JP2013532239A - 活性剤不織布ウェブを含むフィラメント及びその製造方法 - Google Patents
活性剤不織布ウェブを含むフィラメント及びその製造方法 Download PDFInfo
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
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- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
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- D04H3/045—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments in rectilinear paths, e.g. crossing at right angles for net manufacturing
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Abstract
Description
a.1つ以上のフィラメント形成材料と、1つ以上の活性剤と、任意で1つ以上の極性溶媒(水など)を含む、フィラメント形成組成物を用意する工程;
b.このフィラメント形成組成物を紡糸して、1つ以上のフィラメント形成材料と、フィラメントの目的用途の条件に曝した際にフィラメントから放出可能である及び/又は放出される1つ以上の活性剤とを含む、1つ以上のフィラメントにする工程であって、フィラメント内に存在するフィラメント形成材料の総濃度は乾燥フィラメントベースで65重量%未満であり、フィラメント内に存在する活性剤の総濃度は乾燥フィラメントベースで35重量%を超える、工程とを含む。
本明細書で使用するとき、「フィラメント」は、長さがその直径を大きく上回る、すなわち、長さと直径との比が少なくとも約10である、細長い微粒子を意味する。
本発明のフィラメントは、1つ以上のフィラメント形成材料と、1つ以上の活性剤(例えば、1つ以上のフィラメント形成材料と1つ以上の活性剤との混合物)を含み、1つ以上の活性剤は、目的用途の条件に曝した際などにフィラメントから放出可能であり、フィラメント内に存在する1つ以上のフィラメント形成材料の総濃度が乾燥フィラメントベースで65重量%未満であり、フィラメント内に存在する1つ以上の活性剤の総濃度が乾燥フィラメントベースで35重量%を超える、フィラメントが提供される。
フィラメント形成材料は、紡糸プロセスなどによってフィラメントを製造するのに好適な特性を呈するポリマーを製造することができるポリマー又はモノマーなど、任意の好適な材料である。
極性溶媒可溶性材料の非限定例としては極性溶媒可溶性ポリマーが挙げられる。極性溶媒可溶性ポリマーは合成物であっても又は天然由来であってもよく、かつ化学的に及び/又は物理的に修飾されてもよい。一実施例では、極性溶媒可溶性ポリマーは、少なくとも約10,000g/モル、及び/又は少なくとも約20,000g/モル、及び/又は少なくとも40,000g/モル、及び/又は少なくとも80,000g/モル、及び/又は少なくとも約100,000g/モル、及び/又は少なくとも1,000,000g/モル、及び/又は少なくとも3,000,000g/モル、及び/又は少なくとも10,000,000g/モル、及び/又は少なくとも20,000,000g/モル、及び/又は約40,000,000g/モルまでの、及び/又は約30,000,000g/モルまでの重量平均分子量を呈する。
非極性溶媒可溶性材料の非限定例としては非極性溶媒可溶性ポリマーが挙げられる。好適な非極性溶媒可溶性材料の非限定例としては、セルロース、キチン、キチン誘導体、ポリオレフィン、ポリエステル、これらのコポリマー、及びこれらの混合物が挙げられる。ポリオレフィンの非限定例としては、ポリプロピレン、ポリエチレン、及びこれらの混合物が挙げられる。ポリエステルの非限定例としては、ポリエチレンテレフタレートが挙げられる。
活性剤は、例えば、フィラメントの外部の環境に利益をもたらすなど、フィラメントそれ自体以外の何かに利益をもたらすように設計され、そのように意図される添加剤の部類である。活性剤は、フィラメントに意図された使用状況下で、意図された効果を作り出す任意の好適な添加剤であってもよい。例えば、活性剤は、パーソナルクレンジング及び/又はコンディショニング剤、例えばヘアケア剤、例えばシャンプー剤及び/又は染毛剤、ヘアコンディショニング剤、スキンケア剤、日焼け止め剤、及び皮膚コンディショニング剤;ランドリーケア及び/又はコンディショニング剤、例えば布地ケア剤、布地コンディショニング剤、布地柔軟剤、布地防しわ剤、布地ケア帯電防止剤、布地ケア染み除去剤、汚れ放出剤、分散剤、抑泡剤、起泡剤、消泡剤、及び布地リフレッシュ剤;硬質表面ケア剤及び/又はコンディショニング剤、例えば液体及び/又は粉末の食器洗浄剤(手洗い用の食器洗浄及び/又は自動食器洗浄器用途)、及び研磨剤;他の洗浄及び/又はコンディショニング剤、例えば抗菌剤、香料、漂白剤(例えば酸素系漂白剤、過酸化水素、過炭酸塩系漂白剤、過ホウ酸塩系漂白剤、塩素系漂白剤)、漂白活性剤、キレート剤、ビルダー、ローション、増白剤、空気ケア剤、カーペットケア剤、移染防止剤、軟水化剤、硬水化剤、pH調整剤、酵素、凝集剤、発泡剤、防腐剤、化粧剤、化粧除去剤、気泡剤、付着助剤、コアセルベート形成材、粘土、増粘剤、ラテックス、シリカ、乾燥剤、匂い防止剤、制汗剤、冷却剤、加温剤、吸収ゲル剤、消炎剤、染料、顔料、酸及び塩基;液体トリートメント活性剤;農業用活性剤、産業活性剤、摂取可能な活性剤、例えば薬剤、歯ホワイトニング剤、歯ケア剤、マウスウォッシュ剤、歯周歯茎ケア剤、可食剤、食用剤、ビタミン、ミネラル、水処理剤、例えば水浄化及び/又は水消毒剤、並びにこれらの混合物からなる群から選択されてもよい。
好適な界面活性剤の非限定例としては、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤、双極性イオン界面活性剤、両性界面活性剤、及びこれらの混合物が挙げられる。補助界面活性剤もフィラメントに含まれてもよい。例えば、洗濯洗浄剤及び/又は食器洗浄剤としての使用に設計されているフィラメントに関して、界面活性剤の総濃度は、染み及び/又は匂い除去を含む洗浄を提供するのに十分であるべきであり、一般的に約0.5%〜約95%の範囲である。更に、洗濯洗浄剤及び/又は食器洗浄剤用のフィラメントでの使用に設計されている2つ以上の界面活性剤を含む界面活性剤系は、全アニオン性界面活性剤系、アニオン性界面活性剤と非イオン性界面活性剤の混合物を含む混合物タイプの界面活性剤系、又は非イオン性界面活性剤とカチオン性界面活性剤の混合物を含んでもよい。
好適なアニオン性界面活性剤の非限定例としては、アルキルサルフェート、アルキルエーテルサルフェート、分枝状アルキルサルフェート、分枝状アルキルアルコキシレート、分枝状アルコキシレートサルフェート、中鎖分枝状アルキルアリルスルホネート、硫酸化モノグリセリド、スルホン化オレフィン、アルキルアリルスルホネート、一級又は二級アルカンスルホネート、アルキルスルホスクシネート、アシルタウレート、アシルイセチオネート、アルキルグリセリルエーテルスルホン酸塩、スルホン化メチルエステル、スルホン化脂肪酸、アルキルホスフェート、アシルグルタメート、アシルサルコシネート、アルキルスルホアセテート、アシル化ペプチド、アルキルエーテルカルボキシレート、アシルラクチレート、アニオン性フルオロ界面活性剤、ラウロイルグルタミン酸ナトリウム、及びこれらの組み合わせが挙げられる。
好適なカチオン性界面活性剤の非限定例としては、式(I)を有するものが挙げられるが、これに限定されない:
好適な非イオン性界面活性剤の非限定例としては、アルコキシル化アルコール(AE)及びアルキルフェノール、ポリヒドロキシ脂肪酸アミド(PFAA)、アルキルポリグリコシド(APG)、C10〜C18グリセロールエーテル等が挙げられる。
双極性イオン若しくは両性界面活性剤の非限定例としては、二級及び三級アミンの誘導体、複素環式二級及び三級アミンの誘導体、又は四級アンモニウム化合物、四級ホスホニウム化合物若しくは三級スルホニウム化合物の誘導体が挙げられる。双極性界面活性剤の例である、アルキルジメチルベタイン及びココジメチルアミドプロピルベタイン、C8〜C18(例えば、C12〜C18)アミンオキシド、並びに、例えば、アルキル基がC8〜C18、及び特定の実施形態ではC10〜C14であることができるN−アルキル−N,N−ジメチルアミノ−1−プロパンスルホネートなどのスルホ及びヒドロキシベタインを包含するベタインについては、米国特許第3,929,678号の19欄38行〜22欄48行を参照のこと。
両性界面活性剤の非限定例としては、二級若しくは三級アミンの脂肪族誘導体、又は脂肪族ラジカルが直鎖又は分枝鎖であることができる、複素環式二級及び三級アミンの脂肪族誘導体、並びにこれらの混合物が挙げられる。脂肪族置換基のうち1つは少なくとも約8個の炭素原子、例えば約8〜約18個の炭素原子を含有してもよく、少なくとも1つは水可溶化アニオン性基、例えば、カルボキシ基、スルホネート基、サルフェート基を含有する。両性界面活性剤の好適な例については、米国特許第3,929,678号、第19段18〜35行を参照のこと。
上記の界面活性剤に加えて、フィラメントには補助界面活性剤を含有させてもよい。洗濯洗剤及び/又は食器洗浄用洗剤の場合、様々な汚れ及び染みにわたって、及び様々な使用条件下において幅広いスケールの洗浄能力を得るために、それらは典型的には複数のタイプの界面活性剤を含有する。広範囲のこれらの補助界面活性剤を、本発明のフィラメントに使用することができる。アニオン性、非イオン性、両性及び双極性イオン性の部類、並びにこれらの補助界面活性剤の種の一般的な一欄が本明細書において上記に提供され、また米国特許第3,664,961号に見出すことができる。換言すれば、本明細書の界面活性剤系には、非イオン性、カチオン性、アニオン性、双極性イオン性、及びこれらの混合物から選択される1つ以上の補助界面活性剤を含んでもよい。補助界面活性剤は、所望される利益に基づいて選択することができる。界面活性剤系は、約0重量%〜約10重量%、約0.1重量%〜約5重量%、又は約1重量%〜約4重量%の他の補助界面活性剤の組成物を含む。
本発明のアニオン性界面活性剤及び/又はアニオン性補助界面活性剤は、酸形態で存在してもよく、その場合、中和して界面活性剤塩を形成させることができる。一実施例では、フィラメントには界面活性剤塩形態を含ませ得る。典型的な中和剤としては、水酸化物(例えばNaOH又はKOH)などの金属対イオン塩基が挙げられる。酸形態のアニオン性界面活性剤及びアニオン性補助界面活性剤を中和する他の剤としては、アンモニア、アミン、アルカノールアミンが挙げられる。一実施例では、中和剤には、アルカノールアミン、例えばモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、及び当該技術分野において既知の直鎖又は分枝鎖アルカノールアミン、2−アミノ−1−プロパノール、1−アミノプロパノール、モノイソプロパノールアミン、又は1−アミノ−3−プロパノールからなる群から選択されるアルカノールアミンを含む。アミンの中和は全体的に又は部分的な範囲でされてもよく、例えば、アニオン性界面活性剤混合物の一部はナトリウム若しくはカリウムで中和されてもよく、アニオン性界面活性剤混合物の一部はアミン若しくはアルカノールアミンで中和されてもよい。
1つ以上の香料及び/又は香料の原材料、例えば調和剤及び/又はノートを本発明の1つ以上のフィラメントに組み込んでもよい。香料は、アルデヒド香料成分、ケトン香料成分、及びこれらの混合物からなる群から選択される香料成分を含んでもよい。
特定の香料送達系、特定の香料送達系の製造方法、及びこのような香料送達系の使用は、米国特許出願第2007/0275866(A1)号に開示されている。香料送達系の非限定例としては以下のものが挙げられる:
I.ポリマー支援型送達(PAD):この香料送達技術は、香料を送達するのにポリマー性材料を用いるものである。古典的なコアセルベーション、水溶性又は部分水溶性〜非水溶性の荷電又は中性ポリマー、液晶、ホットメルト、ヒドロゲル、香料付与プラスチック、マイクロカプセル、ナノ−、及びマイクロラテックス、ポリマー性フィルム形成剤、ポリマー性吸収剤、ポリマー性吸着剤などが一部の例である。PADとしては、限定されるものではないが、以下のものが挙げられる。
本発明のフィラメントは、1つ以上の漂白剤を含んでもよい。好適な漂白剤の非限定例としては、ペルオキシ酸、過ホウ酸塩、過炭酸塩、塩素系漂白剤、酸素系漂白剤、次亜ハロゲン酸系漂白剤、漂白剤前駆体、漂白活性剤、漂白触媒、過酸化水素、漂白促進剤、光漂白剤、漂白性酵素、フリーラジカル開始剤、過酸素系漂白剤、及びこれらの混合物が挙げられる。
当該技術分野において既知の任意の光学的な増白剤又は他の増白剤は、乾燥フィラメントベースで約0.01重量%〜約1.2重量%の濃度で本発明のフィラメントに組み込まれてもよい。本発明に有用であり得る市販の光増白剤は下位に分類することができ、これはスチルベン、ピラゾリン、クマリン、カルボン酸、メチンシアニン、ジベンゾチオフェン−5,5−ジオキシド、アゾール、5員−及び6−員の複素環、及び他の様々な剤の誘導体を含むが、必ずしもこれらに限定されない。このような増白剤の例は、「The Production and Application of Fluorescent Brightening Agents」(M.Zahradnik,John Wiley & Sons出版、New York(1982))に開示されている。本発明の組成物に有用である光学的な増白剤の具体的な非限定例は、米国特許第4,790,856号及び同第3,646,015号に特定されているものである。
本発明のフィラメントは布地色相剤を含んでもよい。好適な色相剤の非限定例としては、小分子染料及びポリマー染料が挙げられる。適切な小分子染料としては、色指数分類(Colour Index(C.I.))において、ダイレクト・ブルー、ダイレクト・レッド、ダイレクト・バイオレット、アシッド・ブルー、アシッド・レッド、アシッド・バイオレット、ベーシック・ブルー、ベーシック・バイオレット及びベーシック・レッド、又はそれらの混合物に適合する染料からなる群から選択される小分子染料が挙げられる。別の実施例では、適切なポリマー染料としては、Liquitint(登録商標)(Milliken、Spartanburg,South Carolina,USA)の名称で市販されている布地染色性着色剤、並びに少なくとも1つの反応染料と、ヒドロキシル部分、一級アミン部分、二級アミン部分、チオール部分、及びこれらの混合物からなる群から選択される部分を含むポリマーからなる群から選択されるポリマーとから形成される染料−ポリマー共役体からなる群から選択されるポリマー染料が挙げられる。更に別の態様では、適切なポリマー染料としては、Liquitint(登録商標)(Milliken,Spartanburg,South Carolina,USA)バイオレットCT、及びリアクティブブルー、リアクティブバイオレット、又はリアクティブレッド染料で共役されているカルボキシメチルセルロース(CMC)(例えば、Megazyme(Wicklow,Ireland)からAZO−CM−CELLULOSEという商品名(製品コードS−ACMC)で市販されているC.I.リアクティブブルー19で共役されているCMCなど)、アルコキシル化トリフェニルメタンポリマー着色料、アルコキシル化チオフェンポリマー着色料、及びこれらの混合物からなる群から選択されるポリマー染料が挙げられる。
a)[(CH2CR’HO)x(CH2CR”HO)yH]
式中、R’は、H、CH3、CH2O(CH2CH2O)zH、及びこれらの混合物からなる群から選択され、R”はH、CH2O(CH2CH2O)zH、及びこれらの混合物からなる群から選択され、x+y≦5であり、y≧1であり、z=0〜5である。
式中、R’はH、CH3、CH2O(CH2CH2O)zH、及びそれらの混合物からなる群から選択され、R”はH、CH2O(CH2CH2O)zH、及びそれらの混合物からなる群から選択され、x+y≦10であり、y≧1であり、z=0〜5である。
式中、R3はH、(CH2CH2O)zH、及びこれらの混合物からなる群から選択され、z=0〜10であり、
R4は(C1〜C16)アルキル、アリール基、及びこれらの混合物からなる群から選択される。
本発明のフィラメントは、洗浄プロセス中に、染料が1つの布地から他の布地へと移動するのを防止する、1つ以上の移染防止剤を含んでもよい。一般に、このような移染防止剤としては、ポリビニルピロリドンポリマー、ポリアミンN−オキシドポリマー、N−ビニルピロリドン及びN−ビニルイミダゾールのコポリマー、マンガンフタロシアニン、ペルオキシダーゼ、及びこれらの混合物が挙げられる。使用する場合、これらの剤は、典型的に、乾燥フィラメントベースで約0.01重量%〜約10重量%、及び/又は約0.01重量%〜約5重量%、及び/又は約0.05重量%〜約2重量%を構成する。
本発明のフィラメントは、1つ以上のキレート剤、例えば1つ以上の鉄及び/又はマンガン、及び/又は他の金属イオンキレート剤を含有してもよい。このようなキレート剤は、アミノカルボキシレート、アミノホスホネート、多官能置換された芳香族キレート剤、及びこれらの混合物からなる群から選択することができる。使用される場合、これらのキレート剤は一般に、乾燥フィラメントベースで約0.1重量%〜約15重量%、及び/又は約0.1重量%〜約10重量%、及び/又は約0.1重量%〜約5重量%、及び/又は約0.1重量%〜約3重量%を構成する。
泡の形成を低減又は抑制するための化合物を、本発明のフィラメント内に組み込んでもよい。抑泡制は、米国特許第4,489,455号及び同第4,489,574号に記載されているようないわゆる「高濃度洗浄プロセス」において、並びにフロント・ローディング方式の洗濯機において、特に重要なものとなり得る。
高い泡立ちが望まれる場合、起泡促進剤、例えばC10〜C16アルカノールアミドが、典型的に、乾燥フィラメントベースで0重量%〜約10重量%、及び/又は約1重量%〜約10重量%の濃度でフィラメントに組み込まれてもよい。C10〜C14モノエタノール及びジエタノールアミドは、このような起泡促進剤の典型的な部類を示す。上述の、アミンオキシド、ベタイン及びスルタインなどの高起泡補助界面活性剤を含む泡促進剤を使用することも有益である。所望であれば、水溶性マグネシウム及び/又はカルシウム塩、例えばMgCl2、MgSO4、CaCl2、CaSO4等を、乾燥フィラメントベースで約0.1重量%〜約2重量%の濃度でフィラメントに添加して、更なる泡を提供してもよい。
1つ以上の柔軟剤がフィラメント内に存在してもよい。好適な柔軟剤の非限定例としては、エステル第4級アンモニウム化合物、シリコーン(例えばポリシロキサン)、粘土(例えばスメクタイト粘土)、及びこれらの混合物が挙げられる。
本発明のフィラメントは、1つ以上のコンディショニング剤、例えば高融点脂肪族化合物を含んでもよい。高融点脂肪族化合物は、約25℃以上の融点を有し、脂肪族アルコール、脂肪酸、脂肪族アルコール誘導体、脂肪酸誘導体、及びこれらの混合物からなる群から選択されてもよい。低融点(25℃未満)を呈するこのような脂肪族化合物は、コンディショニング剤として含有させることを意図していない。高融点脂肪族化合物の非限定例は、「International Cosmetic Ingredient Dictionary」(Fifth Edition,1993)及び「CTFA Cosmetic Ingredient Handbook」(Second Edition,1992)に見出される。
本発明のフィラメントは、1つ以上の湿潤剤を含有してもよい。本明細書における保湿剤は、多価アルコール、水溶性アルコキシル化非イオン性ポリマー、及びこれらの混合物からなる群より選択される。使用する場合、保湿剤は、乾燥フィラメントベースで、約0.1重量%〜約20重量%、及び/又は約0.5重量%〜約5重量%の濃度でフィラメント内に存在してもよい。
本発明のフィラメントは、非水溶性物質を組成物中に分散させた形態で懸濁化するために、又は組成物の粘度を変性するために有効な濃度で、懸濁化剤を更に含んでもよい。懸濁化剤のこのような濃度は乾燥フィラメントベースで約0.1重量%〜約10重量%、及び/又は約0.3重量%〜約5.0重量%の範囲である。
1つ以上の酵素が本発明のフィラメント内に存在してもよい。好適な酵素の非限定例としては、プロテアーゼ、アミラーゼ、リパーゼ、マンナナーゼ及びエンドグルカナーゼを含むカルボヒドラーゼ、ペクチナーゼ、ヘミセルラーゼ、ペルオキシダーゼ、キシラナーゼ、ホスホリパーゼ、エステラーゼ、クチナーゼ、ケラタナーゼ、レダクターゼ、オキシダーゼ、フェノールオキシダーゼ、リポキシゲナーゼ、リグニナーゼ、プルラナーゼ、タンナーゼ、ペントサナーゼ(penosanase)、マラナーゼ、グルカナーゼ、アラビノシダーゼ、ヒアルロニダーゼ、コンドロイチナーゼ、ラッカーゼ、及びそれらの混合物が挙げられる。
酵素が本発明のフィラメント及び/又は繊維内に存在する場合、酵素安定化系もまた、フィラメント内に含有させてよい。酵素は様々な技法によって安定化させることができる。酵素安定化技法の非限定例は、米国特許第3,600,319号及び同第3,519,570号、欧州特許第199,405号、同第200,586号、及び国際公開第9401532(A)号に開示され、例示されている。
本発明のフィラメントは、1つ以上のビルダーを含んでもよい。好適なビルダーの非限定例としては、ゼオライトビルダー、アルミノケイ酸塩ビルダー、シリケートビルダー、ホスフェートビルダー、クエン酸、クエン酸塩、ニトリロ三酢酸、ニトリロトリアセテート、ポリアクリレート、アクリレート/マレエートコポリマー、及びこれらの混合物が挙げられる。
本発明のフィラメントは、粘土汚れ除去及び再付着防止特性を有する水溶性エトキシル化アミンを含有してもよい。このような水溶性エトキシル化アミンは、乾燥フィラメントベースで、1つ以上の水溶性エトキシル化アミンが約0.01重量%〜約10.0重量%、及び/又は約0.01重量%〜約7重量%、及び/又は0.1重量%〜約5重量%の濃度のになるよう、本発明のフィラメントに存在してもよい。好適な粘土汚れ除去及び再付着防止の非限定例は、米国特許第4,597,898号、同第548,744号、同第4,891,160号、欧州特許出願第111,965号、同第111,984号、同第112,592号、及び国際公開第95/32272号に記載されている。
本発明のフィラメントは、汚れ放出ポリマー(以下「SRA」)を含有してもよい。使用する場合、SRAは一般的に乾燥フィラメントベースで約0.01重量%〜約10.0重量%、及び/又は約0.1重量%〜約5重量%、及び/又は約0.2重量%〜約3.0重量%を構成する。
ポリマー分散剤は有利なことに、乾燥フィラメントベースで、特にゼオライト及び/又は層状のケイ酸ビルダーの存在下で、約0.1重量%〜約7重量%、及び/又は約0.1重量%〜約5重量%、及び/又は0.5重量%〜約4重量%の濃度で、本発明のフィラメントに使用することができる。好適なポリマー分散剤には、ポリマーポリカルボン酸塩及びポリエチレングリコールが挙げられるが、当該技術分野において既知の他の分散剤も使用することができる。例えば、多種多様の修飾された若しくは非修飾のポリアクリレート、ポリアクリレート/メタクリレート(mealeates)、又はポリアクリレート/メタクリレートが非常に有用である。理論に束縛されることを意図していないが、ポリマー分散剤を、他のビルダー(低分子量ポリカルボン酸を含む)と組み合わせて使用した場合、結晶成長防止、粒子状の汚れ放出解膠、及び再付着防止によって、全体的なの洗剤ビルダーの性能が向上されることになる。ポリマー分散剤の非限定例は、米国特許第3,308,067号、欧州特許出願第66915号、欧州特許第193,360号、及び同第193,360号に見出される。
アルコキシル化ポリアミンは、汚れ懸濁化、油脂洗浄、及び/又は粒子洗浄のために本発明のフィラメントに含有させてもよい。このようなアルコキシル化ポリアミンとしては、限定するものではないが、エトキシル化ポリエチレンイミン、エトキシル化ヘキサメチレンジアミン、及びその硫酸化バージョンが挙げられる。ポリアミンのポリプロポキシル化誘導体も、本発明のフィラメントに含まれてもよい。多種多様なアミン及びポリアルキレンイミン(polyaklyeneimine)は様々な度合いまでアルコキシル化してもよく、任意に更に修飾して上記の利点をもたらすこともできる。有用な実施例としては、NH当たり20 EO基までエトキシル化されている600g/モルポリエチレンイミンコアがBASFより入手可能である。
ポリアクリレートから調製されたものなどアルコキシル化ポリカルボン酸塩は、更なる油脂除去性能を提供するために、本発明のフィラメントに含有させてもよい。このような材料はWO 91/08281号及びPCT 90/01815号に記載されている。化学的に、これらの材料は、7〜8のアクリレート単位ごとに1つのエトキシ側鎖を有するポリアクリレートを含む。側鎖は式−(CH2CH2O)m(CH2)nCH3であり、式中、mは2〜3であり、nは6〜12である。側鎖はポリアクリレート「主鎖」にエステル結合され、「櫛形」ポリマータイプの構造を提供する。分子量は通常は約2000〜約50,000の範囲内で変動し得る。このようなアルコキシル化ポリカルボン酸塩を、乾燥フィラメントベースで約0.05重量%〜約10重量%含有させることができる。
本発明のフィラメントは1つ以上の両親媒性グラフトコポリマーを含み得る。好適な両親媒性グラフトコポリマーの例は、(i)ポリエチレングリコール主鎖、及び(ii)ポリ酢酸ビニル、ポリビニルアルコール、及びこれらの混合物から選択される少なくとも1つのペンダント部分を含む。市販されている両親媒性グラフトコポリマーの非限定例は、BASFから供給されているSokalan HP22である。
場合により形成し得る不溶性若しくは可溶性の劣る界面活性剤の形成を減少させるために、40%を超える界面活性剤活性剤をフィラメントが含有する場合、又は界面活性剤を冷水中で使用する場合、本発明のフィラメントには、溶解を促進するために溶解助剤を組み込んでもよい。溶解助剤の非限定例としては、塩化ナトリウム、硫酸ナトリウム、塩化カリウム、硫酸カリウム、塩化マグネシウム、及び硫酸マグネシウムが挙げられる。
本発明のフィラメントは、1つ以上の摂取可能な活性剤を含んでもよい。一実施例では、摂取可能な活性剤は1つ以上のヘルスケア活性剤を含んでもよい。
一実施例では、1つ以上のヘルスケア活性剤(health care actives)(ヘルスケア活性剤(health care active agents))は、フィラメント中に均一に分散させてもよく、又は実質的に均一に分散させてもよい。他の実施例では、1つ以上のヘルスケア活性剤は、フィラメント内に別個の領域として分散させてもよい。更に他の実施例では、少なくとも1つのヘルスケア活性剤は、フィラメント全体に均一に、又は実質的に均一に分散され、少なくとも1つの他のヘルスケア活性剤は、フィラメント内の1つ以上の別個の領域として分散される。更に他の実施例では、少なくとも1つのヘルスケア活性剤は、フィラメント内の1つ以上の別個の領域として分散され、少なくとも1つの他のヘルスケア活性剤は、フィラメント内の第1の別個の領域から1つ以上の別個の領域として分散される。
一実施例では、1つ以上のヘルスケア活性剤は呼吸器系剤であってもよい。呼吸器系剤の非限定例は、抗鼻閉薬、粘液溶解薬、去痰薬、抗ヒスタミン剤、非麻薬系鎮咳薬、鎮痛薬、麻酔剤、植物由来の呼吸器系剤、及びこれらの組み合わせを含んでもよい。呼吸器系剤は呼吸系の状態を治療するために使用されてもよい。呼吸器系の状態の非限定例としては、インフルエンザ、一般的な風邪、肺炎、気管支炎、及び他のウイルス性感染;肺炎、気管支炎、及び他の細菌性感染症、アレルギー、副鼻腔炎;鼻炎、及びこれらの組み合わせを挙げることができる。呼吸器系剤は呼吸器系の利益をもたらし得る。呼吸器系の利益の非限定例としては、呼吸器系症状を治療することが含まれ得る。呼吸器系症状の非限定例としては、鼻詰まり、胸部うっ血、鼻漏、咳、くしゃみ、頭痛、身体の痛み、熱、疲労、すなわち倦怠感、咽頭炎、呼吸困難、副鼻腔の圧迫感、副鼻腔の痛み、及びこれらの組み合わせが挙げられる。
一実施例では、1つ以上のヘルスケア活性剤は胃腸剤であってもよい。胃腸剤の非限定例としては、下痢止め剤、下部消化管剤、下剤、吐き気止め、制酸薬、鼓腸防止剤(anti-flattulents)、H2受容体拮抗薬、プロトンポンプ阻害剤、リパーゼ阻害剤、運搬剤(rafting agent)、プロバイオティクス、プレバイオティクス、食物繊維、酵素、植物由来の胃腸剤、麻酔剤、及びこれらの組み合わせが挙げられ得る。胃腸剤は、胃腸の状態を治療するために使用されてもよい。胃腸の状態の非限定例としては、胃食道逆流症、胃炎、消化性潰瘍、消化不良、過敏性腸症候群、大腸炎、クローン病、バレット食道、ガストリノーマ、下痢、消化不良、便秘、肥満、回腸嚢炎、憩室炎、腸炎(enteritis)、腸炎(enterocolitis)、嚥下障害、炎症性痔、食中毒、及び他の細菌性感染症、インフルエンザ、及び他のウイルス性感染、並びにこれらの組み合わせが挙げられ得る。胃腸剤は、胃腸に関する利益を提供し得る。胃腸に関する利益の非限定例としては、消化バランス、胃腸の症状の治療、及びこれらの組み合わせが挙げられる。胃腸の症状の非限定的な実施例としては、下痢、便秘、胃のむかつき、嘔吐、胸やけ、激しい腹痛、ガス、膨張、腹痛、咽頭炎、嚥下困難、意図していない体重減少、内臓の過敏症、膨満感、消化不良、悪心、胸やけ、急な便意、食欲不振、逆流、おくび、鼓腸、下血、脱水、及びこれらの組み合わせが挙げられ得る。
一実施例では、1つ以上のヘルスケア活性剤は中枢神経系(CNS)作用剤であってもよい。CNS剤の非限定例としては、睡眠助剤、非ステロイド系抗炎症薬、サリチル酸塩、オピオイド鎮痛剤、その他の中枢神経系刺激剤、吐き気止め、及びこれらの組み合わせが挙げられる。吐き気止めは本明細書に記載されている。CNS剤はCNS状態を治療するために使用されてもよい。CNS状態の非限定例としては、不眠症、むずむず脚症候群、ナルコレプシー、疼痛、たばこ依存症、鬱病、多動症候群、注意欠陥多動性障害、及びこれらの組み合わせが挙げられる。疼痛の非限定例としては、頭痛、片頭痛、関節炎、術後痛、歯痛、及びこれらの組み合わせが挙げられる。CNS助剤は、CNSの利益を提供し得る。CNSの利益の非限定例としては、覚醒、通常のサーカディアンリズムの回復、CNS症状の治療、及びこれらの組み合わせが挙げられ得る。CNS症状の非限定例としては、不眠症、異常なサーカディアンリズム、疼痛、炎症、倦怠感、眠気、集中力低下、炎症、嘔吐、悪心、及びこれらの組み合わせが挙げられ得る。
一実施例では、1つ以上のヘルスケア活性剤は抗感染剤であってもよい。抗感染剤の非限定例としては、抗ウイルス剤、抗菌剤、及びこれらの組み合わせが挙げられ得る。病原性感染を治療するために抗感染剤を使用してもよい。病原性感染の非限定例としては、結核、肺炎、食中毒、破傷風、腸チフス、ジフテリア、梅毒、髄膜炎、敗血症、ハンセン病、百日咳、ライム病、壊疽、尿路感染、旅行者下痢、メチシリン耐性黄色ブドウ球菌(MRSA)、淋疾、猩紅熱、コレラ、疱疹、肝炎、ヒト免疫不全ウイルス(HIV)、インフルエンザ、麻疹、ムンプス、ヒト・パピローマウイルス、ポリオウイルス、ジアルジア、マラリア、サナダムシ、線虫、及びこれらの組み合わせが挙げられる。抗感染剤は抗感染利益を提供することができる。抗感染利益の非限定例としては病原性感染症の治療が挙げられる。病原性感染の非限定例としては、熱、炎症、悪心、嘔吐、食欲不振、白血球数の異常、下痢、発疹、皮膚損傷、咽頭炎、頭痛、腹痛、筋肉痛、倦怠感、咳、胸痛、呼吸困難、膀胱炎、及びこれらの組み合わせが挙げられ得る。
一実施例では、1つ以上のヘルスケア活性剤は栄養剤であってもよい。栄養剤の非限定例としては、ビタミン、ミネラル、及び電解質、食物繊維、脂肪酸、及びこれらの組み合わせが挙げられ得る。栄養剤は栄養欠乏症を治療するために使用してもよい。栄養欠乏症の非限定例としては、免疫系の機能低下、新生児の出生異常、心臓疾患、癌、アルツハイマー病、眼の疾患、夜盲症、骨粗鬆症、脚気、ペラグラ、壊血病、くる病、アルコール依存症、過敏性腸症候群(IBS)、低ホルモンレベル、高血圧、及びこれらの組み合わせが挙げられ得る。栄養剤は栄養の利益をもたらし得る。栄養学的な利益の非限定例としては、病気防止、コレステロール低下、エネルギー及び覚醒の増加、老化防止、消化バランスの回復、栄養欠乏症の治療、及びこれらの組み合わせが挙げられ得る。栄養欠乏症の症状の非限定例としては、倦怠感、筋力低下、過敏性、脱毛、意図していない体重減少、意図していない体重増加、創傷治癒遅延、知能低下、ストレス、骨折、視力低下、創傷治癒の速度低下、活動亢しん、皮膚炎、筋痙攣、心不整脈、鬱病、及びこれらの組み合わせが挙げられ得る。
一実施例では、1つ以上のヘルスケア活性剤は全体的な健康剤であってもよい。全体的な健康剤の非限定例としては、エネルギー増加剤、プロバイオティクス、プレバイオティクス、食物繊維、酵素、ビタミン、ミネラル、及び電解質、酸化防止剤、脂肪酸、並びにこれらの混合物が挙げられ得る。プロバイオティクス、プレバイオティクス、食物繊維、酵素、ビタミン、ミネラル、及び電解質、酸化防止剤、並びに脂肪酸は本明細書に記載されている。
本発明のフィラメント及び/又は不織布ウェブには1つ以上の賦形剤を含有させ得る。賦形剤の非限定例としては、フィラメント形成材料、審美剤、及びこれらの組み合わせが挙げられる。フィラメント形成材料の非限定例としては、基幹材料、伸長助剤、レオロジー変性剤、架橋剤、及びこの組み合わせが挙げられる。審美剤の非限定例としては、風味、着色剤、知覚剤(冷却及び/又は加熱剤)、甘味料、唾液分泌剤、及びこれらの組み合わせが挙げられる。
使用され得る着香剤には、天然及び人工香料など、当業者に既知のものが挙げられる。これらの着香剤は、着香芳香族化合物、及び/又は油、含油樹脂、並びに植物、葉、花、果実等、及びこれらの組み合わせ由来の抽出物から選択されてもよい。代表的な着香油には、スペアミント油、桂皮油、ペパーミント油、丁子油、ベイ油、タイム油、ニオイヒバ油、ナツメグの油、セージの油、及び苦扁桃の油が挙げられる。また、有用なのは人工、天然、又は合成の果物の風味、例えばバニラ、チョコレート、コーヒー、ココア、及び柑橘油(レモン、オレンジ、ブドウ、ライム、及びグレープフルーツを含む)、並びに果物エキス(リンゴ、ナシ、モモ、イチゴ、ラズベリー、チェリー、プラム、パイナップル、アプリコット等)である。これらの着香剤は個々に、又は混合して使用することができる。一般に使用される香味としては(個々であろうと又は混合して使用しようと)、ペパーミントなどのミント類、人工バニラ、桂皮誘導体、及び様々な果物の風味が挙げられる。酢酸シンナミル、桂皮アルデヒド、シトラール、ジエチルアセタール、ジヒドロカルビルアセタート、オイゲニルホルメイト、p−メチルアニソール等を含むアルデヒド及びエステルなどの風味もまた使用されてもよい。概ね、「Chemicals Used in Food Processing」(publication 1274 by the National Academy of Sciences,pages 63〜258)に記載されてているものなど、任意の風味又は食物添加剤が使用されてもよい。アルデヒド香料の更なる例としては、アセトアルデヒド(リンゴ);ベンズアルデヒド(チェリー、アーモンド);桂皮アルデヒド(桂皮);シトラール、すなわちαシトラール(レモン、ライム);ネラール、すなわちβシトラール(レモン、ライム);デカナール(オレンジ、レモン);エチルバニリン(バニラ、クリーム);ヘリオトロピン、すなわちピペロナール(バニラ、クリーム);バニリン(バニラ、クリーム);α−アミル桂皮アルデヒド(スパイシーな果物の風味);ブチルアルデヒド(バター、チーズ);バレルアルデヒド(バター、チーズ);シトロネラール(改質剤、多くのタイプ);デカナール(柑橘類);アルデヒドC−8(柑橘類);アルデヒドC−9(柑橘類);アルデヒドC−12(柑橘類);2−エチルブチルアルデヒド(液果類);ヘキセナール、すなわちトランス−2(液果類);トリルアルデヒド(チェリー、アーモンド);ベラトルムアルデヒド(バニラ);2,6−ジメチル−5−ヘプテナール、すなわちメロナール(メロン);2−6−ジメチルオクターナル(青玉果);及び2−ドデセナール(シトラス、マンダリン);チェリー;グレープ、これらの混合物等が挙げられるが、これらに限定されない。
唾液刺激剤の非限定例としては、酸性食品、例えばクエン酸、乳酸、リンゴ酸、コハク酸、アスコルビン酸、アジピン酸、フマル酸、及び酒石酸が挙げられる。
精油であってもよい冷感剤の非限定例としては、モノメンチルスクシネート、メントール(例えばL−メントール)、カンファー、ユーカリ油、ラベンダーオイル(ブルガリアのラベンダーオイル)、チモール、メチルサリシレート、及びこれらの混合物が挙げられる。
本発明のフィラメントに含有させることができる好適な甘味剤の非限定例としては、天然及び人工甘味剤が挙げられる。一実施例では、甘味剤は、以下からなる群から選択される:
A.キシロース、リボース、グルコース(ブドウ糖)、マンノース、ガラクトース、フルクトース(果糖)、ショ糖(砂糖)、マルトース、転化糖(フルクトースとショ糖由来のグルコースとの混合物)、部分的に加水分解したデンプン、コーンシロップ固形物、ジヒドロカルコン、モネリン、ステビオシド、及びグリチルリチンといった、単糖類、二糖類、及び多糖類などの水溶性甘味剤;
B.可溶性サッカリン塩、すなわち、サッカリンナトリウム又はカルシウム塩、シクラメート塩、3,4−ジヒドロ−6−メチル−1,2,3−オキサチアジン−4−オン−2,2−ジオキシドのナトリウム塩、アンモニウム塩、又はカルシウム塩、3,4−ジヒドロ−6−メチル−1,2,3−オキサチアジン−4−オン−2,2−ジオキシドのカリウム塩(アセスルファム−K)、遊離酸型サッカリン等の水溶性人工甘味剤;
C.L−アスパルチル−L−フェニルアラニンメチルエステル(アスパルテーム)及び米国特許第3,492,131号に記載された物質のようなL−アスパラギン酸由来の甘味剤、L−α−アスパルチル−N−(2,2,4,4−テトラメチル−3−チエタニル)−D−アラニンアミド水和物、L−アスパルチル−L−フェニルグリセリン及びL−アスパルチル−L−2,5,ジヒドロフェニル−グリシンのメチルエステル、L−アスパルチル−2,5−ジヒドロ−L−フェニルアラニン、L−アスパルチル−L−(1−シクロヘキシエン)−アラニン等のようなジペプチド系甘味剤;
D.例えば、スクラロースの製品銘柄で既知である一般的な砂糖(スクロース)の塩素化誘導体などの、天然素材の水溶性甘味剤由来の水溶性甘味剤;及び
E.ソーマトコッカス・ダニエリ(ソーマチンI及びII)、及びこれらの混合物などのタンパク質系の甘味剤。
本発明に有用な硫黄沈殿剤としては、金属塩、例えば銅塩及び亜鉛塩が挙げられる。一実施例では、硫黄沈殿剤はグルコン酸銅、クエン酸亜鉛、グルコン酸亜鉛、及びこれらの混合物からなる群から選択される。
動物、例えばヒトによって摂取可能である任意の好適な医薬品組成物、処方箋調剤、又は市販薬剤は、本発明によってフィラメントにより送達され得る。例えば、咳止めシロップを摂取することによって、又は咳止めシロップの1つ以上の成分を含む1つ以上のフィラメントを摂取することによって送達され得る。同様に、胃のむかつき緩和剤、例えばPepto−BISMOL(登録商標)又はその中の成分(例えば次サリチル酸ビスマス)は、本発明のフィラメントによって送達され得る。更に、消毒剤、及び/又は抗菌(antibacterial)、及び/又は抗菌(antimicrobial)(例えばアルコール及び/又は酸による)が、本発明に従うフィラメントによって送達されてもよい。
本発明のフィラメントは1つ以上の着色剤(color agents)、すなわち着色剤(colorants)を含んでもよい。着色剤は、所望の色を作るのに効果的な量で使用され得る。本発明に有用な着色剤には、食品、薬剤、及び化粧品用途に好適な二酸化チタン、天然食物着色剤、及び染料、並びにこれらの混合物などの染料が挙げられる。いくつかの着色剤(color agent)(着色剤(colorants))は、FD&C染料等として既知である。一実施例では、着色剤は水溶性である。好適な着色剤の非限定例としては、FD&C青色2号(これは5,5−インジゴチンジスルホン酸の二ナトリウム塩であり)、緑色3号として既知の染料(トリフェニルメタン染料を含み、かつ4−[4−N−エチル−p−スルホベンジルアミノ)ジフェニル−メチレン]−[1−N−エチル−N−p−ベンジルスルホニウム)−2,5−シクロ−ヘキサジエンイミンの一ナトリウム塩である]、及びこれらの混合物が挙げられる。他の好適なFD&C及びD&C染料及びそれの対応する化学構造の完全な詳細説明は、「Kirk−Othmer Encyclopedia of Chemical Technology」(Volume 5,Pages 857〜884)に見出すことができ、このテキストはしたがって、本明細書において参照により組み込む。
フィラメントに有用な多種多様な他の成分が、フィラメントに含まれてもよい。そのような他の成分の非限定例としては、担体、ヒドロトロープ、加工助剤、染料若しくは顔料、溶媒、及び固体若しくは他の液体の充填剤、エリトロシン、コロイド状シリカ、ろう、プロバイオティクス、サーファクチン(surfactin)、アミノセルロース系のポリマー(aminocellulosic polymers)、リシノール酸亜鉛、香料、マイクロカプセル、ラムノリピド、ソホロリピッド、グリコペプチド、メチルエステルスルホネート、メチルエステルエトキシレート、スルホン化エストリド、開裂可能界面活性剤、バイオポリマー、シリコーン、修飾シリコーン、アミノシリコーン、付着助剤、イナゴマメゴム、カチオン性ヒドロキシエチルセルロースポリマー、カチオン性グアー、ヒドロトロープ(特にキュメンスルホン酸ナトリウム塩、トルエンスルホン酸塩、キシレンスルホン酸塩、及びナフタリン塩)、酸化防止剤、BHT、PVA粒子−封入染料若しくは香料、真珠光沢剤、発泡助剤、色調変更系、シリコーンポリウレタン、乳白剤、錠剤崩壊剤、バイオマス充填剤、高速乾燥シリコーン、グリコールジステアレート、ヒドロキシエチルセルロースポリマー、疎水変性セルロースポリマー若しくはヒドロキシエチルセルロースポリマー、デンプン香料封入、乳化油、ビスフェノール酸化防止剤、微細繊維状セルロース界面活性剤、プロ香料(properfume)、スチレン/アクリレートポリマー、トリアジン、石鹸、スーパーオキシドジスムターゼ、ベンゾフェノンプロテアーゼ阻害剤、官能性を持たせたTiO2、ジブチルホスフェート、シリカ香料カプセル、他の補助成分、ジエチレントリアミン五酢酸、タイロン(1,2−ジヒドロキシベンゼン(diydroxybenzene)−3,5−ジスルホン酸)、ヒドロキシエタンジメチレンホスホン酸、メチルグリシン二酢酸、コリンオキシダーゼ、ペクタートリアーゼ、トリアリールメタンブルー及びバイオレット塩基性染料、メチンブルー及びバイオレット塩基性染料、アントラキノンブルー及びバイオレット塩基性染料、アゾ染料ベーシック・ブルー16、ベーシック・ブルー65、ベーシック・ブルー66、ベーシック・ブルー67、ベーシック・ブルー71、ベーシック・ブルー159、ベーシック・バイオレット19、ベーシック・バイオレット35、ベーシック・バイオレット38、ベーシック・バイオレット48、オキサジン染料、ベーシック・ブルー3、ベーシック・ブルー75、ベーシック・ブルー95、ベーシック・ブルー122、ベーシック・ブルー124、ベーシック・ブルー141、ナイルブルーA及びキサンテン染料ベーシック・バイオレット10、アルコキシル化トリフェニルメタンポリマー着色剤;アルコキシル化チオフェンポリマー着色剤;チアゾリウム染料、雲母、二酸化チタン被覆雲母、オキシ塩化ビスマス、及び他の活性剤が挙げられる。
本発明のフィラメントは、水性洗浄操作(例えば服若しくは食器の洗浄)における使用中に、洗浄水が約5.0〜約12、及び/又は約7.0〜10.5のpHを有するように、配合してもよい。食器洗浄操作の場合では、洗浄水のpHは典型的には約6.8〜約9.0である。服の洗浄の場合では、洗浄水のpHは典型的には7から11の間である。推奨される使用量でのpHを制御する技術には、緩衝剤、アルカリ、酸などの使用を含み、当業者には周知である。これらは、炭酸ナトリウム、クエン酸、若しくはクエン酸ナトリウム、モノエタノールアミン若しくは他のアミン、ホウ酸若しくはホウ酸塩、並びに当該技術分野において既知の他のpH調整化合物の使用を含む。
フィラメントを誘因条件に曝した場合に、1つ以上の活性剤がフィラメントから放出され得る。一実施例では、1つ以上の活性剤は、フィラメント又はフィラメントの一部がその自己同一性、すなわちその物理的構造を失ったときに、フィラメントから、又はフィラメントの一部から放出され得る。例えば、フィラメント形成材料が溶解した、溶融した、又はフィラメント構造が失われるような変形工程を経たときに、フィラメントはその物理的構造を失う。一実施例では、1つ以上の活性剤は、フィラメントの形態が変化した際に、フィラメントから放出される。
本発明のフィラメントはフィラメント形成組成物から製造される。フィラメント形成組成物は極性溶媒系組成物である。一実施例では、フィラメント形成組成物は、1つ以上のフィラメント形成材料及び1つ以上の活性剤を含む水溶性組成物である。
ηは、ダイの条件したでの流体粘度(長さ当たりの質量の単位*時間)であり、
σは流体の表面張力(時間2当たりの質量の単位)である。速度、粘度及び表面張力が一連の一貫した単位で表されるとき、結果として得られる毛管数はそれ自身の単位を持たず、個々の単位は相殺される。
面積=ダイ出口の断面積(長さ2の単位)である。
ηは、ダイの条件したでの流体粘度(長さ当たりの質量の単位*時間)であり、
σは流体の表面張力(時間2当たりの質量の単位)である。速度、粘度及び表面張力が一連の一貫した単位で表されるとき、結果として得られる毛管数はそれ自身の単位を持たず、個々の単位は相殺される。
面積=ダイ出口の断面積(長さ2の単位)である。
一実施例では、フィラメントは伸張助剤を含む。伸長助剤の非限定例としては、ポリマー、他の伸長助剤、及びこれらの組み合わせが挙げられる。
本発明のフィラメントは、あらゆる好適なプロセスによって製造することができる。フィラメントを製造するための好適なプロセスの非限定例を以下に記載する。
a.1つ以上のフィラメント形成材料と、1つ以上の活性剤と、を含むフィラメント形成組成物を用意する工程と、
b.該フィラメント形成組成物を紡糸して、1つ以上のフィラメント形成材料と、フィラメントの形態が変化した際にフィラメントから放出可能である1つ以上の活性剤と、を含む、1つ以上のフィラメントにする工程であって、フィラメント内に存在するフィラメント形成材料の総濃度が乾燥フィラメントベースで65重量%未満であり、フィラメント内に存在する活性剤の総濃度が乾燥フィラメントベースで35重量%を超える、工程とを含む。
本発明の1つ以上の、及び/又は複数のフィラメントは、当該技術分野において既知の任意の好適なプロセスによって不織布を形成してもよい。フィラメント及び/又は不織布に目的とされる用途の状態に曝した際に、本発明のフィラメントから活性剤が送達されるよう不織布ウェブを使用してもよい。
自動食器洗浄機用物品は、1つ以上の本発明のフィラメント及び/又は繊維、及び/又は不織布ウェブ、及び/又はフィルム、並びに界面活性剤活性剤系、並びに、任意に当該技術分野において既知の1つ以上の任意成分(例えば、自動食器洗浄機での食器の洗浄に有用な成分)を含む。これらの任意の成分の例としては、スケール防止、漂白剤、香料、染料、抗菌剤、酵素(例えばプロテアーゼ)、洗浄ポリマー(例えば、アルコキシル化ポリエチレンイミンポリマー)、ヒドロトロープ、泡防止剤、カルボン酸、増粘剤、防腐剤、消毒剤、自動食器洗浄液が全体的に3〜14の(あるいは8〜11)のpHを有するようなpH緩衝系、又はこれらの混合物が挙げられる。自動食器洗浄機用活性剤の例は、米国特許第5,679,630号、同第5,703,034号、同第5,703,034号、同第5,705,464号、同第5,962,386号、同第5,968,881号、同第6,017,871号、同第6,020,294号に記載されている。
食器手洗い用洗浄物品は、本発明の1つ以上のフィラメント、及び/又は繊維、及び/又は不織布ウェブ、及び/又はフィルム、及び界面活性剤系、並びに任意に、洗浄の当該技術分野において既知の1つ以上の任意の成分(例えば手で食器を洗う際に有用である)を含む。これらの任意の成分の例としては、香料、染料、抗菌剤、酵素(例えばプロテアーゼ)、洗浄ポリマー(例えば、アルコキシル化ポリエチレンイミンポリマー)、ヒドロトロープ、ポリマー泡安定剤、漂白剤、ジアミン、カルボン酸、増粘剤、防腐剤、消毒剤、食器洗浄液が全体的に3〜14の(好ましくは8〜11)のpHを有するようなpH緩衝手段、又はこれらの混合物が挙げられる。食器手洗い用洗浄物品の例は、米国特許第5,990,065号、及び同第6,060,122号に記載されている。
硬質表面洗浄物品は、本発明の1つ以上のフィラメント、及び/又は繊維、及び/又は不織布ウェブ、及び/又はフィルム、及び任意に、当該技術分野において既知の1つ以上の任意の成分(例えば硬質表面の洗浄に有用である)、例えば酸性成分、例えば、石炭のかすの良好な除去性能を提供する酸性成分(例えば、ギ酸、クエン酸、ソルビン酸、酢酸、ホウ酸、マレイン酸、アジピン酸、乳酸、リンゴ酸、マロン酸、グリコール酸、又はこれらの混合物)を提供する酸性成分を含む。硬質表面の酸性洗浄物品に含まれ得る成分の例としては、米国特許第7,696,143号に記載のものが挙げられる。あるいは、硬質表面洗浄物品は、アルカリ性成分(例えば、アルカノールアミン(alkanolmine)、炭酸塩、重炭酸塩化合物、又はこれらの混合物)を含む。硬質表面のアルカリ性洗浄物品に含まれ得る成分の例としては、米国特許出願第2010/0206328(A1)号に記載のものが挙げられる。硬質表面を洗浄する方法は、硬質表面を洗浄する方法において、硬質表面洗浄物品を使用すること、又は投与することを含む。一実施形態では、本方法は、硬質表面洗浄物品をバケツ又は同様の容器に投与することと、任意に、物品をバケツに投与する前若しくは投与した後にバケツに水を加えることと、を含む。他の実施形態では、本方法は、硬質表面洗浄物品を便器に投与することと、任意に、便器内の水に物品を溶解した後に、便器の表面を磨くことと、を含む。
本発明の1つ以上のフィラメント、及び/又は繊維、及び/又は不織布、及び/又はフィルムを含む便器洗浄用具のための便器洗浄ヘッドが提供される。トイレ便器洗浄ヘッドは使い捨てであってもよい。便器洗浄ヘッドは、取り外し可能にハンドルに取り付けられてもよく、そのためユーザーの手はこのハンドルによって便器から離れたままである。一実施例では、便器洗浄ヘッドには水分散性シェルを含有させてもよい。同様に、水分散性シェルには、本発明の1つ以上のフィラメント、及び/又は繊維、及び/又は不織布ウェブ、及び/又はフィルムを含有させてもよい。この水分散性シェルはコア部を包んでもよい。このコア部には、少なくとも1つの顆粒状材料を含有させてもよい。コア部に含まれる顆粒状材料には、界面活性剤、有機酸、香料、消毒剤、漂白剤、洗剤、酵素、微粒子、又はこれらの混合物が含まれ得る。任意に、コア部はセルロースを含まなくてもよく、かつ本発明の1つ以上のフィラメント、及び/又は繊維、及び/又は不織布ウェブ、及び/又はフィルムを含んでもよい。好適な便器洗浄ヘッドの例は、本発明の譲受人に譲渡された米国特許出願シリアル番号第12/901,804号(P&G Case 11892)に従って製造され得る。デンプン材料を含有する好適な便器洗浄ヘッドは、本発明の譲受人に譲渡された米国特許出願シリアル番号第13/073,308号(P&G Case 12048)、同第13/073,274号(P&G Case 12049)、及び/又は同第13/07,3346号(P&G Case 12054)に従って製造され得る。本発明の便器洗浄ヘッドを便器表面と接触させる工程を含む、便器表面の洗浄方法が提供される。
本発明に従う1つ以上の布地ケア活性剤を含む不織布ウェブ又はフィルムは、布地物品を処理する方法に利用することもできる。布地物品を処理する方法は、(a)布地物品を洗浄する前に、布地物品を前処理する工程と、(b)不織布ウェブ若しくはフィルムを水と接触させることによって形成された洗浄液と、布地物品を接触させる工程と、(c)布地物品を、乾燥機内で不織布ウェブ若しくはフィルムと接触させる工程と、(d)不織布ウェブ若しくはフィルムの存在下で布地物品を乾燥機内で乾燥させる工程と、(e)これらの組み合わせ、からなる群から選択される1つ以上の工程を含んでもよい。
本発明の不織布ウェブはフィルムに変換されてもよい。本発明に従う不織布ウェブからフィルムを製造するプロセスの例は、
a.フィラメント形成材料からなる、例えば極性溶媒可溶性フィラメント形成材料からなる、複数のフィラメントを含む不織布ウェブを提供する工程と、
b.不織布ウェブをフィルムに変換する工程と、を含む。
本発明に従うフィラメントの非限定例は、小型装置26を使用することによって製造され、その略図は図5及び6に示されている。バッチ操作に適した加圧されたタンク28は、フィラメント形成組成物30(例えば布地ケア組成物及び/又は食器洗浄用組成物として有用なフィラメントを製造するのに好適であるフィラメント形成組成物)で充填される。
2 McIntyre Group Ltd(University Park,IL)のMackam HPL−28ULS
3 UCARE(商標)ポリマーLR−400、Amerchol Corporation(Plaquemine,Louisiana)から入手可能。
2 McIntyre Group Ltd(University Park,IL)のMackam HPL−28ULS
3 UCARE(商標)ポリマーLR−400、Amerchol Corporation(Plaquemine,Louisiana)から入手可能。
4 平均分子量8,000,000、Sigma Aldrich、カタログ番号372838から入手可能
* 算出値
* 計算値
別途記載のない限り、定義の欄で記載されたものを包含する本明細書に記載された全ての試験及び次の試験方法は、約73°F±4°F(約23℃±2.2℃)及び相対湿度50%±10%に調節された部屋で、試験前2時間にわたって調整した試料に対して行なわれる。本明細書に記載されるように調整した試料は、本発明の目的上、乾燥試料(例えば「乾燥フィラメント」)であると見なされる。更に、全ての試験はこのような調節された部屋の中で行われる。
フィラメント、及び/又は繊維、及び/又は不織布ウェブ内に存在する含水量(含湿量)は、以下の含水量試験方法を使用して測定される。
装置及び材料:
600mLビーカー
電磁撹拌器(Labline Model No.1250又は同等物)
磁気撹拌棒(5cm)
温度計(1〜100℃+/−1℃)
ステンレス鋼製型板(3.8cm×3.2cm)
タイマー(0〜300秒、秒数には四捨五入が含まれる)
3.8cm×3.2cmの開口部を有する35mmのスライド台(Polaroid Corporationより入手可能)
35mmのスライド台ホルダー
以下の特性を有するCincinnati市の水道水又はそれと同様のもの:CaCO3として総硬度=155mg/L;カルシウム含有量=33.2mg/L;マグネシウム含有量=17.5mg/L;リン酸塩含有量=0.0462
1.開口面積の寸法24×36mm(すなわち3.8cm×3.2cmの試料)を備える35mmのスライド台内に試料が確実にフィットするように、テンプレートを使用して、試験すべき(「試料」)フィルム又は不織布ウェブから試料を3つ切り出す。フィルム又は不織布ウェブの横方向に沿って、フィルム又は不織布ウェブの領域を均一に離間させて試料を切り出す。
2.3つの試料のそれぞれを別個の35mmスライド台に固定する。
3.磁気撹拌棒を600mLのビーカー内に定置する。
4.500mL以上のCincinnati水道用水を入手し、温度計で水温を測定し、必要な場合は、水の温度を、それが試験温度、すなわち5℃を維持するように調節する。水の温度が5℃になった時点で、500mLの水を600mLのビーカーに充填する。
5.次いで、ビーカーを電磁攪拌器上に定置する。攪拌器のスイッチを入れて、水の中で渦が発生し、かつ渦の底部が600mLビーカーの400mLのマークにくるまで、撹拌速度を調節する。
6.試料を固定した35mmのスライド台を、35mmのスライド台をビーカー内の水の中に下げるように設計されたホルダーに取り付ける(例えば、35mmのスライド台を、600mLビーカー内に存在する水の中に配置するように設計された35mmのスライド台ホルダーのワニ口クランプ)。35mmmのスライド台の長端が、600mLビーカー内に存在する水の表面と平行になるように、35mmスライド台の1つの長端の中央で、35mmスライド台をワニ口クランプによって保持する。この設置により、フィルム又は不織布の表面は、水の流れと垂直に配置される。35mmのスライド台及びスライド台ホルダーの配置がわずかに修正された実施例が、米国特許第6,787,512号の図1〜3に示されている。
7.一回の動作で、35mmのスライド台ホルダー(これはビーカー内の水の中心上に35mmスライド台を配置する)を降下させ、35mmスライド台に固定されたフィルム若しくは不織布の露出した表面積全体に、水が接触するのに十分であるように、35mmのスライド台を水中に沈ませる。フィルム又は不織布の露出した表面積全体に水が接触したら即タイマーを開始させる。フィルム又は不織布が分断されると分解が生じる。見えるフィルム又は不織布の全てがスライド台から放出されたとき、35mmスライド台を水から引き揚げて、同時に溶解していないフィルム又は不織布の断片に関して水を観察し続ける。全てのフィルム又は不織布の断片がもはや水中に見えなくなった場合に、溶解が生じている。
8.各試料の3つの複製品が実施される。
9.試験された試料のg当たりの崩壊及び融解時間の値(これは試料の秒/g(s/g)の単位である)を入手するために、それぞれの崩壊及び融解時間は、試料の重量によって正規化される。3つの複製品の試験された試料のg当たりの平均崩壊及び溶解時間が記録される。
不織布ウェブ又はフィルム内の別個のフィラメント、すなわち1つのフィラメントの直径は、走査型電子顕微鏡(SEM)又は光学顕微鏡、及び画像解析ソフトウェアを使用することによって決定される。フィラメントが測定のために適切に拡大されるように、200〜10,000倍の倍率が選択される。SEMを使用するときに、電子ビームにおけるフィラメントの帯電及び振動を避けるために、試料は金又はパラジウム化合物でスパッタされる。SEM又は光学顕微鏡を用いて撮られた画像(モニタースクリーン上)から、フィラメントの寸法を決定するための手動の手順が使用される。マウス及びカーソルツールを使用して、無作為に選択されたフィラメントの縁部を探し、次いでフィラメントの反対の縁部までその幅を(すなわち、その点において、フィラメントに対して垂直に)測定する。目盛りのある、較正された画像解析ツールは、例えば、μmでの実際の読取値を得るための目盛りを提供する。不織布ウェブ又はフィルム内のフィラメントに関して、いくつかのフィラメントがSEM又は光学顕微鏡を使用して、不織布ウェブの試料の中から無作為に選択される。不織布ウェブ又はフィルム(若しくは製品内のウェブ)の少なくとも2つの部分が切り出され、この方法で試験される。統計学的分析のために、そのような測定を少なくとも合計100回行い、次いで全てのデータを記録する。記録されたデータは、フィラメントの直径の平均値(平均)、フィラメント直径の標準偏差、及びフィラメント直径の中位径を算出するために使用される。
不織布ウェブ又はフィルムの厚さは、不織布ウェブ試料又はフィルム試料から5つの試料へと切り出された各試料が、VIR Electronic Thickness Tester Model II(Thwing−Albert Instrument Company(Philadelphia,PA)から入手可能)のロードフット搭載面よりも大きな寸法であるように切り出すことによって測定される。典型的に、ロードフット搭載面は約20.25cm2(3.14in2)の円形の表面積を有する。試料を水平な平面とロードフット搭載面との間に押し込める。ロードフット搭載面は、15.5g/cm2までの封圧を試料に印加する。各試料のキャリパーとは、平面とロードフット搭載面との間に結果として生じる隔たりである。キャリパーは5つの試料の平均キャリパーとして算出される。結果をミリメートル(mm)で記録する。
本発明のフィラメント形成組成物の剪断粘度は、毛管レオメーターである、Goettfert USA(Rock Hill SC,USA)で製造されたGoettfert Rheograph 6000を使用して測定する。測定は、1.0mmの直径D及び30mmの長さL(すなわちL/D=30)を有するキャピラリーダイを用いて行う。レオメーターの20mmのバレルの下端にダイを取り付け、75℃のダイ試験温度に保持する。ダイ試験温度に予め熱した60gのフィラメント形成組成物の試料を、レオメーターのバレル領域に充填する。試料から全ての混入空気を取り除く。一連の選択された速度、1,000〜10,000秒−1で、試料をバレルからキャピラリーダイを通して押す。見かけの剪断粘度は、試料がバレルからキャピラリーダイを通って進む時に試料に生じる圧力低下及びキャピラリーダイを通る試料の流量から、レオメーターのソフトウェアを用いて計算することができる。log(見かけの剪断粘度)は、log(剪断速度)に対してプロットされ、このプロットはη=Kγn−1によって指数法則に適合させることができ、式中、Kは材料の粘性定数であり、nは材料の薄化係数であり、γは剪断速度である。本明細書のフィラメント形成組成物の報告される見かけの剪断粘度は、剪断速度3,000秒−11に対する補間により指数法則関係を用いて計算される。
繊維性構造体試料の坪量は、12の個々の繊維性構造体試料を選択し、それぞれ6つの個々の試料の積み重ね体を2つ製造することにより測定される。個々の試料が互いに穿孔線で接続されている場合、個々の試料を積み重ねる際に穿孔線を同じ側にそろえる必要がある。精密カッターを使用して、各積み重ね体を正確に8.9cm(3.5インチ)×8.9cm(3.5インチ)の正方形に切り出す。2つの切り取った正方形の積み重ね体を合わせて、12の正方形の厚さの坪量パッドを製造する。次に、最小感度限界が0.01gの上皿天秤で坪量パッドの重量を測定する。上皿天秤は、気流遮蔽壁を使用して気流及び他の障害から保護する必要がある。上皿天秤の読み取り値が一定になったら、重量を記録する。以下のように坪量を計算する。
材料(例えばポリマー)の重量平均分子量(Mw)は、混合ベッドカラムを使用して、ゲル透過クロマトグラフィー(GPC)によって決定される。以下の構成要素を有する高性能液体クロマトグラフ(HPLC):Millenium(登録商標)、Model 600Eポンプ、システムコントローラ及びコントローラーのソフトウェアバージョン3.2、Model 717 Plusオートサンプラー及びCHM−009246カラムヒーター(全てWaters Corporation(Milford,MA,USA)が使用される)。カラムは、600mmの長さ及び7.5mmの内径を有する、PLゲル20μm混合Aカラム(ゲル分子量は1,000g/モルから40,000,000g/モルの範囲)であり、ガードカラムはPLゲル20μm、長さ50mm、IDは7.5mmである。カラム温度は55℃であり、インジェクション体積は200μLである。検出器は、Wyatt Technology(Santa Barbara,CA,USA)製のAstra(登録商標)ソフトウェア、バージョン4.73.04検出器ソフトウェア、K5セル及び690nmレーザーを有するレーザー光散乱検出器を備える、DAWN(登録商標)Enhanced Optical System(EOS)である。奇数が振られた検出器のゲインは101に設定する。偶数が振られた検出器のゲインは20.9に設定する。Wyatt TechnologyのOptilab(登録商標)示差屈折率計を50℃に設定する。ゲインは10に設定する。移動相は、0.1% w/v LiBrを備えるHPLC等級のジメチルスルホキシドであり、移動相の流量は1mL/分、無勾配である実行時間は30分である。
フィラメント組成物測定用にフィラメントを調製するために、フィラメントの外面上に存在する任意の除去可能であるコーティング組成物及び/又は材料を除去することによって、フィラメントを調整する。例えば、フィラメントを3回、蒸留水で洗浄するなどする。次いで、フィラメントは含水量が10%未満になるまで、23℃±2.2℃(73°F±4°F)で風乾する。調整したフィラメントの化学分析を次いで完了させ、フィラメント形成材料、及びフィラメント内に存在する活性剤に関して、フィラメントの組成の構成を決定する。
Claims (15)
- 1つ以上のフィラメント形成材料と、フィラメントの形態が変化した際にフィラメントから放出可能である1つ以上の活性剤とを含むフィラメントであって、前記フィラメント内に存在する前記1つ以上のフィラメント形成材料の総濃度が乾燥フィラメントベースで65重量%未満であり、前記フィラメント内に存在する前記1つ以上の活性剤の総濃度が乾燥フィラメントベースで35重量%を超える、フィラメント。
- 前記フィラメント内に存在する前記1つ以上の活性剤の総濃度が、乾燥フィラメントベースで少なくとも40重量%である、請求項1に記載のフィラメント。
- 前記フィラメント内に存在する前記1つ以上の活性剤の総濃度が、乾燥フィラメントベースで80重量%を超える、請求項1又は2に記載のフィラメント。
- 前記1つ以上のフィラメント形成材料及び前記1つ以上の活性剤が、前記活性剤に対する前記フィラメント形成材料の重量比が3.5以下になるよう前記フィラメント内に存在する、請求項1〜3のいずれか一項に記載のフィラメント。
- 前記1つ以上のフィラメント形成材料が極性溶媒に可溶性の材料を含む、請求項1〜4のいずれか一項に記載のフィラメント。
- 前記1つ以上のフィラメント形成材料がポリマーを含み、好ましくは該ポリマーが、プルラン、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ポリビニルピロリドン、カルボキシメチルセルロース、アルギン酸ナトリウム、キサンタンガム、トラガカントガム、グアーガム、アカシアガム、アラビアガム、ポリアクリル酸、メチルメタクリレートコポリマー、カルボキシビニルポリマー、デキストリン、ペクチン、キチン、レバン、エルシナン、コラーゲン、ゼラチン、ゼイン、グルテン、大豆タンパク質、カゼイン、ポリビニールアルコール、デンプン、デンプン誘導体、ヘミセルロース、ヘミセルロース誘導体、タンパク質、キトサン、キトサン誘導体、ポリエチレングリコール、テトラメチレンエーテルグリコール、ヒドロキシメチルセルロース、及びこれらの混合物からなる群から選択され、より好ましくは該ポリマーが、ポリビニールアルコール、デンプン、又はデンプン誘導体を含む、請求項1〜5のいずれか一項に記載のフィラメント。
- 前記フィラメントが更に可塑剤を含み、好ましくは該可塑剤が、グリセリン、エチレングリコール、ポリエチレングリコール、プロピレングリコール、グリシドール、尿素、ソルビトール、キシリトール、マルチトール、糖類、エチレンビスホルムアミド、アミノ酸、及びこれらの混合物からなる群から選択される、請求項1〜6のいずれか一項に記載のフィラメント。
- 前記1つ以上の活性剤が界面活性剤を含み、好ましくは該界面活性剤が、アニオン性界面活性剤、カチオン性界面活性剤、非イオン性界面活性剤、双極性イオン界面活性剤、両性界面活性剤、及びこれらの混合物からなる群から選択される、請求項1〜7のいずれか一項に記載のフィラメント。
- 前記フィラメントが2つ以上の異なるフィラメント形成材料を含む、請求項1〜8のいずれか一項に記載のフィラメント。
- 前記フィラメントが2つ以上の異なる活性剤を含む、請求項1〜9のいずれか一項に記載のフィラメント。
- 前記フィラメントが溶解助剤を更に含む、請求項1〜10のいずれか一項に記載のフィラメント。
- 本明細書において記載される含水量試験方法に従って測定した場合に、前記フィラメントが0%〜20%の含水量を呈し、好ましくは、本明細書において記載される含水量試験方法に従って測定した場合に、前記フィラメントが0%超〜15%未満の含水量を呈する、請求項1〜11のいずれか一項に記載のフィラメント。
- 請求項1〜12のいずれか一項に記載のフィラメントを製造する方法であって、
a.1つ以上のフィラメント形成材料と、1つ以上の活性剤と、を含むフィラメント形成組成物を用意する工程と、
b.該フィラメント形成組成物を紡糸して、1つ以上のフィラメント形成材料と、フィラメントの形態が変化した際にフィラメントから放出可能である1つ以上の活性剤と、を含む、1つ以上のフィラメントにする工程であって、フィラメント内に存在するフィラメント形成材料の総濃度が乾燥フィラメントベースで65重量%未満であり、フィラメント内に存在する活性剤の総濃度が乾燥フィラメントベースで35重量%を超える、工程とを含む、方法。 - 好ましくは、前記1つ以上の活性剤が布地ケア活性剤を含む、請求項1〜12のいずれか一項に記載の1つ以上のフィラメントを含む不織布ウェブ。
- 処理が必要な布地物品を処理する方法であって、請求項14に記載の不織布ウェブで布地物品を処理する工程を含み、好ましくは該処理工程が、
a.前記布地物品を洗浄する前に前記布地物品を前処理する工程と、
b.不織布ウェブを水と接触させることによって形成された洗浄液と、前記布地物品を接触させる工程と、
c.前記布地物品と前記不織布ウェブを乾燥機内で接触させる工程と、
d.乾燥機内に不織布ウェブが存在する状態で布地物品を乾燥させる工程と、
e.これらの組み合わせ、からなる群から選択される1つ以上の工程と、を含む、方法。
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WO2012003319A2 (en) | 2012-01-05 |
WO2012003319A3 (en) | 2012-02-23 |
CA2803629A1 (en) | 2012-01-05 |
US11434586B2 (en) | 2022-09-06 |
ZA201209584B (en) | 2014-05-28 |
BR112013000101A2 (pt) | 2016-05-17 |
CN103025929B (zh) | 2015-11-25 |
CN103025929A (zh) | 2013-04-03 |
US20120237576A1 (en) | 2012-09-20 |
CN105332075A (zh) | 2016-02-17 |
EP2588653B1 (en) | 2018-06-20 |
US11970789B2 (en) | 2024-04-30 |
CN105332075B (zh) | 2017-11-24 |
JP5859526B2 (ja) | 2016-02-10 |
US20230075745A1 (en) | 2023-03-09 |
EP2588653A2 (en) | 2013-05-08 |
RU2012158239A (ru) | 2014-08-10 |
CA2803629C (en) | 2015-04-28 |
RU2541949C2 (ru) | 2015-02-20 |
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