｅ³は炭素数３〜６のエポキシ化アルキル基、ヒドロキシ基が置換していてもよい炭素数１〜６のハロゲン化アルキル基、又はカルボキシ基若しくは炭素数２〜６のカルボキシアルキル基若しくはそれらの誘導体を示し、ｎ、Ａ、Ｅ²及びＲは前記と同じ意味を示す。〕で表されるポリオキシアルキレン化剤と反応させ、所望により更にスルホン化剤（ビニルスルホン酸、ヒドロキシ基が置換していてもよい炭素数１〜５のハロアルカンスルホン酸、炭素数２〜６のエポキシ基を有するスルホン酸及びそれらの塩）と反応させることにより製造できる。
【００５２】
前記アレルゲン低減化剤としての前記多糖誘導体は、ダニアレルゲンに対してその抗原性を減弱又は消失させる作用を有する。従って、該多糖誘導体は、各種アレルゲンに対してアレルギー反応惹起能力を減弱又は消失させ、アレルゲン低減化剤として有用である。
前記アレルゲン低減化剤としての前記多糖誘導体によるアレルゲン低減化効果は、ダニアレルゲン、ハウスダスト、スギ花粉アレルゲン、ネコなどのペットアレルゲンに対して特に有効である。
【００５３】
前記アレルゲン低減化剤は、水性洗浄剤中に前記多糖誘導体の合計で、０．００５〜２重量％、更に０．０１〜１重量％、特に０．０５〜０．５重量％となるように配合するのが、アレルゲンの低減化、洗浄性及び被清掃面の仕上がり性の面で好ましい。
【００５４】
前記界面活性剤としては、陰イオン界面活性剤、非イオン界面活性剤、陽イオン界面活性剤及び両性界面活性剤の何れもが用いられ、特に洗浄性と仕上がり性の両立の面から、ポリオキシアルキレン（アルキレンオキサイド付加モル数１〜２０）アルキル（炭素数８〜２２の直鎖又は分岐鎖）エーテル、アルキル（炭素数８〜２２の直鎖又は分岐鎖）グリコシド（平均糖縮合度１〜５）、ソルビタン脂肪酸（炭素数８〜２２の直鎖又は分岐鎖）エステル、及びアルキル（炭素数６〜２２の直鎖又は分岐鎖）グリセリルエーテル等の非イオン活性剤並びにアルキルカルボキシベタイン、アルキルスルホベタイン、アルキルヒドロキシスルホベタイン、アルキルアミドカルボキシベタイン、アルキルアミドスルホベタイン、アルキルアミドヒドロキシスルホベタイン等のアルキル炭素数８〜２４の両性界面活性剤が好適に用いられる。界面活性剤は、水性洗浄剤中に、０．０１〜１．０重量％、特に０．０５〜０．５重量％含有されることが、洗浄性及び被清掃面の仕上がり性の面で好ましい。
【００５５】
前記アルカリ剤としては、水酸化ナトリウム等の水酸化物、炭酸ナトリウム等の炭酸塩、硫酸水素ナトリウム等のアルカリ性の硫酸塩、第１リン酸ナトリウム等のリン酸塩、酢酸ナトリウム、コハク酸ナトリウム等の有機アルカリ金属塩、アンモニア、モノ、ジ又はトリエタノールアミン等のアルカノールアミン、２−アミノ−２−メチル−１−プロパノール等のβ−アミノアルカノール並びにモルホリン等が挙げられ、特に感触とｐＨの緩衝性の点でモノ、ジ又はトリエタノールアミン等のアルカノールアミン、２−アミノ−２−メチル−１−プロパノール等のβ−アミノアルカノール並びにモルホリンが好ましい。アルカリ剤は、水性洗浄剤中に、０．０１〜１重量％、特に０．０５〜０．５重量％含有されることが、洗浄性及び感触の面で好ましい。
【００５６】
前記増粘剤としては、天然多糖類、セルロース系高分子及びデンプン系高分子等の半合成高分子、ビニル系高分子及びポリエチレンオキシド等のその他合成高分子、粘土鉱物等の水溶性高分子が挙げられる。特にベタツキ感、ヌルツキ感の低いポリアクリル酸系増粘剤若しくはアクリル酸・メタクリル酸アルキル共重合体系増粘剤又はこれらの混合物が好ましい。これらアクリル酸系増粘剤は、ナトリウム塩の状態で粘性を発現するのが好ましい。増粘剤は、水性洗浄剤中に、０．０１〜２重量％、特に０．０２〜１重量％含有されることが、被清掃面の仕上がり性の点で好ましい。
【００５７】
前記水溶性溶剤としては、１価アルコール、多価アルコール及びその誘導体から選ばれる１種以上のものが好適である。特に仕上がり性の点から蒸気圧２６７Ｐａ（２ｍｍＨｇ）以上のものが好ましい。例えば、エタノール、イソプロピルアルコール、プロパノール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等が好ましい。該水溶性溶剤は、前記水性洗浄剤中に、１〜５０重量％、特に１〜２０重量％含有されることが、臭い及び皮膚刺激性の低減の点から好ましい。
【００５８】
前記水性洗浄剤には、前記アレルゲン低減化剤としての前記多糖誘導体と既知の抗アレルゲン物質として知られる、タンニン酸や、茶抽出物、ハイドロキシアパタイト、エピカテキン、エピガロカテキンガレート、エピガロカテキンガレート、没食子酸（特開平６−２７９２７３号公報）やアレルゲン補足物質であるスメクタイト等の粘土鉱物、アレルゲン除去剤として知られるヒドロキシ安息香酸化合物（特開平１１−２９２７１４号公報）等とを適宜の割合で組み合せて配合することができる。
【００５９】
前記水性洗浄剤には、前述の成分に加えて除菌剤を含有させることもできる。これによって、前記水性洗浄剤に、洗浄効果に加えて除菌効果を付与することができる。該除菌剤としては、過酸化水素、次亜塩素酸、次亜塩素酸ナトリウム、第４級アンモニウム塩、安息香酸ナトリウム、パラオキシ安息香酸ナトリウム、ポリリジンのような天然除菌剤等が挙げられ、特に第４級アンモニウム塩、ポリリジン等の天然除菌剤が配合安定性及び除菌性能の点から好ましく用いられる。該除菌剤は、前記水性洗浄剤中に、０．００５〜２重量％、特に０．０１〜１重量％含有されることが、除菌効果と皮膚刺激性低減とのバランスの点から好ましい。
【００６０】
前記水性洗浄剤には、殺ダニ剤、忌避剤、防黴剤、色素（染料、顔料）、キレート剤、ワックス剤等、消臭剤及び芳香剤等を含有させることもできる。
【００６１】
前記殺ダニ剤としては、ｄ−フェノトリン（３−フェノキシベンジル ｄ−シス／トランス−クリサンテマート）、ペルメトリン（３−フェノキシベンジル ｄｌ−シス／トランス−２，２−ジメチル−３−（２’，２’−ジクロロビニル）−シクロプロパンカルボキシレート）、レスメトリン（（５−ベンジル−３−フリル）メチル ｄｌ−シス／トランス−クリサンテマート）、アレスリン（ｄｌ−３−アリル−２−メチル−４−オキソ−２−シクロペンテニル ｄｌ−シス／トランス−クリサンテマート）、フタルスリン（（Ｎ−３，４，５，６，−テトラヒドロ−フタルイミド）メチル ｄｌ−シス／トランス−クリサンテマート）、エムペントリン（１−エチニル−２−メチル−２−ペンテニル ｄｌ−シス／トランス−クリサンテマート）、ｄ，ｄＴ８０−プラレトリン（ｄ−２−メチル−４−オキソ−３−プロパルギルシクロペント−２−エニル ｄ−シス／トランス−クリサンテマート）等の合成ピレスロイドやその誘導体が、また、ヒノキチオール、ベンジルベンゾエイト、ジャスモン酸誘導体などの天然精油成分由来の抗ダニ物質が挙げられる。
【００６２】
前記ダニ忌避剤としては、例えばジエチルアシド、ジメチルフタレート、ジブチルフタレート、ＭＧＫリペレント ３２６、ダブトレックス、２−エチル１，３−ヘキサンジオール等が使用できる。
【００６３】
前記殺ダニ剤の共力剤及び／又は殺ダニ剤としては、例えばピペロニルブトキサイド、オクタクロロジプロピルエーテル、Ｎ−（２−エチルヘキシル）−１−イソプロピル−４−メチルビシクロ〔２，２，２〕オクト−５−エン−２，３−ジカルボキシイミド、Ｎ−（２−エチニル）−ビシクロ〔２，２，１〕−ヘプタ−５−エン−２，３−ジカルボキシイミド等が使用できる。
【００６４】
屋内塵性ダニ類の餌となり、それ自体の抗原性もありえるカビ或いは細菌の増殖を抑制する殺菌剤、防黴剤としては、チアベンダゾール、トリクロサン、クロルヘキシジン、ジンクピリチオン、クロルキシレノール、デンシル、塩化ベンザルコニウム、ジクロフルアニド、安息香酸ナトリウム、ｐ−オキシ安息香酸メチル、フェノキシエタノール、エタノールおよび、キトサン、カテキン、チモール、ヒノキチオール、孟宗竹エキス、カラシ精油、ワサビ精油等の天然由来成分が挙げられる。
【００６５】
前記水性洗浄剤の媒体である水は、該水性洗浄剤中に、５０〜９９．９重量％、特に８０〜９９重量％含有されることが、被清掃面の仕上がり性の点から好ましい。
【００６６】
シート部材２には前記水性洗浄剤が含浸されて本実施形態の拭き取りシート１が形成される。これにより、湿式シートとしての特性が発現する。水性洗浄剤としては、２５℃での粘度が２０〜３００００ｍＰａ・ｓのものが用いられる。この範囲の粘度の水性洗浄剤を用いることにより、（１）清掃初期に床に放出される水性洗浄剤の量が低減されて、清掃の最初から最後までの水性洗浄剤の放出量が均一になり、（２）広い面積の被清掃面に対する清掃持続性が向上し、（３）清掃初期でも水性洗浄剤の放出量が低いので、拭き取りシートの被清掃面に対する摩擦抵抗値が低下し、（４）清掃初期でも水性洗浄剤の放出量が低いので、拭き取りシート表面の繊維自由度が大きく、髪の毛や綿ボコリを繊維によって絡み取って保持するという利点がある。水性洗浄剤の粘度が２０ｍＰａ・ｓ未満であると、清掃初期に床に放出される水性洗浄剤の量を低減させにくい。３００００Ｐａ・ｓを超えると、水性洗浄剤をシート部材に含浸することが困難になってしまう。清掃初期の水性洗浄剤放出量の低減及びシート部材への水性洗浄剤の含浸工程でのハンドリング性を一層向上させる点から、前記粘度は１００〜１０００ｍＰａ・ｓ、特に３００〜８００ｍＰａ・ｓであることが好ましい。
【００６７】
前記粘度はブルックフィールド型粘度計を用いて測定される。使用ローター及び回転数は、水性洗浄剤の粘度に応じて適宜変更する。
【００６８】
前記水性洗浄剤は、水不溶性の固体粒子を実質的に含んでいないことが好ましい。水性洗浄剤に水不溶性の固体粒子が配合された場合、被清掃面にその固体粒子が残留し、二度拭きを要する。ただし、不純物等として微量、例えば０．１重量％程度まで含まれていても差し支えはない。
【００６９】
本実施形態の拭き取りシート１は、図２に示すように、清掃部１１と該清掃部１１に連結された棒状の把手１２とを具備した掃除具１０における該清掃部１１に装着されて用いられる。詳細には、清掃具１０は、拭き取りシート１が装着可能である平坦な清掃部１１、及び清掃部１１と自在継手１３を介して連結した棒状の把手１２から構成されており、拭き取りシート１は、清掃部１１に設けられた放射状のスリットを形成する可撓性の複数の片部１４によって固定されるようになされている。
【００７０】
本実施形態の拭き取りシートによれば、洗浄剤の安定した徐放性が得られ、操作性が良く、床の広面積を清掃することができる。
【００７１】
本発明は前記実施形態に制限されない。例えば、前記実施形態における拭き取りシート１は、三層構造のシート部材にアレルゲン低減化剤含水性洗浄剤が含浸されてなるものであるが、該シート部材に代えて、単層、二層又は四層以上の構造のシートを用いてもよい。例えば、前記実施形態において、内層２の片面にのみ外層３を積層してもよい。
【００７２】
また、前記実施形態における拭き取りシート１の表面における凸部及び凹部の形状は、シートの製造のし易さや、拭き取りシート１の操作性等に応じて種々の形状とすることができる。
【００７３】
本発明の拭き取りシートは、その拭き取り対象物に特に制限はない。前記実施形態のような床以外に、例えば、壁、天井、柱等の建物の構造物の表面のほか、テーブル、ソファー等の家具、テレビ等の家電製品、台所用品、パソコン等のＯＡ機器類、衣類、寝具類、鞄、バッグ等物品の他、人体、ペットなどの動物、観葉植物などアレルゲンの付着対象となるもの全てに適用することができる。
【００７４】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。
【００７５】
〔製造例１〕
重量平均分子量１５０万、ヒドロキシエチル基の置換度１．８のヒドロキシエチルセルロース（ＨＥＣ−ＱＰ１００ＭＨ，ユニオンカーバイド社製）８０ｇ、８０％イソプロピルアルコール６４０ｇ及び４８％水酸化ナトリウム水溶液５．３４ｇを混合してスラリー液を調製し、窒素雰囲気下室温で３０分間攪拌した。この溶液に次式：
【００７６】
【化２】

【００７７】
で表されるポリオキシアルキレン化剤１２．７８ｇを加え、８０℃で８時間反応させてポリオキシアルキレン化を行った。反応終了後、反応液を酢酸で中和し、反応生成物をろ別した。反応生成物をイソプロピルアルコール５００ｇで２回、減圧下６０℃で１昼夜乾燥し、ポリオキシアルキレン化されたヒドロキシエチルセルロース誘導体（化合物１）７２．０ｇを得た。
得られたヒドロキシエチルセルロース誘導体のポリオキシアルキレン基を含む置換基の置換度は０．００４であった。
【００７８】
〔製造例２〕
製造例１及びＷＯ００／７３３５１号公報記載の方法に準じ、表１に示す化合物２〜１６を得た。
【００７９】
〔製造例３〕
（１）攪拌機、温度計及び冷却管を備えた１０００mLのガラス製セパラブル反応容器に、重量平均分子量約１５０万、ヒドロキシエチル基の置換度１．８のヒドロキシエチルセルロース（HEC-QP100M、ユニオンカーバイド社製）８０ｇ、８０％イソプロピルアルコール６４０ｇ及び４８％水酸化ナトリウム水溶液５．５ｇを加えてスラリー液を調製し、窒素雰囲気下室温で３０分間攪拌した。これにステアリルグリシジルエーテル２．５２ｇを加え、８０℃で８時間反応させて疎水化を行った。疎水化反応終了後、反応液を酢酸で中和し、反応生成物をろ別した。反応生成物を５０℃のイソプロピルアルコール５００ｇで２回、次いでアセトン５００ｇで２回洗浄し、減圧下７０℃で１昼夜乾燥し、疎水化されたヒドロキシエチルセルロース誘導体７２．８ｇを得た。
【００８０】
（２）攪拌機、温度計及び冷却管を備えた５００mLのガラス製セパラブル反応容器に、（１）で得られた疎水化ヒドロキシエチルセルロース誘導体２０．０ｇ、７０％イソプロピルアルコール２００ｇ及び４８％水酸化ナトリウム水溶液１．３７ｇを仕込んでスラリー液を調製し、窒素気流下室温で３０分間攪拌した。反応液に３−クロロ−２−ヒドロキシプロパンスルホン酸ナトリウム２８ｇ及び４８％水酸化ナトリウム水溶液１１．９ｇを加え、５０℃で３時間スルホン化を行った。反応終了後、反応液を塩酸で中和し生成物をろ別した。生成物を７０％イソプロピルアルコール３４０ｇで１回、次いでイソプロピルアルコール１２０ｇで２回洗浄後、減圧下７０℃で１昼夜乾燥し、３−ステアリルオキシ−２−ヒドロキシプロピル基と３−スルホ−２−ヒドロキシプロピル基で置換されたヒドロキシエチルセルロース誘導体（化合物１７）１８．３ｇを得た。
【００８１】
得られたヒドロキシエチルセルロース誘導体の３−ステアリルオキシ−２−ヒドロキシプロピル基の置換度は０．００３、３−スルホ−２−ヒドロキシプロピル基の置換度は０．２１０であった。
【００８２】
〔製造例４〕
製造例３の方法に準じて表１に示す化合物１８を得た。
【００８３】
〔製造例５〕
重量平均分子量約８０万、ヒドロキシエチル基の置換度１．８のヒドロキシエチルセルロース（HEC-QP15000H、ユニオンカーバイド社製）８０ｇ、イソプロピルアルコール６４０ｇ及びｐ−トルエンスルホン酸２．０ｇを混合してスラリー液を調製し、窒素雰囲気下室温で３０分間攪拌した。この溶液に次式
【００８４】
【化３】

【００８５】
で表される化合物１５ｇを加え、８０℃で８時間反応させてポリオキシアルキレン化を行った。反応終了後、反応液を４８％水酸化ナトリウム水溶液で中和し、反応生成物をろ別した。反応生成物を８０％イソプロピルアルコール５００ｇで２回、イソプロピルアルコール５００ｇで２回洗浄し、減圧下７０℃で１昼夜乾燥し、ヒドロキシエチルセルロース誘導体（化合物１９）７３．４ｇを得た。
得られたヒドロキシエチルセルロース誘導体のポリオキシアルキレン基を含む置換基の置換度は０．０１０であった。
【００８６】
〔製造例６〕
（１）ばれいしょでんぷん（片山化学社製）８０ｇ、５０％イソプロピルアルコール６４０ｇ及び４８％水酸化ナトリウム水溶液５．５ｇを混合してスラリー液を調製し、窒素雰囲気下室温で３０分間攪拌した。この溶液に次式
【００８７】
【化４】

【００８８】
で表される化合物１９．０ｇを加え、８０℃で８時間反応させてポリオキシアルキレン化を行った。反応終了後、反応液を酢酸で中和し、反応生成物をろ別した。反応生成物を５０％のイソプロピルアルコール５００ｇで２回、次いでアセトン５００ｇで２回洗浄し、減圧下７０℃で１昼夜乾燥し、ポリオキシアルキレン化されたでんぷん誘導体６９．４ｇを得た。
得られたでんぷん誘導体のポリオキシアルキレン量を含む置換基の置換度は０．００５であった。
（２）（１）で得られたポリオキシアルキレン化でんぷん３５．５ｇ、７０％イソプロピルアルコール３５０ｇ及び４８％水酸化ナトリウム水溶液２．４ｇを混合してスラリー液を調製し、窒素雰囲気下室温で３０分間攪拌した。反応液にモノクロロ酢酸ナトリウム２５．１ｇ及び４８％水酸化ナトリウム水溶液１８．０ｇを加え、５０℃で５時間カルボキシメチル化を行った。反応終了後、反応液を酢酸で中和し生成物をろ別した。生成物を７０％イソプロピルアルコール４００ｇで３回、イソプロピルアルコール３００ｇで２回洗浄後、減圧下７０℃で１昼夜乾燥し、ポリオキシアルキレン化及びカルボキシメチル化されたでんぷん誘導体（化合物２０）３３．８ｇを得た。得られたでんぷん誘導体のカルボキシメチル化度は０．４８であった。
【００８９】
【表１】

【００９０】
次に、上述のようにして製造した化合物のアレルゲン低減化効果を下記試験例１及び試験例２により調べた。
【００９１】
〔試験例１〕
（１）本発明のセスキテルペンアルコールは、１％溶液となるよう、蒸留水で調製した。室内環境アレルゲンとして、ヒョウヒダニアレルゲンであるＤｅｒｆ２量をマウスモノクローナル抗体によるサンドイッチＥＬＩＳＡ法により、アサヒビール社製のＤｅｒｆ２抗体、標識抗体を用いて測定した。
アレルゲン低減化効果は、蒸留水で同様の処理をしたときのＤｅｒｆ２量を１としてコントロールに対する比で表した。
【００９２】
（２）トリイスクラッチエキス「ダニ」（鳥居製薬社製）を透析チューブに入れ、１０％ＰＢＳ溶液で一晩透析し（４℃）、エキス中に含まれるグリセロールを除去した。本透析ダニエキスの濃度が、０．５mg／mLとなるようにＰＢＳで調製した。このダニエキス５０μＬと蒸留水で調製した１％サンプル溶液５０μＬを１．５mLのシリコナイズトマイクロチューブに入れ、ｖｏｒｔｅｘで撹拌後、室温で２時間静置した。コントロールとして、サンプルの代わりに同量の蒸留水を用いた。ポジコンとして、同量の１％タンニン酸を用いた。次に、１１．２５％ＢＳＡ（ＰＢＳに溶解）４００μＬを各チューブに加えて反応を停止させ、１５，０００rpm、室温で１０分間遠心分離し、上清をＥＬＩＳＡに供した。上記反応液中のＤｅｒｆ２量をアサヒビール社製抗Ｄｅｒｆ２モノクローナル抗体（１５Ｅ１１）、ＨＲＰ標識抗Ｄｅｒｆ２モノクローナル抗体（１３Ａ４）、検量線作成用Ｄｅｒｆ２抗原としてＤｅｒｆ２を用いて、添付のプロトコールに従い測定した。
蒸留水を用いたときのＤｅｒｆ２量を１として各サンプルで処理したＤｅｒｆ２量の比を求めた。結果を表２に示す。
【００９３】
【表２】

【００９４】
以上より本化合物１は、高いアレルゲン低減化効果を有していた。
【００９５】
〔試験例２〕
酵素標識抗ＩｇＥ抗体を用いて検出する試薬である抗原特異的ＩｇＥ抗体検出試薬クイーデルアレルギースクリーン（Xenith Biomed社製）を用いて、ディップスティック上に固相されたアレルゲン（ハウスダスト、コナヒョウヒダニ、ヤケヒョウヒダニ、ネコ上皮、スギ、ブタクサなど）とアレルギー患者ＩｇＥ抗体との反応性を以下のように測定した。
湿潤箱内に上記アレルゲンスティックをパッドが上になるように置き、パッド上に１％に調製した本発明品１００μＬ／stickを含浸させ室温で２時間静置させる。洗瓶に入れた生理食塩水で各々のパッドを均一に３０秒間洗浄したのち、アレルギー患者血清５０μＬ／stickをパッド上に静かに滴下し均一に広げる。湿潤箱に蓋をして１８時間室温で静置する。反応終了後、洗瓶に入れた生理食塩水で各々のパッドを均一に２０秒間洗浄する。
酵素標識抗ＩｇＥ抗体を約１mL試験管に分注し、洗浄したアレルゲンスティックの余分な水分を振り切り、試験管にパッドを下方にして入れ、室温で３０分間反応させる。反応終了後、水道水で各々パッドを均一に２分間洗浄する。この時、パッドについた赤色が消えることを確認する。基質液を約１mL試験管に分注し、洗浄したアレルゲンスティックの余分な水分を振り切り、試験管にパッドを下方にして入れ、室温で３０分間反応させる。反応終了後、パッドの面を裏側にして、パッドに含んだ水分をペーパータオルで押さえるようにして吸い取り、反応を停止させる。次に画像解析装置で青色発色強度を測定し、蒸留水で処理したときのアレルギー患者ＩｇＥによる発色強度をコントロールとして、アレルゲン低減化剤による反応性の低減性を次式により計算した。結果を表３及び表４に示す。
アレルゲン低減化効果（％）＝１００−（本発明品処理した際のＩｇＥ反応強度−陰性コントロールの反応強度）／（蒸留水処理したコントロールＩｇＥ反応強度−陰性コントロールの反応強度）×１００
【００９６】
【表３】

【００９７】
【表４】

【００９８】
この結果、製造された各化合物１〜２２は高いアレルゲン低減効果を有していた。
【００９９】
次に、下記実施例及び比較例のように拭き取りシートを作製し、それらの拭き取り性能およびアレルゲン低減化効果を下記のように評価した。それらの結果を表５に示す。
【０１００】
〔実施例１〕
芯がポリプロピレンからなり鞘がポリエチレンからなる芯鞘構造で、立体クリンプ形状をもつ低融点繊維（２．８ｄｔｅｘ×５１ｍｍ、鞘成分の融点１３０℃）を用いて坪量２７ｇ／ｍ²のエアースルー不織布を作製した。繊維同士を温度１４０℃で熱接着させた。このエアースルー不織布の破断強度は、流れ方向（ＭＤ）が１６６０ｃＮ／２５ｍｍ、幅方向（ＣＤ）が２２０ｃＮ／２５ｍｍであった。
【０１０１】
一方、レーヨン繊維（１．７ｄｔｅｘ×４０ｍｍ）と、アクリル繊維（０．９ｄｔｅｘ×５１ｍｍ）と、芯がポリプロピレンからなり鞘がポリエチレンからなる芯鞘繊維（１．０ｄｔｅｘ×３８ｍｍ）とを、重量比５０／２５／２５の比率で混合し、常法のカード機で作製した坪量１９ｇ／ｍ²の繊維ウエブを、前記エアースルー不織布の上下に積層した。次いで、低エネルギー条件でウォーターニードリング処理を施し、エアースルー不織布と繊維ウエブとを交絡させて繊維自由度の高い表面層を有する坪量６５ｇ／ｍ²の複合スパンレース不織布を調製した。超音波エンボス機を用い、調製した不織布の全面にダイヤ柄の凹凸模様からなるエンボス加工を施してシート状部材を得た。
【０１０２】
水／アレルゲン低減化剤／エタノール／２−アミノ−２−メチル−１−プロパノール／ドデシルグルコシド（縮合度１．４）／増粘剤（カーボポールＥＴＤ２０２０、日光ケミカル社製）／クエン酸３ナトリウム＝９３．５０１／０．１／６／０．１４５／０．１／０．１２／０．０３４（重量比）からなるアレルゲン低減化剤含水性洗浄剤（粘度：７００ｍＰａ・ｓ／２５℃）を、得られた不織布に含浸させて床用拭き取りシートを調製した。なお、アレルゲン低減化剤には、前記製造例の化合物４を用いた。該水性洗浄剤の含浸率は、不織布重量に対して２５０％であった。尚、カーボポールＥＴＤ２０２０はアクリル酸・メタクリル酸アルキル（炭素数１０〜３０）共重合体である。水性洗浄剤を含浸した状態での拭き取りシートの破断強度は、流れ方向（ＭＤ）が３１２０ｃＮ／２５ｍｍ、幅方向（ＣＤ）が４１０ｃＮ／２５ｍｍであった。
【０１０３】
〔実施例２〕
樹脂製ネット（ポリプロピレン製の格子状ネット繊維間距離８ｍｍ、線径３００μｍ）の両面にポリエステル繊維（１．６ｄｔｅｘ×５１ｍｍ）、レーヨン繊維（１．７ｄｔｅｘ×４４ｍｍ）と、アクリル繊維（０．９ｄｔｅｘ×５１ｍｍ）を重量比５０／２５／２５の比率で混合し、上方の常法のカード機で作製した坪量３０ｇ／ｍ² の繊維ウエブを積層した。次いで、低エネルギー条件でウォーターニードリング処理を施し、同時に支持体の形状に賦形して不織布（シート状部材）を得た。得られた不織布に実施例１で用いたアレルゲン低減化剤含洗浄剤（粘度７００ｍＰａ・ｓ／２５℃）を不織布重量に対して２５０％含浸させた。水性洗浄剤を含浸した状態での拭き取りシートの破断強度は、流れ方向（ＭＤ）が３８３３ｃＮ／２５ｍｍ、幅方向（ＣＤ）が１１８２ｃＮ／２５ｍｍであった。
【０１０４】
〔比較例１〕
アレルゲン低減化剤含洗浄剤を含浸させなかった以外は、実施例１と同様にして拭き取りシートを作製した。
【０１０５】
〔比較例２〕
アレルゲン低減化剤含洗浄剤を含浸させなかった以外は、実施例２と同様にして拭き取りシートを作製した。
【０１０６】
得られた拭き取りシートについて、下記１）〜８）のように拭き取り性能を評価した。
【０１０７】
１）洗浄剤放出量
拭き取りシートをクイックルワイパー〔花王（株）製〕に装着してフローリングを６畳拭き続けた時の１畳あたりに放出される洗浄液量を測定した。１畳拭くごとに拭き取りシートを清掃部ヘッドから外してその重量を測定することで洗浄液量を測定した。清掃方法は約９０ｃｍの距離を１往復拭くのを１ストロークとし、それを１畳の長手方向（１８０ｃｍ）に２列、短手方向（９０ｃｍ）に４列拭いて１畳の清掃を完結した。
【０１０８】
２）拭き取りシートの表面層の繊維自由度の指標となる静摩擦抵抗値
前述した方法に従い測定した。尚、４００ｇの荷重は、クイックルワイパー〔花王（株）製〕に、拭き取りシートを装着して床を清掃した場合にシートにかかる平均荷重にほぼ相当する。
【０１０９】
３）凸部の面積率
前述の方法に従い測定した。
【０１１０】
４）髪の毛の捕集率
クイックルワイパー〔花王（株）製〕に、拭き取りシートを装着した。３０ｃｍ×６０ｃｍのフローリング（松下電工製、ウッディタイルＭＴ６１３Ｔ）上に約１０ｃｍの髪の毛を５本散布し、その上に拭き取りシートを乗せて一定のストローク（６０ｃｍ）で２往復清掃して拭き取りシートに捕集された髪の毛の本数を測定した。この操作を連続６回実施して、３０本中何本の髪の毛が捕集されたかを測定した。捕集された髪の毛の数を３０で除し、これに１００を乗じて、その値を髪の毛の捕集率（％）とした。
【０１１１】
５）ダスト（土ぼこり）の捕集性
クイックルワイパー〔花王（株）製〕に、拭き取りシートを装着した。１００ｃｍ×１００ｃｍのフローリング（松下電工製、ウッディタイルＭＴ６１３Ｔ）上にＪＩＳ試験用ダスト７種（関東ローム層、細粒）を０．１ｇ散布し（ハケを用いて全面に均一散布）、フローリングを１往復で４列清掃した。この操作を連続６回した後、汚れた拭き取りシートを乾燥させて重量（シート＋洗浄剤不揮発成分＋ダスト）を測定し、含浸前に測定したシート重量と理論上残留する洗浄剤不揮発成分重量を差し引いてダストの捕集量を算出した。捕集されたダストの重量を、散布した全ダスト重量（０．６ｇ＝０．１ｇ×６回）で除し、これに１００を乗じて、その値をダストの捕集率（％）とした。
【０１１２】
６）６畳目の醤油乾燥汚れの除去性
フローリング（面積：１畳）上に市販の醤油を１滴（０．０２ｇ）たらして、ドライヤーで乾燥させた。クイックルワイパー〔花王（株）製〕に、拭き取りシートを装着して別のきれいなフローリングを５畳分連続して清掃した後に、乾燥した醤油汚れが付着したフローリング１畳を清掃して以下の基準で評価を行った。尚、先に清掃する５畳分のフローリングは洗浄剤放出量の測定時と同様な方法で清掃し、醤油汚れの付着したフローリングは汚れの上のみを拭いて、その清掃回数と汚れ落ちの関係を評価した。
○：１０往復以下の清掃で完全に汚れが除去できた。
○〜△：１５往復の清掃で完全に汚れが除去できた。
△：２０往復の清掃で完全に汚れが除去できた。
△〜×：３０往復の清掃で完全に汚れが除去できた。
×：３０往復を超えても完全に汚れは除去できなかった。
【０１１３】
７）仕上がり性
クイックルワイパー〔花王（株）製〕に、拭き取りシートを装着して、１００×１００ｃｍのきれいなフローリングを清掃した。乾燥後のフローリングの仕上がり性を、蛍光灯にかざして以下の３段階で目視評価した。
○：洗浄剤成分の残留痕（拭き筋等）がない。
△：洗浄剤成分の残留痕（拭き筋等）が若干ある。
×：洗浄剤成分の残留痕（拭き筋等）がある。
【０１１４】
８）１畳目清掃時のワイパーの操作性及び拭き始めのワイパー操作荷重
クイックルワイパー〔花王（株）製〕に、拭き取りシートを装着して、フローリング板（松下電工製 ウッデイタイルＥタイプ ＫＥＲ５０１）を片手で拭き始める時のワイパーの操作性を以下の４段階で目視評価した。
○：ほとんど抵抗感を感じない。
○〜△：やや抵抗感を感じるが、片手で拭ける。
△：抵抗感を感じるが、片手で拭ける。
×：大きな抵抗感があり、片手で拭いた時にワイパーの柄がたわむ。
また、図４に示すようにクイックルワイパー３０の清掃ヘッド部３１と柄３２の間に圧縮荷重測定用のロードセル３３を装着し、このクイックルワイパー３０を用いて、前記フローリング３４を拭き始めた時の圧縮荷重を測定した。
【０１１５】
〔アレルゲン低減化効果の評価〕
下記のように花粉の除去効果を調べ、アレルゲン低減化効果を４段階で評価した。
３０ｃｍ角のガラス板の表面にスギ花粉５０ｍｇを散布し、得られた拭き取りシートで拭き取った後、ｐＨ７．４±０．１に調整したリン酸バッファー液（ＫＨ₂ＰＯ₄、ＮａＣｌ、Ｎａ₂ＰＯ₄・７Ｈ₂Ｏをそれぞれ０．１４４ｇ／Ｌ、９．００ｇ／Ｌ、０．７９５ｇ／Ｌとなるように蒸留水に溶解したもの）５０ｍＬで、前記ガラス板の表面に残留した花粉を洗い流した。そして、洗い流した該液から下記方法を用いて花粉アレルゲン量を定量し、残留花粉量とした（この花粉量を残留花粉量という。）。
【０１１６】
＜花粉アレルゲン量の定量＞
下記定量法を用いてサンプル中のＣｒｙ ｊ１及びＣｒｙ ｊ２を定量し、その和を以てサンプル中のスギ花粉アレルゲン量とした。
【０１１７】
〔Ｃｒｙ ｊ１のＥＬＩＳＡ定量法〕
１．モノクロナール抗体Ａｂ−Ｃｒｙ ｊ１ ｍＡｂ ０１３（生化学工業（株）製）をＰＢＳで２μｇ／ｍＬの濃度に希釈し、マイクロプレート（住友ベークライト製、ＥＬＩＳＡ ＰＬＡＴＥ Ｈ ＴＹＰＥ）の各ウェルに５０μＬずつ分注し、室温で２時間静置する。
２．マイクロプレートをＰＢＳで３回洗浄する。
３．１％ＢＳＡを含むＰＢＳ（大日本製薬製、ブロックエース）を各ウェルに２００μＬずつ分注し、室温で１時間静置してブロッキングを行う。
４．Ｔｗｅｅｎ２０（ＳＩＧＭＡ）を０．０５質量％含有するＰＢＳ（以下、Ｔ−ＰＢＳという。）でマイクロプレートを３回洗浄する。
５．スタンダードとして精製Ｃｒｙ ｊ１（生化学工業（株）製）を４ｎｇ／ｍＬからｎ＝５管Ｔ−ＰＢＳで２ⁿ倍希釈し、各々５０μＬを各ウェルに分注し、さらに陰性対照としてＣｒｙ ｊ１の替わりにＴ−ＰＢＳを５０μＬ加えたウェルを用意する。測定する試料は、Ｔ−ＰＢＳで適宜希釈してから各ウェルに５０μＬずつ分注し、室温で２時間静置する。
６．マイクロプレートをＴ−ＰＢＳで３回洗浄する。
７．至適濃度のＰｅｒｏｘｉｄａｓｅ Ｃｏｎｊｕｇａｔｅｄ Ａｂ−Ｃｒｙｊ１ ｍＡｂ ０５３（生化学工業（株）製）を各ウェルに５０μＬ分注し、室温で２時間静置する。
８．マイクロプレートをＴ−ＰＢＳで３回洗浄する。
９．ペルオキシダーゼ用発色キット（住友ベークライト製）を用いて発色を行う。先ず発色剤１０ｍＬに基質液を０．１ｍＬ加えて混和して発色液とする。この発色液を各ウェルに１００μＬずつ分注し、室温で発色させる。その後停止液を各ウェルに１００μＬずつ分注して反応を止め、プレートリーダーで４５０ｎｍにおける吸光度を測定する。
１０．スタンダードの吸光度から得られる検量線を用いて測定する試料のＣｒｙ ｊ１濃度を算出する。
【０１１８】
〔Ｃｒｙ ｊ２ のＥＬＩＳＡ定量法〕
１．モノクロナール抗体Ａｂ−Ｃｒｙ ｊ２ ｍＡｂ Ｔ２７（生化学工業（株）製）をＰＢＳで２μｇ／ｍＬの濃度に希釈し、マイクロプレート（住友ベークライト製、ＥＬＩＳＡ ＰＬＡＴＥ Ｈ ＴＹＰＥ）の各ウェルに５０μＬずつ分注し、室温で２時間静置する。
２．マイクロプレートをＰＢＳで３回洗浄する。
３．１％ＢＳＡを含むＰＢＳ（大日本製薬製、ブロックエース）を各ウェルに２００μＬずつ分注し、室温で１時間静置してブロッキングを行う。
４．Ｔ−ＰＢＳでマイクロプレートを３回洗浄する。
５．スタンダードとして精製Ｃｒｙ ｊ２（生化学工業（株）製）を１０ｎｇ／ｍＬからｎ＝５管Ｔ−ＰＢＳで２ⁿ倍希釈し、各々５０μＬを各ウェルに分注し、さらに陰性対照としてＣｒｙ ｊ２の替わりにＴ−ＰＢＳを５０μＬ加えたウェルを用意する。測定する試料は、Ｔ−ＰＢＳで適宜希釈してから各ウェルに５０μＬずつ分注し、室温で２時間静置する。
６．マイクロプレートをＴ−ＰＢＳで３回洗浄する。
７．至適濃度のＰｅｒｏｘｉｄａｓｅ Ｃｏｎｊｕｇａｔｅｄ Ａｂ−Ｃｒｙｊ２ ｐＡｂ（生化学工業（株）製）を各ウェルに５０μＬ分注し、室温で２時間静置する。
８．マイクロプレートをＴ−ＰＢＳで３回洗浄する。
９．ペルオキシダーゼ用発色キット（住友ベークライト製）を用いて発色を行う。先ず発色剤１０ｍＬに基質液を０．１ｍＬ加えて混和して発色液とする。この発色液を各ウェルに１００μＬずつ分注し、室温で発色させる。その後停止液を各ウェルに１００μＬずつ分注して反応を止め、プレートリーダーで４５０ｎｍにおける吸光度を測定する。
１０．スタンダードの吸光度から得られる検量線を用いて測定する試料のＣｒｙ ｊ２濃度を算出する。
【０１１９】
上述のようにして求めたスギ花粉アレルゲン量をから、下記式により花粉低減化率をもとめその値を指標として下記の４段階で評価した。
花粉低減化率（％）＝（残留花粉量／比較例１の残留花粉量）×１００
◎：花粉量低減化率が３０％未満である。
○：花粉量低減化率が３０％以上５０％未満である。
△：花粉低減化率が５０％以上８０％未満である。
×：花粉低減化率が８０％以上である。
【０１２０】
【表５】

【０１２１】
表５に示すように、実施例の拭き取りシート（本発明品）は、比較例の拭き取りシートに比べて、拭き取り操作によって対象物表面に存在するアレルゲンを低減化することが分かった。
【０１２２】
【発明の効果】
本発明の拭き取りシートによれば、拭き取り操作によって対象物表面に存在するアレルゲンを低減化することができる。
【図面の簡単な説明】
【図１】本発明の拭き取りシートの一実施形態を模式的に示す斜視図である。
【図２】本発明の拭き取りシートが掃除具に装着された状態を示す斜視図である。
【図３】拭き取りシートの静摩擦抵抗値の測定方法を示す模式図である。
【図４】拭き始めのワイパー操作荷重の測定方法を示す模式図である。
【符号の説明】
１ 床用拭き取りシート
２ シート部材
３ 内層
４ 外層
５ 凸部
６ 凹部
１０ 掃除具
１１ 清掃部
１２ 把手[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a wiping sheet, and more particularly, to a wet wiping sheet having a function of reducing allergens present on the surface of an object to be wiped.
[0002]
[Prior art and problems to be solved by the invention]
Allergic diseases such as atopic dermatitis, allergic rhinitis, and asthma have been increasing in recent years and have become important social problems. One factor contributing to the increase in allergic diseases is the increase in allergens in the environment. Especially, due to the improved airtightness of houses, conditions suitable for tick breeding in the room have been established, and the amount of indoor allergens such as mite allergens has increased. Increase is a problem.
[0003]
As a technique for suppressing the growth of allergens in a room, a technique described in Patent Document 1 below is known. In this technology, the cleaning tool that adsorbs and holds dust and dust in the room is treated with an oil containing a drug having acaricidal activity and mite growth-inhibiting activity, and the growth of mites adsorbed and held by the cleaning tool is increased. It is something to be suppressed.
[0004]
However, this technology can suppress the growth of ticks caused by ticks adsorbed and held by a cleaning tool, but it has no effect on allergens that soar during cleaning. Since allergenicity remains in yafun, it cannot be said to be a fundamental method for reducing the amount of allergen.
[0005]
[Patent Document 1]
JP-A-10-75924
[0006]
Therefore, an object of this invention is to provide the wiping sheet which can reduce the allergen which exists in the target object surface by wiping operation.
[0007]
[Means for Solving the Problems]
As a result of searching for substances that can stably inactivate allergens in the environment and have no adverse effects on the environment and the human body, the present inventors have induced allergic reactions to allergens. It has been found that it has an effect of reducing ability and is useful as an allergen reducing agent.
[0008]
The present invention has been made based on the above knowledge, and is a wiping sheet in which an allergen reducing agent is included in a sheet member, wherein the allergen reducing agent is a polysaccharide derivative having a cellulose ether or starch ether as a main chain. Yes, some or all of the hydrogen atoms of the hydroxy group are represented by the following general formula (1):
-E ¹ -(OA) _n -E ² -R (1)
[Where E ¹ Represents an alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxy group or an oxo group, n represents a number of 0 to 50, and n A's are the same or different and have 1 to 6 carbon atoms. Represents an alkylene group, E ² Represents an ether bond or an oxycarbonyl group, and R represents an alkyl group having 4 to 30 carbon atoms that may be substituted by a hydroxy group, a sulfoalkyl group having 1 to 5 carbon atoms that may be substituted by a hydroxy group, or a group thereof. Indicates salt. A wipe sheet comprising a polysaccharide derivative substituted with a group represented by the formula:
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below based on preferred embodiments with reference to the drawings. Below, based on one Embodiment which applied the wiping sheet | seat of this invention to the cleaning sheet for floors, it demonstrates.
[0010]
As shown in FIG. 1, the wiping sheet 1 is a sheet member 2 containing an allergen reducing agent. The wiping sheet 1 of this embodiment is a wet wiping sheet in which an allergen reducing agent is included in the sheet member 2 by impregnating the sheet member 2 with an aqueous cleaning agent containing the allergen reducing agent.
[0011]
The sheet member 2 is a laminated sheet in which an inner layer 3 and a pair of outer layers 4 and 4 sandwiching the inner layer 3 from above and below are integrated.
[0012]
The aqueous cleaning agent containing the allergen reducing agent is preferably impregnated in an amount of 100 to 1000% by weight per sheet member weight (that is, based on the weight of the wiping sheet 1 in an unimpregnated state (dry state)). If the impregnation rate is less than 100% by weight, sufficient cleaning performance against stains and dirt may not be obtained, and if it exceeds 1000% by weight, the amount of cleaning agent released to the floor will increase so much that Dirt and dirt will remain, and some woody floors may be adversely affected. From the viewpoint of further improving the cleaning property, the impregnation ratio of the aqueous cleaning agent is preferably 150 to 350% by weight, particularly 200 to 300% by weight. The sheet member is impregnated with the aqueous cleaning agent so that the sheet member is impregnated with the aqueous cleaning agent and the excess aqueous cleaning agent is removed as it is or by mangle treatment, and then the weight of the sheet member is not affected. Measured under load.
[0013]
The sheet member (that is, the wiping sheet 1 before impregnated with the aqueous cleaning agent containing the allergen reducing agent) 2 has a basis weight of 40 to 200 g / m. ² It is preferable that The basis weight of the sheet member is 40 g / m ² If it is less than this, it becomes difficult to impregnate the cleaning agent in an amount necessary for wiping a large area floor. 200 g / m ² If it exceeds 1, the operability may be inferior due to an increase in weight, and the cost will be increased. The basis weight is 50 to 150 g / m. ² , Especially 55-100 g / m ² It is more preferable that The thickness is 3 g / m in a dry state. ² Is preferably 0.2 to 10 mm, more preferably 0.4 to 5 mm, and particularly preferably 0.6 to 2 mm in terms of followability to uneven floors and cost.
[0014]
The outer layer 4 constituting the sheet member 2 constitutes a surface layer of the wiping sheet 1 of the present embodiment, and is a part that contacts the floor when the wiping sheet 1 is used. The outer layer 4 is preferably composed of a nonwoven fabric composed of fibers having a fiber length of 20 mm or more, particularly 30 to 100 mm, particularly 35 to 65 mm, in terms of sufficiently expressing the surface strength of the wiping sheet 1. A nonwoven fabric composed of fibers having a fiber length of 20 mm or more does not require that the fiber length of all the constituent fibers be 20 mm or more, and is inevitably mixed in the raw material of the nonwoven fabric and / or in the production process. It is permissible to include fibers with a fiber length of less than 20 mm. In the present embodiment, the outer layer 4 corresponds to the surface layer, but when the sheet impregnated with the cleaning agent has a single layer structure, the surface layer in the sheet is the surface of the sheet. And an area in the vicinity thereof.
[0015]
As shown in FIG. 1, the sheet member 2 is subjected to heat embossing in a rhombus lattice shape, and a linear shape that divides each convex portion 5 from a large number of convex portions 5 formed on the surface thereof. And the recess 6. The concave portion 6 is more consolidated than the convex portion 5 by application of heat and pressure by hot embossing. The area of the convex portion 5 is 30 to 95%, particularly 40 to 85%, especially 50 to 80% of the apparent area of the cleaning surface of the wiping sheet 1, and the collection of hair and cotton dust when cleaning is performed. This is preferable from the standpoint of achieving both compatibility and operability of the cleaning tool. Here, the apparent area of the cleaning surface of the wiping sheet 1 refers to the area when the cleaning surface of the wiping sheet 1 is viewed in plan.
[0016]
The area of the convex part 5 is measured as follows. In other words, a wiping sheet (10 cm x 10 cm) impregnated with a predetermined amount of aqueous cleaning agent is spread to one sheet, and a penmanship practice half-paper that darkens the wetted parts [Black Kuretake Seidou Co., Ltd. Placed on KN37-10]. A 10 cm × 10 cm acrylic plate (25 g) was placed on the wiping sheet, and a weight of 2000 g was placed thereon, and a load was applied for 60 seconds. Thereafter, the weight and the acrylic plate are quickly removed, and the area of the half-darkened portion of the semi-paper is obtained using an image analyzer [manufactured by Nexus Corp., New Qube], and this value is calculated as the area of the convex portion 5. did. Furthermore, the area of the convex part 5 is 100 cm. ² The value divided by (apparent area of the cleaning surface of the wiping sheet) was defined as the area ratio of the convex portion 5.
[0017]
Although the pattern shape of the recessed part 6 formed by the said embossing is not specifically limited to what is shown in FIG. 1, It is preferable that it is a pattern which has a continuous linear shape, curved shape, or both in part. In particular, it is preferable in terms of maintaining the surface strength of the wiping sheet 1 that the continuous linear recesses 6 intersect each other and the protrusions 5 closed by the recesses 6 are formed. When the recess 6 is linear or curved, the line width is preferably 0.5 to 3 mm. Further, the distance between the recesses 6 is appropriately adjusted according to characteristics required for the wiping sheet 1. Further, an emboss pattern obtained by combining the continuous linear pattern and the discontinuous dot pattern is also preferably used.
[0018]
As described above, the outer layer 4 of the sheet member 2 is preferably made of a nonwoven fabric. As the nonwoven fabric, a spunlace nonwoven fabric capable of expressing a low fiber entangled state is preferable from the viewpoint of the texture of the sheet and the entanglement properties of hair and cotton dust.
[0019]
The fibers constituting the outer layer 4 preferably include hydrophilic cellulose fibers and low-melting point thermoplastic fibers from the viewpoint of maintaining cleanability, operability, and sheet strength.
[0020]
The hydrophilic cellulose fibers are preferably contained in an amount of 30 to 98% by weight, particularly 50 to 90% by weight, based on the weight of the outer layer 4, from the viewpoint of efficiently removing stain stains and dirt. This is because the hydrophilic cellulose fiber is excellent in the property of reabsorbing dirty liquid in which dirt and dirt are dissolved and dispersed. Examples of the hydrophilic cellulose fiber include rayon and cotton fiber.
[0021]
The low-melting point thermoplastic fibers are contained in an amount of 2 to 70% by weight, particularly 10 to 50% by weight, based on the weight of the outer layer 4, so that the sheet strength after heat embossing is improved and the operability is good. It is preferable from the point which becomes.
[0022]
As the low melting point thermoplastic fiber, those having a melting point of 200 ° C. or lower are preferable, and those having a melting point of 170 ° C. or lower are particularly preferable. Specifically, polyethylene-based fibers, polypropylene-based fibers, low-melting-type polyethylene terephthalate-based fibers, polyvinyl alcohol fibers, and low-melting fibers of these fibers are sheath components, and core-sheath fibers having high-melting fibers as core components, And side-by-side fibers of low-melting fibers and high-melting fibers.
[0023]
From the viewpoint of improving the cleanability, operability, and texture of the sheet, the outer layer 4 can contain other synthetic fibers in addition to the hydrophilic cellulose fibers and the low-melting thermoplastic fibers. Examples of other synthetic fibers include polyester fibers, polyacrylonitrile fibers, nylon fibers, acetate fibers, polyvinyl alcohol fibers, and polyvinyl chloride fibers.
[0024]
Although there is no restriction | limiting in particular in the fiber diameter of the fiber which comprises the outer layer 4, A thing of 3.3 dtex or less is preferable, and the thing of 0.5-2.0 dtex is especially more preferable from the surface of the entanglement property of hair and cotton dust. Moreover, there is no restriction | limiting in particular also in the fiber length of this fiber, Both a long fiber filament and a short fiber staple fiber can be used.
[0025]
The basis weight of the outer layer 4 is 8 to 70 g / m in relation to the basis weight described above with respect to the sheet member. ² , Especially 15-30g / m ² It is preferable that Moreover, the thickness (thickness of each outer layer 4) is preferably 0.05 to 5 mm, and is 0.1 to 2 mm, particularly 0.2 to 1 mm from the viewpoint of the ability to collect hair and cotton dust and cost. Is more preferable.
[0026]
For the inner layer 3 constituting the sheet member, various sheet materials such as paper, nonwoven fabric, woven fabric, and resin net can be used. These sheet materials preferably have a high strength, for example, a breaking strength of 200 cN / 25 mm or more from the viewpoint of maintaining the strength of the wiping sheet. The basis weight of the sheet member is 100 g / m ² In the case of the following, the inner layer 3 is preferably low-density and bulky from the viewpoint of retaining the aqueous cleaning agent and expressing the strength, thickness feeling and cushioning properties of the sheet member. As a constituent material of the inner layer 3 having such properties, for example, a nonwoven fabric such as a thermal bond (air-through) nonwoven fabric, a spunlace nonwoven fabric, and an airlaid nonwoven fabric is preferable. The higher the breaking strength is, the more preferable, but in reality, the upper limit is about 100 N / 25 mm.
[0027]
When the inner layer 3 is composed of fibers, hydrophilic fibers such as rayon, cotton, pulp, and polyvinyl alcohol fibers can be used as the fibers. Moreover, it is also preferable to mainly use hydrophobic fibers from the viewpoint of increasing the thickness of the inner layer 3 and improving cushioning properties. Examples thereof include polyolefin fibers such as polyethylene and polypropylene, polyamide fibers such as polyester fibers and nylon, polyacrylonitrile fibers, and composite fibers such as core-sheath fibers and side-by-side fibers of these fibers. It is preferable that the three-dimensional crimp is applied to these fibers from the viewpoint of increasing the thickness of the inner layer 3 and improving the cushioning property. Moreover, when forming an uneven | corrugated | grooved part in the surface of the sheet | seat member 2 by heat processing, a heat shrinkable fiber and a heat crimpable fiber are used.
[0028]
When the inner layer 3 is composed of fibers, the fiber diameter of the fibers is not particularly limited, but 1 to 7 dtex is preferable from the viewpoint of increasing the thickness and cushioning properties. Moreover, there is no restriction | limiting in particular also in the fiber length of this fiber, Both a long fiber filament and a short fiber staple fiber can be used.
[0029]
The basis weight of the inner layer 3 is 20 to 150 g / m in relation to the basis weight described above for the sheet member. ² , Especially 25-80g / m ² It is preferable that Moreover, it is preferable that the thickness is 0.2-4.8 mm, 0.4-3 mm from the point which raises thickness and cushioning property, and the point which satisfies the cost without a feeling of resistance to disposable, especially 0.6- More preferably, it is 2 mm.
When the inner layer is formed of a resin net, the basis weight of the inner layer is 3 to 150 g / m. ² In particular, it is preferably 5 to 50 g / m. In this case, the basis weight of the outer layer is increased as necessary. Furthermore, in this case, it is preferable to reduce the amount of the hydrophilic cellulose fiber in the outer layer from the relationship between the operability and the amount of the detergent released to the floor, and it is preferably 10 to 80% by weight, particularly 20 to 60% by weight of the outer layer. It is preferable to make it weight%. Since the thermoplastic fiber can exhibit strength by spunlace processing, it does not need to be heat embossed, so it does not need to be mixed, and 20 to 90% by weight of the outer layer together with the synthetic fiber, especially 40 to 80% It is preferable that
[0030]
The sheet member 2 composed of the inner layer 3 and the outer layer 4 described above is preferably manufactured by the following method, for example. First, a spunlace nonwoven fabric with a low degree of entanglement and a high degree of fiber freedom that will be the outer layer 4 is produced. Separately from this, a low-density and bulky thermal bond nonwoven fabric to be the inner layer 3 is produced. The outer layer 4 is arranged on both surfaces of the inner layer 3 and heat embossing is performed to integrate the three members to form a sheet member.
[0031]
As another preferable production method, first, a fiber web produced by a card method or the like is superposed on both surfaces of the thermal bond nonwoven fabric to be the inner layer 3, and then an entanglement treatment (water needling treatment) using a high-pressure water flow. To form a spunlace nonwoven fabric constituting the outer layer 4 by entanglement between the fibers of the fiber web, and the fiber web is integrated in an entangled state with the inner layer 3 made of a thermal bond nonwoven fabric. Manufacture composite spunlace nonwoven fabric. The nonwoven fabric obtained in this way is a nonwoven fabric-like fiber assembly (spunlace nonwoven fabric) formed by entanglement of fiber webs on both sides of a thermal bond nonwoven fabric, which is a sheet material, together with the entanglement of its constituent fibers. The sheet material is also integrated in an entangled state. This is then subjected to hot embossing to form a sheet member.
[0032]
Whatever manufacturing method is used, from the viewpoint of effectively entwining hair and cotton dust, the degree of freedom of each fiber of the surface layer that contacts the floor during use is increased, that is, the surface layer is lowered. It is preferable that the fiber is entangled.
[0033]
The static friction resistance value can be adopted as an index of the fiber entanglement state of the surface layer in the wiping sheet 1 of the present embodiment. The static friction resistance value is measured by the method shown in FIG. That is, a weight 21 (total weight 400 g including sandpaper) 21 with a sandpaper (3M water resistant paper Techno sander particle size No. 1200) 20 is firmly fixed on a horizontal base 23. Further, the sandpaper is placed on the surface of the wiping sheet 22 (200 mm × 280 mm) impregnated with the aqueous detergent so that the sand surface of the sandpaper faces the wiping sheet. A thread 24 is attached to the side surface of the weight, and the other end of the thread 24 is attached to a load cell 26 of a tensile tester (Orientic, RTM-25) via a pulley 25. The tensile tester is operated and the weight 21 is moved horizontally by 30 mm at a speed of 500 mm / min. The initial maximum static frictional resistance value at that time is measured, and this is used as an index of the fiber entanglement degree of the surface layer. The measurement is performed in the sheet flow direction (MD) and the width direction (CD) in the wiping sheet manufacturing process. The sandpaper is replaced with a new one after each measurement.
[0034]
In the surface layer of the wiping sheet impregnated with the aqueous cleaning agent, the fiber is caught in the sandpaper as the fiber is in a low entanglement state, that is, the degree of freedom of each fiber is high. Tends to show a high value.
[0035]
It is preferable that the static friction resistance value of the surface layer in the wiping sheet 1 serving as an index of the fiber entanglement state is 900 to 2500 cN. If it is less than 900 cN, it becomes difficult to obtain good entanglement of hair and cotton dust. If it exceeds 2500 cN, the surface strength of the sheet may be weakened, and the fibers may be caught by burrs or the like on the floor board, and the operability of the mop may become heavy. A more preferable static friction resistance value is in the range of 1100 to 2200 cN, particularly 1200 to 2000 cN. The static friction resistance value is most preferably within the above range in any of the MD and CD directions of the wiping sheet 1, but it is sufficient if the static friction resistance value in at least one of the directions is within the above range.
[0036]
The sheet member 2 has a breaking strength of 200 cN / 25 mm or more, and particularly 300 to 8000 cN / 25 mm, which suppresses fiber dropping from the surface layer and entanglement of hair and cotton dust. It is preferable from the point. As for the breaking strength, at least one of the flow direction (MD) and the width direction (CD) of the sheet member satisfies the above value.
[0037]
The aqueous cleaning agent preferably contains water as a medium and contains an allergen reducing agent, a surfactant, an alkali agent, a thickener and a water-soluble solvent. All the components contained in the aqueous cleaning agent are preferably substantially water-soluble. The non-volatile residual component contained in the aqueous cleaning agent is preferably 10% by weight or less in terms of finish after cleaning, particularly 5% by weight or less, and particularly preferably 1% by weight or less.
[0038]
The allergen reducing agent is a polysaccharide derivative having cellulose ether or starch ether as a main chain, and part or all of the hydrogen atoms of the hydroxy group are represented by the following general formula (1):
-E ¹ -(OA) _n -E ² -R (1)
[Where E ¹ Represents an alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxy group or an oxo group, n represents a number of 0 to 50, and n A's are the same or different and have 1 to 6 carbon atoms. Represents an alkylene group, E ² Represents an ether bond or an oxycarbonyl group, and R represents an alkyl group having 4 to 30 carbon atoms that may be substituted by a hydroxy group, a sulfoalkyl group having 1 to 5 carbon atoms that may be substituted by a hydroxy group, or a group thereof. Indicates salt. ] A polysaccharide derivative substituted with a group represented by the formula:
[0039]
The polysaccharide derivative as the allergen reducing agent has cellulose ether or starch ether as a main chain, and as the cellulose ether or starch ether, a part of hydrogen atoms of a hydroxyl group in cellulose or starch is an alkyl group. And / or an alkyl ether substituted with a hydroxyalkyl group is preferred.
Preferable examples of the cellulose ether include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxyethyl ethyl cellulose, hydroxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and the like. Propyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose and the like are preferable.
[0040]
Preferable examples of the starch ether include methyl starch, ethyl starch, hydroxyethyl starch, hydroxymethylhydroxyethyl starch, and hydroxypropyl starch, and hydroxyethyl starch and hydroxypropyl starch are preferred.
[0041]
In the cellulose ether or starch ether, an alkyl group or a hydroxyalkyl group may be further substituted on the hydroxy group of the hydroxyalkyl group to form, for example, a polyoxyethylene chain.
Therefore, the substitution degree of the alkyl group or hydroxyalkyl group in the cellulose ether or the starch ether can be a substitution degree exceeding 3.0 per constituent monosaccharide residue, from 0.01 to 3.5, and more preferably from 0.00. 1 to 3, more preferably 1 to 3, particularly preferably 1.5 to 2. The weight average molecular weight is preferably in the range of 10,000 to 2,000,000, 50,000 to 1,500,000, particularly 100,000 to 600,000.
[0042]
In the polysaccharide derivative as the allergen reducing agent, a part or all of the hydrogen atoms of the hydroxy group of the cellulose ether or starch ether are represented by the following formula (1): -E ¹ -(OA) _n -E ² -R is substituted with a group represented by -R, and the degree of substitution is 0.0001 to 1.0, more preferably 0.0005 to 0.5, and still more preferably 0.001 to 0.00. The range of 1 is preferable, and 0.001 to 0.05 is particularly preferable.
[0043]
An example of the partial structure of the polysaccharide derivative when hydroxyethyl cellulose is used as the main chain is as follows.
[0044]
[Chemical 1]

[0045]
In formula (1), E ¹ The alkylene group having 1 to 6 carbon atoms which may be substituted by the hydroxy group or oxo group represented by the formula may be either a straight chain or branched chain, and a straight chain alkylene group having 2 or 3 carbon atoms is particularly preferable. . Specifically, for example, ethylene group, propylene group, trimethylene group, 2-hydroxytrimethylene group, 1-hydroxymethylethylene group, 1-oxoethylene group, 1-oxotrimethylene group, 1-methyl-2-oxoethylene Group is preferable, and 2-hydroxytrimethylene group and 1-hydroxymethylethylene group are particularly preferable.
[0046]
In formula (1), the alkylene group having 1 to 6 carbon atoms which is the same or different and represented by A may be either a straight chain or branched chain, and a straight chain alkylene group having 2 or 3 carbon atoms is particularly preferable. Specifically, for example, an ethylene group, a propylene group, and a trimethylene group are preferable, and an ethylene group is particularly preferable.
[0047]
The degree of polymerization of (—OA—) represented by n is 0 to 50, but 0 to 40, more preferably 0 to 30, more preferably 0 to 20, and more preferably 10 to 20 in terms of the allergen reducing effect, 10-15 are especially preferable. The n A's may be the same or different. Here, n means the average number of moles added.
[0048]
In formula (1), E ² Is an ether bond or an oxycarbonyl group (—OCO— or —COO—), and an ether bond is preferred.
[0049]
In formula (1), the alkyl group having 4 to 30 carbon atoms which may be substituted by the hydroxy group represented by R may be either a straight chain or branched chain, having 5 to 25 carbon atoms, and further 6 to 20 carbon atoms. In particular, a linear alkyl group having 6 to 20 carbon atoms is preferred. Specifically, for example, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an isostearyl group, and the like are preferable, and a dodecyl group, a hexadecyl group, and an octadecyl group are particularly preferable.
[0050]
Examples of the sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by the hydroxy group represented by R include a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfo-2-hydroxypropyl group, and a 2-sulfo group. Examples thereof include a -1- (hydroxymethyl) ethyl group, among which a 3-sulfo-2-hydroxypropyl group and a 2-sulfoethyl group are preferable.
All or part of the sulfoalkyl group may be a salt with a group 1 or group 2 element such as Na, K, Ca or Mg, an amine or an organic cation such as ammonium.
Further, the substitution degree of the sulfoalkyl group is preferably in the range of 0 to 1.0, more preferably 0 to 0.8, and particularly preferably 0 to 0.5 per constituent monosaccharide residue.
[0051]
The polysaccharide derivative as the allergen reducing agent may be produced according to the method described in WO00 / 73351. For example, cellulose ether or starch ether is represented by the following general formula (2).
E ^Three -(OA) _n -E ² -R (2)
[Where E ^Three Is an epoxidized alkyl group having 3 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxy group, a carboxy group or a carboxyalkyl group having 2 to 6 carbon atoms or a derivative thereof. N, A, E ² And R have the same meaning as described above. And a sulfonating agent (vinylsulfonic acid, haloalkanesulfonic acid having 1 to 5 carbon atoms optionally substituted with a hydroxy group, optionally having 2 to 6 carbon atoms). And a sulfonic acid having an epoxy group and a salt thereof).
[0052]
The polysaccharide derivative as the allergen reducing agent has an action of reducing or eliminating the antigenicity of mite allergen. Therefore, the polysaccharide derivative attenuates or eliminates allergic reaction-inducing ability for various allergens and is useful as an allergen reducing agent.
The allergen reducing effect of the polysaccharide derivative as the allergen reducing agent is particularly effective for pet allergens such as mite allergen, house dust, cedar pollen allergen, and cat.
[0053]
The allergen reducing agent is 0.005 to 2% by weight, more preferably 0.01 to 1% by weight, and particularly 0.05 to 0.5% by weight in total of the polysaccharide derivative in the aqueous detergent. Mixing is preferable in terms of allergen reduction, cleanability, and finish of the surface to be cleaned.
[0054]
As the surfactant, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant is used. Alkylene (alkylene oxide addition mole number 1 to 20) alkyl (linear or branched chain having 8 to 22 carbon atoms) ether, alkyl (linear or branched chain having 8 to 22 carbon atoms) glycoside (average degree of sugar condensation 1 to 5) ), Nonionic active agents such as sorbitan fatty acid (straight or branched chain having 8 to 22 carbon atoms) ester, alkyl (straight or branched chain having 6 to 22 carbon atoms) glyceryl ether, and alkylcarboxybetaine and alkylsulfobetaine , Alkylhydroxysulfobetaine, alkylamidocarboxybetaine, alkylamidosulfobetaine, alkylamidohydro 8-24 amphoteric surfactants alkyl carbon atoms such as shea sulfobetaine is preferably used. The surfactant is preferably contained in the aqueous cleaning agent in an amount of 0.01 to 1.0% by weight, particularly 0.05 to 0.5% by weight in terms of cleaning properties and finish of the surface to be cleaned. .
[0055]
Examples of the alkali agent include hydroxides such as sodium hydroxide, carbonates such as sodium carbonate, alkaline sulfates such as sodium hydrogen sulfate, phosphates such as primary sodium phosphate, sodium acetate, sodium succinate and the like. Organic alkali metal salts, ammonia, alkanolamines such as mono, di or triethanolamine, β-aminoalkanols such as 2-amino-2-methyl-1-propanol, morpholine, etc. From the viewpoint of properties, alkanolamines such as mono, di or triethanolamine, β-aminoalkanols such as 2-amino-2-methyl-1-propanol, and morpholine are preferred. The alkali agent is preferably contained in the aqueous cleaning agent in an amount of 0.01 to 1% by weight, particularly 0.05 to 0.5% by weight, in terms of cleaning properties and feel.
[0056]
Examples of the thickener include natural polysaccharides, semi-synthetic polymers such as cellulose polymers and starch polymers, other synthetic polymers such as vinyl polymers and polyethylene oxide, and water-soluble polymers such as clay minerals. Can be mentioned. Particularly preferred are polyacrylic acid thickeners, acrylic acid / alkyl methacrylate copolymer thickeners or mixtures thereof having low stickiness and nulliness. These acrylic thickeners preferably exhibit viscosity in the form of a sodium salt. The thickener is preferably contained in the aqueous cleaning agent in an amount of 0.01 to 2% by weight, particularly 0.02 to 1% by weight, in terms of the finish of the surface to be cleaned.
[0057]
The water-soluble solvent is preferably one or more selected from monohydric alcohols, polyhydric alcohols and derivatives thereof. In particular, a vapor pressure of 267 Pa (2 mmHg) or higher is preferable in terms of finish. For example, ethanol, isopropyl alcohol, propanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and the like are preferable. The water-soluble solvent is preferably contained in the aqueous cleaning agent in an amount of 1 to 50% by weight, particularly 1 to 20% by weight, from the viewpoint of reducing odor and skin irritation.
[0058]
The aqueous detergent includes the tannic acid, tea extract, hydroxyapatite, epicatechin, epigallocatechin gallate, epigallocatechin gallate, known as the allergen reducing agent and the polysaccharide derivatives and known anti-allergen substances. , Gallic acid (JP-A-6-279273), clay minerals such as smectite which is an allergen supplement, hydroxybenzoic acid compound (JP-A-11-292714) known as an allergen remover, and the like at appropriate ratios. Can be combined and blended.
[0059]
The aqueous cleaning agent may contain a disinfectant in addition to the above components. Thereby, in addition to the cleaning effect, a sterilizing effect can be imparted to the aqueous cleaning agent. Examples of the disinfectant include hydrogen peroxide, hypochlorous acid, sodium hypochlorite, quaternary ammonium salt, sodium benzoate, sodium paraoxybenzoate, natural disinfectants such as polylysine, and the like. In particular, natural disinfectants such as quaternary ammonium salts and polylysine are preferably used from the viewpoint of blending stability and disinfection performance. The disinfectant is preferably contained in the aqueous cleaning agent in an amount of 0.005 to 2% by weight, particularly 0.01 to 1% by weight from the viewpoint of the balance between the disinfecting effect and the reduction of skin irritation. .
[0060]
The aqueous detergent may contain an acaricide, a repellent, an antifungal agent, a coloring matter (dye, pigment), a chelating agent, a wax agent, a deodorant and an aromatic.
[0061]
Examples of the acaricide include d-phenothrin (3-phenoxybenzyl d-cis / trans-chrysantemate), permethrin (3-phenoxybenzyl dl-cis / trans-2,2-dimethyl-3- (2 ′, 2'-dichlorovinyl) -cyclopropanecarboxylate), resmethrin ((5-benzyl-3-furyl) methyl dl-cis / trans-chrysantemate), allethrin (dl-3-allyl-2-methyl-4- Oxo-2-cyclopentenyl dl-cis / trans-chrysanthemate), phthalthrin ((N-3,4,5,6, -tetrahydro-phthalimido) methyl dl-cis / trans-chrysanthemate), empentrin (1 -Ethynyl-2-methyl-2-pentenyl dl-cis / trans-chrysanthemate) Synthetic pyrethroids such as d, dT80-prarethrin (d-2-methyl-4-oxo-3-propargylcyclopent-2-enyl d-cis / trans-chrysantemate) and derivatives thereof are also hinokitiol, benzylbenzo Examples include anti-mite substances derived from natural essential oil components such as eight and jasmonic acid derivatives.
[0062]
As the mite repellent, for example, diethyl acid, dimethyl phthalate, dibutyl phthalate, MGK repellent 326, Dovetrex, 2-ethyl 1,3-hexanediol and the like can be used.
[0063]
Examples of the acaricide and / or acaricide include piperonyl butoxide, octachlorodipropyl ether, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2,2 , 2] oct-5-ene-2,3-dicarboximide, N- (2-ethynyl) -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide, etc. it can.
[0064]
Antibacterial and fungicidal agents that suppress the growth of fungi or bacteria that can feed on house dust mites and have their own antigenic properties include thiabendazole, triclosan, chlorhexidine, zinc pyrithione, chlorxylenol, dencil, benzalkonium chloride , Diclofluuride, sodium benzoate, methyl p-oxybenzoate, phenoxyethanol, ethanol, and naturally-occurring components such as chitosan, catechin, thymol, hinokitiol, scorpion bamboo extract, mustard essential oil, and wasabi essential oil.
[0065]
Water, which is a medium of the aqueous cleaning agent, is preferably contained in the aqueous cleaning agent in an amount of 50 to 99.9% by weight, particularly 80 to 99% by weight, from the viewpoint of the finish of the surface to be cleaned.
[0066]
The sheet member 2 is impregnated with the aqueous cleaning agent to form the wiping sheet 1 of the present embodiment. Thereby, the characteristic as a wet sheet expresses. As the aqueous cleaning agent, those having a viscosity at 25 ° C. of 20 to 30000 mPa · s are used. By using an aqueous detergent having a viscosity in this range, (1) the amount of aqueous detergent released to the floor at the beginning of cleaning is reduced, and the amount of aqueous detergent released from the beginning to the end of cleaning is uniform. (2) Improved cleaning sustainability for a large area to be cleaned, (3) Since the amount of water-based cleaning agent released is low even at the initial stage of cleaning, the frictional resistance value for the surface to be cleaned of the wiping sheet decreases, ( 4) Since the release amount of the aqueous cleaning agent is low even at the initial stage of cleaning, there is an advantage that the degree of freedom of fiber on the surface of the wiping sheet is large, and hair and cotton dust are entangled and held by the fiber. When the viscosity of the aqueous cleaning agent is less than 20 mPa · s, it is difficult to reduce the amount of the aqueous cleaning agent released to the floor at the initial stage of cleaning. If it exceeds 30000 Pa · s, it will be difficult to impregnate the sheet member with the aqueous cleaning agent. The viscosity is 100 to 1000 mPa · s, particularly 300 to 800 mPa · s, from the viewpoint of reducing the amount of aqueous detergent released at the initial stage of cleaning and further improving the handleability in the step of impregnating the sheet member with the aqueous detergent. Is preferred.
[0067]
The viscosity is measured using a Brookfield viscometer. The rotor used and the number of rotations are appropriately changed according to the viscosity of the aqueous cleaning agent.
[0068]
It is preferable that the aqueous cleaning agent does not substantially contain water-insoluble solid particles. When water-insoluble solid particles are blended in the aqueous cleaning agent, the solid particles remain on the surface to be cleaned and need to be wiped twice. However, there is no problem even if a very small amount of impurities, for example, about 0.1% by weight is contained.
[0069]
As shown in FIG. 2, the wiping sheet 1 of the present embodiment is used by being attached to the cleaning unit 11 in a cleaning tool 10 including a cleaning unit 11 and a rod-like handle 12 connected to the cleaning unit 11. . Specifically, the cleaning tool 10 includes a flat cleaning unit 11 to which the wiping sheet 1 can be attached, and a rod-shaped handle 12 connected to the cleaning unit 11 via a universal joint 13. These are fixed by a plurality of flexible pieces 14 that form radial slits provided in the cleaning section 11.
[0070]
According to the wiping sheet of this embodiment, the stable sustained release property of the cleaning agent is obtained, the operability is good, and a large area of the floor can be cleaned.
[0071]
The present invention is not limited to the embodiment. For example, the wiping sheet 1 in the above embodiment is a sheet member having a three-layer structure impregnated with an allergen-reducing agent-containing water-containing detergent, but instead of the sheet member, a single layer, two layers or four layers are used. You may use the sheet | seat of the structure more than a layer. For example, in the embodiment, the outer layer 3 may be laminated only on one side of the inner layer 2.
[0072]
Moreover, the shape of the convex part and the recessed part in the surface of the wiping sheet 1 in the said embodiment can be made into various shapes according to the ease of manufacture of a sheet | seat, the operativity of the wiping sheet 1, etc.
[0073]
The wiping sheet of the present invention is not particularly limited in the wiping target. In addition to the floor as in the above embodiment, for example, the surface of a building structure such as a wall, ceiling, or pillar, furniture such as a table or sofa, home appliances such as a television, kitchen appliances, OA equipment such as a personal computer. In addition to articles such as clothing, bedding, bags, bags, etc., the present invention can be applied to all objects to which allergens adhere, such as human bodies, animals such as pets, and houseplants.
[0074]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.
[0075]
[Production Example 1]
A slurry prepared by mixing 80 g of hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of 1,500,000 and a substitution degree of hydroxyethyl group of 1.8, 640 g of 80% isopropyl alcohol, and 5.34 g of 48% aqueous sodium hydroxide solution. A solution was prepared and stirred at room temperature for 30 minutes under a nitrogen atmosphere. In this solution:
[0076]
[Chemical 2]

[0077]
A polyoxyalkylenating agent represented by the formula (12) was added and reacted at 80 ° C. for 8 hours to effect polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was dried twice with 500 g of isopropyl alcohol and dried overnight at 60 ° C. under reduced pressure to obtain 72.0 g of a polyoxyalkylenated hydroxyethyl cellulose derivative (Compound 1).
The degree of substitution of the substituent containing the polyoxyalkylene group in the obtained hydroxyethyl cellulose derivative was 0.004.
[0078]
[Production Example 2]
Compounds 2 to 16 shown in Table 1 were obtained according to the method described in Production Example 1 and WO00 / 73351.
[0079]
[Production Example 3]
(1) In a 1000 mL glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide Co., Ltd.) having a weight average molecular weight of about 1,500,000 and a hydroxyethyl group substitution degree of 1.8 ) 80 g, 80% isopropyl alcohol 640 g, and 48% sodium hydroxide aqueous solution 5.5 g were added to prepare a slurry, which was stirred at room temperature for 30 minutes in a nitrogen atmosphere. To this, 2.52 g of stearyl glycidyl ether was added and reacted at 80 ° C. for 8 hours for hydrophobicity. After completion of the hydrophobic reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 72.8 g of a hydrophobized hydroxyethyl cellulose derivative.
[0080]
(2) 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 200 g of 70% isopropyl alcohol, and 48% aqueous sodium hydroxide solution in a 500 mL glass separable reaction vessel equipped with a stirrer, thermometer and condenser. 1.37g was prepared and the slurry liquid was prepared, and it stirred for 30 minutes at room temperature under nitrogen stream. To the reaction solution, 28 g of sodium 3-chloro-2-hydroxypropanesulfonate and 11.9 g of 48% aqueous sodium hydroxide solution were added, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid and the product was filtered off. The product was washed once with 340 g of 70% isopropyl alcohol and then twice with 120 g of isopropyl alcohol, and then dried at 70 ° C. for one day under reduced pressure to give 3-stearyloxy-2-hydroxypropyl group and 3-sulfo-2-hydroxy group. 18.3 g of a hydroxyethylcellulose derivative (compound 17) substituted with a propyl group was obtained.
[0081]
The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group of the obtained hydroxyethyl cellulose derivative was 0.003, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.210.
[0082]
[Production Example 4]
The compound 18 shown in Table 1 was obtained according to the method of Production Example 3.
[0083]
[Production Example 5]
A slurry liquid was prepared by mixing 80 g of hydroxyethyl cellulose having a weight average molecular weight of about 800,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-QP15000H, manufactured by Union Carbide), 640 g of isopropyl alcohol and 2.0 g of p-toluenesulfonic acid. Prepared and stirred for 30 minutes at room temperature under nitrogen atmosphere. In this solution
[0084]
[Chemical 3]

[0085]
15 g of the compound represented by the above formula was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with 48% aqueous sodium hydroxide solution, and the reaction product was filtered off. The reaction product was washed twice with 500 g of 80% isopropyl alcohol and twice with 500 g of isopropyl alcohol, and dried under reduced pressure at 70 ° C. for one day to obtain 73.4 g of a hydroxyethyl cellulose derivative (Compound 19).
The degree of substitution of the substituent containing the polyoxyalkylene group in the obtained hydroxyethyl cellulose derivative was 0.010.
[0086]
[Production Example 6]
(1) 80 g of potato starch (manufactured by Katayama Chemical Co., Ltd.), 640 g of 50% isopropyl alcohol and 5.5 g of 48% aqueous sodium hydroxide were mixed to prepare a slurry, and stirred at room temperature for 30 minutes in a nitrogen atmosphere. In this solution
[0087]
[Formula 4]

[0088]
19.0 g of the compound represented by the formula (1) was added and reacted at 80 ° C. for 8 hours to carry out polyoxyalkyleneation. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of 50% isopropyl alcohol, then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 69.4 g of a polyoxyalkylenated starch derivative.
The degree of substitution of the substituent containing the amount of polyoxyalkylene in the obtained starch derivative was 0.005.
(2) A slurry solution was prepared by mixing 35.5 g of the polyoxyalkylenated starch obtained in (1), 350 g of 70% isopropyl alcohol and 2.4 g of a 48% aqueous sodium hydroxide solution. Stir for minutes. To the reaction solution, 25.1 g of sodium monochloroacetate and 18.0 g of 48% aqueous sodium hydroxide solution were added, and carboxymethylation was performed at 50 ° C. for 5 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid and the product was filtered off. The product was washed with 400 g of 70% isopropyl alcohol three times and twice with 300 g of isopropyl alcohol, and then dried under reduced pressure at 70 ° C. for one day to obtain 33.8 g of a polyoxyalkylenated and carboxymethylated starch derivative (Compound 20). Got. The degree of carboxymethylation of the obtained starch derivative was 0.48.
[0089]
[Table 1]

[0090]
Next, the allergen reducing effect of the compound produced as described above was examined by Test Example 1 and Test Example 2 below.
[0091]
[Test Example 1]
(1) The sesquiterpene alcohol of the present invention was prepared with distilled water so as to be a 1% solution. As an indoor environmental allergen, the amount of Derf2 which is a leopard mite allergen was measured by a sandwich ELISA method using a mouse monoclonal antibody using a Derf2 antibody and a labeled antibody manufactured by Asahi Breweries.
The allergen-reducing effect was expressed as a ratio with respect to the control where the amount of Derf2 when the same treatment was performed with distilled water was 1.
[0092]
(2) Triis scratch extract “Tani” (manufactured by Torii Pharmaceutical Co., Ltd.) was placed in a dialysis tube and dialyzed overnight with a 10% PBS solution (4 ° C.) to remove glycerol contained in the extract. The dialysis mite extract was prepared with PBS so that the concentration of the dialysis mite extract was 0.5 mg / mL. 50 μL of this mite extract and 50 μL of a 1% sample solution prepared with distilled water were placed in a 1.5 mL siliconized microtube, stirred with vortex, and allowed to stand at room temperature for 2 hours. As a control, the same amount of distilled water was used instead of the sample. The same amount of 1% tannic acid was used as the positive control. Next, 400 μL of 11.25% BSA (dissolved in PBS) was added to each tube to stop the reaction, centrifuged at 15,000 rpm for 10 minutes at room temperature, and the supernatant was subjected to ELISA. The amount of Derf2 in the reaction solution was measured according to the attached protocol using Asahi Breweries anti-Derf2 monoclonal antibody (15E11), HRP-labeled anti-Derf2 monoclonal antibody (13A4), and Derf2 as a calibration curve preparation Derf2.
The ratio of the amount of derf2 treated with each sample was determined with the amount of derf2 when distilled water was used as 1. The results are shown in Table 2.
[0093]
[Table 2]

[0094]
As mentioned above, this compound 1 had the high allergen reduction effect.
[0095]
[Test Example 2]
Antigen-specific IgE antibody detection reagent, Quidel allergy screen (manufactured by Xenith Biomed), which is a reagent to be detected using an enzyme-labeled anti-IgE antibody, and allergens immobilized on a dipstick (House dust, Kona leopard mite, Yake leopard mite) , Cat epithelium, cedar, ragweed, etc.) and allergic patient IgE antibodies were measured as follows.
Place the allergen stick in a wet box with the pad on top, impregnate the pad with 100 μL / stick of the present invention prepared to 1%, and let stand at room temperature for 2 hours. After each pad is uniformly washed with physiological saline in a washing bottle for 30 seconds, 50 μL / stick of allergic patient serum is gently dropped onto the pad and spread evenly. Cover the wet box and let stand at room temperature for 18 hours. After completion of the reaction, each pad is uniformly washed with physiological saline contained in a washing bottle for 20 seconds.
Dispense the enzyme-labeled anti-IgE antibody into about 1 mL test tube, shake off excess water from the washed allergen stick, place the pad downward in the test tube, and allow to react at room temperature for 30 minutes. After completion of the reaction, wash each pad uniformly with tap water for 2 minutes. At this time, confirm that the red color on the pad disappears. Dispense approximately 1 mL of the substrate solution into the test tube, shake off excess water from the washed allergen stick, place the pad downward in the test tube, and allow to react at room temperature for 30 minutes. After completion of the reaction, the pad surface is turned to the back, and moisture contained in the pad is sucked up with a paper towel to stop the reaction. Next, the blue color development intensity was measured with an image analyzer, and the reactivity reduction by the allergen reducing agent was calculated by the following formula using the color development intensity by the allergic patient IgE when treated with distilled water as a control. The results are shown in Tables 3 and 4.
Allergen reduction effect (%) = 100- (IgE reaction intensity when treated with the present invention-negative control reaction intensity) / (distilled water-treated control IgE reaction intensity-negative control reaction intensity) × 100
[0096]
[Table 3]

[0097]
[Table 4]

[0098]
As a result, each of the produced compounds 1 to 22 had a high allergen reducing effect.
[0099]
Next, wiping sheets were prepared as in the following Examples and Comparative Examples, and their wiping performance and allergen reducing effect were evaluated as follows. The results are shown in Table 5.
[0100]
[Example 1]
Using a core-sheath structure in which the core is made of polypropylene and the sheath is made of polyethylene, a low-melting fiber (2.8 dtex × 51 mm, melting point of sheath component 130 ° C.) having a three-dimensional crimp shape is used, and the basis weight is 27 g / m ² An air-through nonwoven fabric was prepared. The fibers were thermally bonded at a temperature of 140 ° C. The breaking strength of the air-through nonwoven fabric was 1660 cN / 25 mm in the flow direction (MD) and 220 cN / 25 mm in the width direction (CD).
[0101]
On the other hand, a rayon fiber (1.7 dtex × 40 mm), an acrylic fiber (0.9 dtex × 51 mm), and a core-sheath fiber (1.0 dtex × 38 mm) whose core is made of polypropylene and whose sheath is made of polyethylene are weight ratio 50. A basis weight of 19 g / m prepared by a conventional card machine mixed at a ratio of 25/25 ² The fiber web was laminated on the top and bottom of the air-through nonwoven fabric. Next, a water needling treatment is performed under low energy conditions, and an air-through nonwoven fabric and a fiber web are entangled to have a surface layer having a high degree of fiber freedom. ² A composite spunlace nonwoven fabric was prepared. Using an ultrasonic embossing machine, the entire surface of the prepared nonwoven fabric was embossed with an uneven pattern of diamond pattern to obtain a sheet-like member.
[0102]
Water / allergen reducing agent / ethanol / 2-amino-2-methyl-1-propanol / dodecyl glucoside (condensation degree 1.4) / thickening agent (Carbopol ETD2020, manufactured by Nikko Chemical Co.) / Trisodium citrate = Allergen-reducing agent water-containing detergent (viscosity: 700 mPa · s / 25 ° C.) comprising 93.501 / 0.1 / 6 / 0.145 / 0.1 / 0.12 / 0.034 (weight ratio) The resulting nonwoven fabric was impregnated to prepare a floor wiping sheet. In addition, the compound 4 of the said manufacture example was used for the allergen reducing agent. The impregnation ratio of the aqueous cleaning agent was 250% with respect to the weight of the nonwoven fabric. Carbopol ETD2020 is an acrylic acid / alkyl methacrylate (C10-30) copolymer. The breaking strength of the wiping sheet in the state impregnated with the aqueous detergent was 3120 cN / 25 mm in the flow direction (MD) and 410 cN / 25 mm in the width direction (CD).
[0103]
[Example 2]
Polyester fiber (1.6 dtex × 51 mm), rayon fiber (1.7 dtex × 44 mm) and acrylic fiber (0.9 dtex ×) on both sides of a resin net (polypropylene lattice net fiber distance 8 mm, wire diameter 300 μm) 51 mm) was mixed at a weight ratio of 50/25/25, and a basis weight of 30 g / m prepared by a conventional card machine above. ² The fiber web was laminated. Subsequently, the water needling process was performed on low energy conditions, and it shape | molded simultaneously to the shape of the support body, and obtained the nonwoven fabric (sheet-like member). The obtained non-woven fabric was impregnated with the allergen-reducing agent-containing cleaning agent (viscosity 700 mPa · s / 25 ° C.) used in Example 1 at 250% with respect to the non-woven fabric weight. The breaking strength of the wiping sheet in the state impregnated with the aqueous detergent was 3833 cN / 25 mm in the flow direction (MD) and 1182 cN / 25 mm in the width direction (CD).
[0104]
[Comparative Example 1]
A wipe sheet was produced in the same manner as in Example 1 except that the allergen reducing agent-containing detergent was not impregnated.
[0105]
[Comparative Example 2]
A wipe sheet was prepared in the same manner as in Example 2 except that the allergen reducing agent-containing cleaning agent was not impregnated.
[0106]
About the obtained wiping sheet | seat, the wiping performance was evaluated like following 1) -8).
[0107]
1) Amount of cleaning agent released
The amount of the cleaning liquid released per 1 tatami when the wiping sheet was mounted on a quick wiper [manufactured by Kao Corporation] and the flooring was wiped 6 tatami mats was measured. The amount of cleaning liquid was measured by removing the wiping sheet from the cleaning unit head and measuring its weight each time one tatami mat was wiped. In the cleaning method, one reciprocal wiping at a distance of about 90 cm was taken as one stroke, and two rows were wiped in the longitudinal direction (180 cm) of one tatami mat and four rows in the short direction (90 cm) to complete the cleaning of one tatami mat.
[0108]
2) Static friction resistance value which is an index of the degree of freedom of fiber of the surface layer of the wiping sheet
Measurement was performed according to the method described above. The load of 400 g substantially corresponds to the average load applied to the sheet when the wiping sheet is attached to a quick wiper (manufactured by Kao Corporation) and the floor is cleaned.
[0109]
3) Area ratio of convex part
Measurement was performed according to the method described above.
[0110]
4) Hair collection rate
A wiping sheet was attached to a quickle wiper (manufactured by Kao Corporation). Spread 5 hairs of about 10 cm on a 30 cm x 60 cm flooring (Matsushita Electric Works, Woodytile MT613T), place a wiping sheet on it and clean it twice with a fixed stroke (60 cm) and capture it on the wiping sheet. The number of hairs collected was measured. This operation was carried out 6 times in succession to determine how many of 30 hairs were collected. The number of collected hairs was divided by 30 and multiplied by 100 to obtain the value as the hair collection rate (%).
[0111]
5) Collectability of dust
A wiping sheet was attached to a quickle wiper (manufactured by Kao Corporation). Disperse 0.1g of 7 kinds of JIS test dust (Kanto loam layer, fine particles) on 100cm x 100cm flooring (Matsushita Electric Works, Woody tile MT613T) (spreading uniformly over the entire surface), 1 flooring 4 rows were cleaned in the round trip. After this operation was repeated six times, the soiled wipe sheet was dried and the weight (sheet + detergent non-volatile component + dust) was measured. The amount of dust collected was calculated by subtraction. The weight of the collected dust is divided by the total dust weight (0.6 g = 0.1 g × 6 times), and this is multiplied by 100 to obtain the dust collection rate (%). .
[0112]
6) Removability of 6th tatami mat soy sauce
One drop (0.02 g) of commercially available soy sauce was placed on the flooring (area: 1 tatami mat) and dried with a dryer. A quick wiper (made by Kao Co., Ltd.) is attached with a wiping sheet and another clean flooring is continuously cleaned for 5 tatami mats. Was evaluated. In addition, the flooring for 5 tatami mats to be cleaned first is cleaned in the same way as when measuring the amount of detergent released. Evaluated.
○: Dirt was completely removed by cleaning 10 cycles or less.
○ to Δ: Dirt was completely removed by 15 reciprocating cleanings.
Δ: Dirt was completely removed by 20 reciprocating cleanings.
Δ to X: Dirt was completely removed by 30 reciprocating cleanings.
X: Dirt was not completely removed even after exceeding 30 reciprocations.
[0113]
7) Finishability
A wiping sheet was attached to a quickle wiper (manufactured by Kao Corporation), and a clean flooring of 100 × 100 cm was cleaned. The finish of the flooring after drying was visually evaluated in the following three stages over a fluorescent lamp.
○: There is no residual trace (wiping lines, etc.) of the cleaning agent component.
Δ: There are some residual traces (such as wipes) of the cleaning component.
X: Residual traces (such as wipes) of the cleaning component are present.
[0114]
8) Wiper operability when cleaning the 1st tatami mat and wiper operation load at the beginning of wiping
A wiper sheet (made by Kao Corporation) is attached to the quick wiper and the wiper operability when starting to wipe the flooring board (Wooden tile E type KER501 made by Matsushita Electric Works) with one hand is visually evaluated in the following four stages. did.
○: There is almost no resistance.
○ to Δ: Feels somewhat resistant, but can be wiped with one hand.
Δ: Feels resistance but can be wiped with one hand.
X: There is a great resistance and the handle of the wiper bends when wiped with one hand.
Further, as shown in FIG. 4, a load cell 33 for measuring a compressive load is mounted between the cleaning head portion 31 and the handle 32 of the quick wiper 30, and the floor 34 is started to be wiped by using the quick wiper 30. The compression load at the time was measured.
[0115]
[Evaluation of allergen reduction effect]
The pollen removal effect was examined as described below, and the allergen reduction effect was evaluated in four stages.
After spraying 50 mg of cedar pollen on the surface of a 30 cm square glass plate and wiping with the obtained wiping sheet, phosphate buffer solution (KH adjusted to pH 7.4 ± 0.1) ₂ PO _Four , NaCl, Na ₂ PO _Four ・ 7H ₂ The pollen remaining on the surface of the glass plate was washed away with 50 mL of O dissolved in distilled water so as to be 0.144 g / L, 9.00 g / L, and 0.795 g / L, respectively. Then, the amount of pollen allergen was quantified from the washed-out liquid using the following method to obtain the amount of residual pollen (this amount of pollen is referred to as the amount of residual pollen).
[0116]
<Quantification of pollen allergen amount>
Cry j1 and Cry j2 in the sample were quantified using the following quantitative method, and the sum was used as the amount of cedar pollen allergen in the sample.
[0117]
[ELISA quantification method of Cry j1]
1. Monoclonal antibody Ab-Cry j1 mAb 013 (Seikagaku Corporation) was diluted with PBS to a concentration of 2 μg / mL, and 50 μL was dispensed into each well of a microplate (Sumitomo Bakelite, ELISA PLATE H TYPE). And let stand at room temperature for 2 hours.
2. Wash the microplate 3 times with PBS.
3. PBS (Dainippon Pharmaceutical Co., Ltd., Block Ace) containing 1% BSA is dispensed at 200 μL per well and allowed to stand at room temperature for 1 hour for blocking.
4). The microplate is washed three times with PBS containing 0.05% by mass of Tween 20 (SIGMA) (hereinafter referred to as T-PBS).
5). Purified Cry j1 (manufactured by Seikagaku Corporation) as a standard 2 from 4 ng / mL to n = 5 tube T-PBS ⁿ Dilute twice, dispense 50 μL of each into each well, and prepare a well with 50 μL of T-PBS added instead of Cry j1 as a negative control. The sample to be measured is appropriately diluted with T-PBS, dispensed in 50 μL per well, and allowed to stand at room temperature for 2 hours.
6). Wash the microplate 3 times with T-PBS.
7). 50 μL of Peroxidase Conjugated Ab-Cryj1 mAb 053 (manufactured by Seikagaku Corporation) at an optimal concentration is dispensed into each well and left at room temperature for 2 hours.
8). Wash the microplate 3 times with T-PBS.
9. Color is developed using a peroxidase coloring kit (manufactured by Sumitomo Bakelite). First, 0.1 mL of a substrate solution is added to 10 mL of color former and mixed to obtain a color developer. Dispense 100 μL of this color developing solution into each well and develop color at room temperature. Thereafter, 100 μL of stop solution is dispensed into each well to stop the reaction, and the absorbance at 450 nm is measured with a plate reader.
10. The Cry j1 concentration of the sample to be measured is calculated using a calibration curve obtained from the absorbance of the standard.
[0118]
[ELISA quantitative method of Cry j2]
1. Monoclonal antibody Ab-Cry j2 mAb T27 (Seikagaku Corporation) was diluted with PBS to a concentration of 2 μg / mL, and 50 μL was dispensed into each well of a microplate (Sumitomo Bakelite, ELISA PLATE H TYPE). And let stand at room temperature for 2 hours.
2. Wash the microplate 3 times with PBS.
3. PBS (Dainippon Pharmaceutical Co., Ltd., Block Ace) containing 1% BSA is dispensed at 200 μL per well and allowed to stand at room temperature for 1 hour for blocking.
4). Wash the microplate 3 times with T-PBS.
5). Purified Cry j2 (manufactured by Seikagaku Corporation) as a standard 2 from 10 ng / mL to n = 5 tube T-PBS ⁿ Dilute twice, dispense 50 μL of each into each well, and prepare a well containing 50 μL of T-PBS instead of Cry j2 as a negative control. The sample to be measured is appropriately diluted with T-PBS, dispensed in 50 μL per well, and allowed to stand at room temperature for 2 hours.
6). Wash the microplate 3 times with T-PBS.
7). An optimal concentration of Peroxidase Conjugated Ab-Cryj2 pAb (manufactured by Seikagaku Corporation) is dispensed into each well in an amount of 50 μL and allowed to stand at room temperature for 2 hours.
8). Wash the microplate 3 times with T-PBS.
9. Color is developed using a peroxidase coloring kit (manufactured by Sumitomo Bakelite). First, 0.1 mL of a substrate solution is added to 10 mL of color former and mixed to obtain a color developer. Dispense 100 μL of this color developing solution into each well and develop color at room temperature. Thereafter, 100 μL of stop solution is dispensed into each well to stop the reaction, and the absorbance at 450 nm is measured with a plate reader.
10. The Cry j2 concentration of the sample to be measured is calculated using a calibration curve obtained from the absorbance of the standard.
[0119]
From the amount of cedar pollen allergen determined as described above, the pollen reduction rate was determined by the following formula and evaluated using the value as an index in the following four stages.
Pollen reduction rate (%) = (residual pollen amount / residual pollen amount in Comparative Example 1) × 100
A: Pollen amount reduction rate is less than 30%.
○: Pollen amount reduction rate is 30% or more and less than 50%.
Δ: Pollen reduction rate is 50% or more and less than 80%.
X: Pollen reduction rate is 80% or more.
[0120]
[Table 5]

[0121]
As shown in Table 5, it was found that the wiping sheet of the example (product of the present invention) reduced allergens present on the surface of the object by wiping operation as compared with the wiping sheet of the comparative example.
[0122]
【The invention's effect】
According to the wiping sheet of the present invention, allergens present on the surface of an object can be reduced by a wiping operation.
[Brief description of the drawings]
FIG. 1 is a perspective view schematically showing an embodiment of a wiping sheet of the present invention.
FIG. 2 is a perspective view showing a state in which the wiping sheet of the present invention is mounted on a cleaning tool.
FIG. 3 is a schematic diagram showing a method for measuring a static friction resistance value of a wiping sheet.
FIG. 4 is a schematic diagram showing a method for measuring a wiper operation load at the start of wiping.
[Explanation of symbols]
1 Floor wiping sheet
2 Sheet member
3 Inner layer
4 outer layer
5 Convex
6 recess
10 Cleaning tool
11 Cleaning Department
12 Handle

Claims (3)

A wiping sheet containing an allergen reducing agent in the sheet member,
The allergen reducing agent is a polysaccharide derivative having cellulose ether or starch ether as a main chain, and a part or all of the hydrogen atoms of the hydroxy group are represented by the following general formula (1):
-E ^1- (OA) _n -E ² -R (1)
[Wherein E ¹ represents an alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxy group or an oxo group, n represents a number of 0 to 50, and n A's are the same or different, An alkylene group having 1 to 6 carbon atoms; E ² represents an ether bond or an oxycarbonyl group; and R is an alkyl group having 4 to 30 carbon atoms which may be substituted by a hydroxy group or a hydroxy group. Or a C1-C5 sulfoalkyl group or a salt thereof. ]
A wipe sheet comprising a polysaccharide derivative substituted with a group represented by: The wipe sheet according to claim 1, wherein the sheet member is impregnated with an aqueous cleaning agent containing the allergen reducing agent. The wiping sheet according to claim 1 or 2 used for wiping the floor.

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