JP2007512211A - 超疎液性表面、その作製法及び用途 - Google Patents
超疎液性表面、その作製法及び用途 Download PDFInfo
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Abstract
【選択図】なし
Description
本出願は2003年4月28日出願の“超疎液性表面、その組立法及び使用法”と題する米国暫定出願No.60/466,229による利益及び優先権を主張する。この先行出願は全体をここに援用する。
本発明は、主としてナノ技術の分野に関する。更に詳しくは本発明は、外生的な(exogenous)疎水性、疎液性又は両疎媒性の材料を含有し、超疎水性、超疎油性及び/又は超両疎媒性の特性を示すナノ繊維及びナノ繊維構造に関する。
材料のはっ水性又は疎水性は、美的用途から工業的用途に至るまで無数の用途に極めて重要である。例えば氷/雪の堆積又は浸水を受けやすい表面には、疎水性の向上が望ましいことが多い。また他の例では、疎油性(はつ油性)及び/又は両疎媒性(はっ水兼はつ油性)も用途となる(例えば油性流体の輸送又は貯蔵等)。このような疎液性(例えば疎水性、疎油性、両疎媒性等)を得ようとする多くの研究は、各種被覆又は表面組織の変性による用途に焦点を絞っている。例えば材料の疎液性向上には、従来、炭化水素及び弗素を含有する化合物やワックスが使用されてきた。最近、他の方法は或る種の、又は或る程度の疎液性を得るため、表面の粗面化を利用している。
種々の局面において、本発明は少なくとも第一表面と、1種以上の外生的疎液性材料を含む複数のナノ繊維とを含有する超疎液性基体を含む。幾つかの実施態様では、ナノ繊維は固体ナノ繊維及び/又は結晶性ナノ繊維を含む。各種実施態様のナノ繊維の表面密度(例えば表面上又は基体上)は、10μ2当り約1以下のナノ繊維〜1μ2当り約200のナノ繊維、1μ2当り約1以下のナノ繊維〜1μ2当り約150以上のナノ繊維、1μ2当り約10以下のナノ繊維〜1μ2当り約100以上のナノ繊維、1μ2当り約25以下のナノ繊維〜1μ2当り約75以上のナノ繊維が可能である。種々の実施態様では基体は、第一表面の被覆率が約0.01〜約50%、約0.25〜約40%、約0.5〜約30%、約1〜約20%、約5〜約15%、約0.1〜約5%、又は約1%であるナノ繊維を任意に含有できる。ナノ繊維の長さは、約1〜約200μ、約5〜約150μ、約10〜約125μ、又は約50〜約100μである。幾つかの実施態様ではナノ繊維の直径は、約5nm〜約1μ、約20nm〜約250nm、約40nm〜約200nm、約50nm〜約150nm、又は約75nm〜約100nmである。なお他の実施態様ではナノ繊維の高さ対直径アスペクト比は、約2:1;約2000:1;約2:1〜約40:1又はそれ以上;約5:1〜約30:1又はそれ以上;又は約10:1〜約20:1又はそれ以上である。
図1A、1Bは、液滴と基体表面との相互作用を示す概略図である。
本発明は、ナノ繊維を超疎液性(例えば超疎水性)にするため、外生的疎液性材料で処理したか、又は該材料を含有するナノ繊維基体を有する。特に、特定の操作理論又は機構に束縛されるものではないが、ここで説明するナノ繊維表面は、疎液性増大処理を行うと、独特の接触特性が得られ、実際に超疎液性(例えば超疎水性)になるものと考えられる。例えばナノ繊維表面にメチル基、弗素基等を添加すると、極超疎液性表面が得られる。したがって、このような超疎液性表面に塗布した水は、球形となり、水流と同様に表面を転がり落ちる。テフロン(登録商標)のような他の非濡れ性疎水性表面でもこのような極限特性は示さない。したがって、本発明は、はっ水及び/又ははつ油(例えばグリース)被覆又はバイオ不活性層を所望する用途や、分離用仮想表面、流動用、例えばパイプ、マニホールド、チャンネル、細管、ミクロ流動導管等の流体導管の低摩擦被覆や、水上及び海上用、例えば船舶/潜水艦、魚雷、及び更には玩具、噴水(fountains)のような美的構造物にも任意に使用される。
本発明を詳細に説明する前に、特定の構成に限定されず、勿論、変化できる(例えば或る範囲の長さ、密度等に任意に存在するナノ繊維と被覆との各種組合わせ)ことを理解すべきである。またここで使用した用語は、単に特定の実施態様を説明するためのもので、限定を意図するのではないことを理解すべきである。明細書及び付属の特許請求の範囲に記載した単数形の冠詞は、特に明確に規定しない限り、複数形を含む。したがって、“1つのナノ繊維”は、複数のこの種のナノ繊維を含む等である。
液体(例えば水ベース、油性ベース等)の滴を表面に置くと、液滴は、液体及び基体の表面張力、表面の平滑性、粗さ等の要因により、ある程度まで表面に広がる。例えば基体の疎液性は、基体の表面エネルギーを低下させる各種の被覆により向上できる。疎液性の数量化は、表面上の液滴の接触表面角度(又は接触角)の程度として表現できる。
(1) cosθ=(γSV−γSL)/γLV
で表わされる。ここでγSV 、γSL及びγLVは、それぞれ固体/蒸気界面、固体/液体界面及び液体/蒸気界面の表面エネルギー(即ち、単位面積当りの間隙の自由エネルギー)であり、θは、液滴と基体表面との接触角である。例えば基体210上の液滴200を示す図2、及び基体310上の液滴300を示す図3参照。したがって、表面エネルギーが低下すると、疎液性は向上する(また、その逆)。平滑面に対しては、CF3末端の基体で最大約120°の接触角が得られた。
(2) cosθ’=r(γSV−γSL)/γLV=rcosθ
が使用される。式中、rは表面の“粗さ係数”で、表面の実面積と表面の予想幾何面積との比率である。Wenzelの式は、
(3) cosθW=rcosθγ
ここでθWはWenzel角度、θγはYoung角度である。Wenzel解析の粗さは本来、非常に小さく、基体と液体間に気泡を形成するほど大きくはない。
(4) cosθ’=fcosθ+(1−f)cos180°
= cosθ+f−1
により測定される。ここでθ’は、液体と空気/基体表面との接触角を表わす。この式で、空気/液体接触角は180°と推定する。また式中、fは固体表面積分数Σa/Σ(a+b)(“a”は基体表面と液体との接触面積であり、面積“b”は液体と、液体及び基体間に閉じ込められた空気との接触面積である)に等しい。図4参照。図4から判るように、液滴400は特定点(即ち、高くした点又は粗面化点)でだけ粗面基体410と接触する。図4、6等での表示は、解析を容易にするため、誇張して示した。こうして例えば“a”で表わされる領域は、均一なもの、頂部が平坦なもの等として表わした。Cassieの式は
(5) cosθCB=fSLcosθγ−fLA
のように変形できる。ここでfSLは固体/液体界面の分数被覆度(fractional coverage)、fLAは液体/空気界面の分数被覆度である。
本発明のナノ繊維は、他の異なる一方法で任意に作製され、ここに示した例及び検討は、限定するものとみなすべきではない。したがって、ここに具体的に説明しない手段で作製したが、外生的要素(例えば通常は疎液性部分等)を含むと共に、ここで述べた超疎液性パラメーターの範囲内にある手段により作製したナノ繊維は、なお本発明のナノ繊維である。
本発明の一局面は、例えば本発明の基体表面上の、ナノ繊維の密度である。前述のように、表面の超疎液性には、通常、表面粗さという概念が含まれる。例えば前記式2〜5参照。したがって、粗さの程度を変化させる、ナノ繊維の密度は、本発明の超疎液性と関係があると考えられる。更に重要なことは、この密度を制御する能力が表面全体の超疎液性水準を制御する独特の能力を与えることである。要するに、外生的材料の疎液性は、ナノ繊維密度との組合わせで、本発明の超疎液性に影響を与えると考えられることである。
本発明は、ナノ繊維の作製手段により限定されないことは理解されよう。好ましい実施態様ではナノ繊維は、無機材料、通常、シリコン及び/又は酸化珪素で構成され、通常、固体結晶性構造である。無機ナノ繊維の形成は、いずれも本発明に受け入れやすい当業者に周知の多数の異なる方法で可能である。例えばUSP 5,230,957;同5,537,000;同6,128,214;同6,225,198;同6,306,736;同6,314,019;同6,322,901;同6,501,091;及び国際特許出願公開No.WO 02/17632及びWO 01/03208参照。これら各特許の十分な開示は、あらゆる目的のため、全体をここに援用した。
通常の実施態様では、本発明の超疎液性ナノ繊維は、外生的疎液性材料(例えば疎水性材料、疎油性材料、両疎媒性材料等)を含有する。通常、このような材料は、本発明ナノ繊維の“被覆”形態を取る。しかし、他の実施態様では、ナノ繊維は、ナノ繊維全体を覆う薬品の層又は被覆を有するという慣用的な意味では被覆されていない。例えば幾つかの実施態様は、ナノ繊維の表面を任意に変化させて、超疎液性にするが、慣用的な意味ではナノ繊維の表面を被覆又は包囲しない成分(例えば薬品、レーザー、周囲条件への暴露等)で本発明のナノ繊維を処理する工程を含む。このような幾つかの実施態様では、ナノ繊維の変化した表面は、被覆と言える。
本発明の超疎液性表面は、非常に多くの異なる用途に任意に使用される。基本的には超疎液性表面を所望するかどうかで本発明は任意に利用できる。したがって、ここで請求し、説明した用途/方法は、例示であり、限定されないことは理解されよう。こうして、これらナノ繊維及び/又はその利用を含む他の説明しなかった用途/方法も本発明の特徴である。ナノ繊維表面の、例えば医療用への他の多数の使用例については、例えば以下の文献に見られる。いずれも“Nanofiber Surfaces for use in Enhanced Surface Area Applications”と題するUSSN 60/468,390(2003年5月6日出願)、USSN 60/468,606(2003年5月5日出願)、USSN 10/792,402(2004年3月2日出願);“Medical Device Applications of Nonostructured Surfaces”と題するUSSN 60/549,711(2004年3月2日出願);“Porous Substrates,Articles,Systems and Compositions comprising Nanofibers and Methods of Their use and Production”と題するUSSN 60/541,463(2004年2月2日出願);及び“Superhydrophobic Surfaces,Methods of Their Construction and Uses Thereof”と題するUSSN 60/466,229(2003年4月28日出願)。これらの文献はあらゆる目的のため、全体をここに援用した。
本発明の他の用途は、食材の付着を防止すると共に、調理容器をきれいにしやすくするため、調理機具、例えばポット、パン、調理容器等に使用することが挙げられる。当業者ならば、現在の調理器具のテフロン(登録商標)被覆によるような同様の用途について熟知している。
本発明は織物の製造(例えば耐汚染布等の製造、又は細胞及び/又はバクテリアの成長を防止する各種織布又はその他の織物フォーマット医療機器)に任意に使用できる。例えば織布又は不織布の雨用具(例えばレインコート等)も任意に本発明の超疎水性ナノ繊維を含有できる。
例1:超疎液性ナノ繊維の作製
酸化物表面を有する4インチのシリコンウエーハの表面にシリコンナノ繊維(ここではナノワイヤー)を作った。ナノワイヤーは、金コロイド開始CVD法で成長させた。ワイヤーの長さは、数μ〜約100μに変化させた。ワイヤーの幅は、約500nmであった。この表面に水滴を迅速にうまく塗布すし、ナノワイヤー間の気泡が充満するまで広げた。
例1の第二の局面で作った5cm2ウエーハ基体(即ち、弗素化モノマーで機能化したウエーハで、ナノワイヤーは、この弗素化モノマーで“被覆”されている)を1.9度の角度で置いた。30μlの水滴をウエーハの高い方の端部に置いた。水滴は3秒以内でウエーハの反対端部に転げ落ちた。したがって、滑り角度は2度未満である。鉱油の油滴もウエーハの高い方の端部に置くと、同様に反対端部に滑り落ちた。したがって、この処理ウエーハが超両疎媒性であることを示している。
Scotch(登録商標)透明テープ(3M)の1インチ片を、例1のTri−Sil(登録商標)処理ナノワイヤーウエーハに張り付けた。このテープを手でウエーハからゆっくり引き剥がした。可視検査すると、ウエーハの茶色の被覆ナノ繊維は、テープ片の表面に移行していた。テープ片に塗布した水滴は、例1の水滴と同様、ビーズ化して、テープを転がり落ちた。したがって、処理ナノワイヤーは、ナノワイヤーが成長した表面から第二の表面に移行することが判る。重要なことは、処理ナノワイヤーの超疎液性が第二表面にも移行させることである。
110 広がった液滴
120 基体
200 液滴
210 基体
300 液滴
310 基体
400 液滴
410 粗面基体
600 液滴
610 ナノ繊維
620 基体
630 液滴
640 ナノ繊維
650 基体
700 基体
710 ナノ繊維
720 外生的疎液性材料の被覆
800 接触点
900 接触点
1100 接触点
θ 接触角
b 粗面
Claims (63)
- 少なくとも第一表面と、1種以上の外生的疎液性材料を含む複数のナノ繊維とを含有する超疎液性基体。
- 前記ナノ繊維が非炭素材料を含む請求項1に記載の基体。
- 前記ナノ繊維がシリコンを含む請求項1に記載の基体。
- 前記ナノ繊維が固体ナノ繊維を含む請求項1に記載の基体。
- 前記ナノ繊維が結晶性ナノ繊維を含む請求項1に記載の基体。
- 前記ナノ繊維の表面密度が10μ2当り約1のナノ繊維〜1μ2当り約200以上のナノ繊維である請求項1に記載の基体。
- 前記ナノ繊維の表面密度が1μ2当り約10のナノ繊維〜1μ2当り約100以上のナノ繊維である請求項1に記載の基体。
- 前記ナノ繊維の表面密度が1μ2当り約25のナノ繊維〜1μ2当り約75以上のナノ繊維である請求項1に記載の基体。
- 前記ナノ繊維の第一表面の被覆率が約0.01〜約50%である請求項1に記載の基体。
- 前記ナノ繊維の第一表面の被覆率が約0.5〜約30%である請求項1に記載の基体。
- 前記ナノ繊維の第一表面の被覆率が約5〜約15%である請求項1に記載の基体。
- 前記ナノ繊維の第一表面の被覆率が約1%である請求項1に記載の基体。
- 前記ナノ繊維の長さが約1〜約200μである請求項1に記載の基体。
- 前記ナノ繊維の長さが約10〜約125μである請求項1に記載の基体。
- 前記ナノ繊維の長さが約1〜約50又は約100μである請求項1に記載の基体。
- 前記ナノ繊維の直径が約5nm〜約1μである請求項1に記載の基体。
- 前記ナノ繊維の直径が約40〜約200nmである請求項1に記載の基体。
- 前記ナノ繊維の直径が約75〜約100nmである請求項1に記載の基体。
- 前記ナノ繊維の高さ対直径アスペクト比が約2:1〜約40:1又はそれ以上である請求項1に記載の基体。
- 前記ナノ繊維の高さ対直径アスペクト比が約5:1〜約30:1又はそれ以上である請求項1に記載の基体。
- 前記ナノ繊維の高さ対直径アスペクト比が約10:1〜約20:1又はそれ以上である請求項1に記載の基体。
- 前記表面がシリコン、ガラス、透明基体、半透明基体、やや不透明基体、石英、プラスチック、金属、重合体、TiO、ZnO、ZnS、ZnSe、ZnTe、CdS、CdSe、CdTe、HgS、HgSe、HgTe、MgS、MgSe、MgTe、CaS、CaSe、CaTe、SrS、SrSe、SrTe、BaS、BaSe、BaTe、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、PbS、PbSe、PbTe、AlS、AlP、AlSb、SiO1、SiO2、炭化珪素、窒化珪素、ポリアクリロニトリル(PAN)、ポリエーテルケトン、ポリイミド、芳香族重合体又は脂肪族重合体を含有する請求項1に記載の基体。
- 前記外生的材料が1種以上の疎水性材料、疎油性材料又は両疎媒性材料を含む請求項1に記載の基体。
- 前記外生的材料がテフロン(登録商標)、Tri−sil,トリデカフルオロ1,1,2,2,テトラヒドロオクチル−1−トリクロロシラン、弗化物含有化合物、シラン含有化合物、PTFE、ヘキサメチルジシラザン、脂肪族炭化水素含有分子、芳香族炭化水素含有分子、ハロゲン含有分子及びパラリエンよりなる群から選ばれた1種以上の材料を含む請求項1に記載の基体。
- 前記基体上の液滴が少なくとも約160〜約179.5°以上の接触角を示す請求項1に記載の基体。
- 前記基体上の液滴が少なくとも約170〜約179.5°以上の接触角を示す請求項1に記載の基体。
- 前記基体上の液滴が少なくとも約175〜約179.5°以上の接触角を示す請求項1に記載の基体。
- 前記基体上の液滴が少なくとも約178〜約179.5°以上の接触角を示す請求項1に記載の基体。
- 前記ナノ繊維が少なくとも第一表面上で成長したナノ繊維を含む請求項1に記載の基体。
- 前記ナノ繊維が第二表面上で成長し、前記第一表面に移行したナノ繊維を含む請求項1に記載の基体。
- 少なくとも第一表面と複数のナノ繊維とを含み、基体上の液滴が少なくとも160°又はそれ以上の接触角を示す超疎液性基体であって、該ナノ繊維は1種以上の外生的疎液性材料を含むと共に、約0.01〜約50%の基体表面被覆率を有し、かつ約2:1〜約40:1又は約100:1〜約2000:1の長さ対直径アスペクト比を有する該超疎液性基体。
- 請求項1又は25に記載した1種以上の超疎液性基体を有するシステム又は装置。
- 1つ以上の液滴を用意する工程、第一表面と外生的疎液性材料を含む複数のナノ繊維とを含有する1種以上の基体を用意する工程、及び該液滴を該1種以上の基体と接触させる工程を含む、1つ以上の液滴と基体との接触角を少なくとも160°にする方法。
- 前記液滴が油性及び/又は非油性である請求項33に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を有する、1つ以上の表面領域を持った基体を用意し、これにより超疎液性基体を形成する工程、及び該基体を第一媒体及び1種以上の第二媒体と物理的に接触させる工程を含む、第一媒体と1種以上の第二媒体との交換方法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項35に記載の方法。
- 前記第一媒体が複数のナノ繊維間に単独で配置され、前記1種以上の第二媒体が複数のナノ繊維の上に単独で配置される請求項35に記載の方法。
- 前記第一及び第二媒体が気体及び液体よりなる群から選ばれる請求項35に記載の方法。
- 交換が熱交換を含む請求項35に記載の方法。
- 交換が、第一及び/又は第二媒体内に成分が存在する、第一媒体と1種以上の第二媒体間の1種以上の成分の交換を含む請求項35に記載の方法。
- 1種以上の材料で処理した複数のナノ繊維を有する1つ以上の表面領域を持った基体を含むチャンネルを用意し、これにより超疎液性基体を作製する工程、及び該チャンネルに材料を流す工程を含む、チャンネル内の流れ抵抗を低下させる方法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項41に記載の方法。
- 前記材料が気体、液体又は固体を含む請求項41に記載の方法。
- 前記チャンネルがミクロ流動チャンネルである請求項41に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を含む1つ以上の表面領域を持った壁を有する容器を用意し、これにより超疎液性壁を作製する工程、及び該壁と物理的に接触した被輸送材料を用意する工程を含む、容器中での該材料の残存閉込みを少なくするため、材料を容器中で貯蔵又は輸送する方法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項45に記載の方法。
- 前記材料が気体、液体又は固体を含む請求項45に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を含む1つ以上の表面領域を持った基体を用意し、これにより超疎液性基体を作製する工程、及び該基体をH2O含有の液体又は気体の存在下に0℃以下に冷却する工程を含む、基体への氷の堆積を防止又は低減する方法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項48に記載の方法。
- 前記基体が航空機の機体、配線又は部品を含む請求項48に記載の方法。
- 前記基体が加熱される請求項48に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を含む1つ以上の表面領域を持った少なくとも1つの壁を有する容器を用意し、これにより超疎液性容器壁を作製する工程、及び該容器の内容物を1種以上用意する工程を含む、容器からの漏れを防止又は低減する方法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項52に記載の方法。
- 前記容器が地下貯蔵槽を含む請求項52に記載の方法。
- 前記容器の内容物が毒物、廃棄物又は危険物である請求項52に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を含む1つ以上の表面領域を持った少なくとも1つの基体を有する部品を用意し、これにより超疎液性基体を作製する工程、及び該基体と物理的に接触した水を用意する工程を含む、領域への水の侵入を防止又は低減する方法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項56に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を含む1つ以上の表面領域を持った少なくとも1つの基体を用意し、これにより超疎液性基体を作製する工程、該表面領域内のナノ繊維の1つ以上の所定領域をエッチング又は除去することにより超疎液性基体のパターン領域とナノ繊維を含まない裸表面のパターン領域とを作製する工程、該裸領域のパターン領域内に優先的に定住する1種以上のインク又は染料を供給する工程、及び該基体を1つ以上の第二基体と接触させることにより裸表面のパターン領域に対応するパターン状で第二基体にインク又は染料を移行させる工程を含むプラテン印刷法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項58に記載の方法。
- 1種以上の外生的材料で処理した複数のナノ繊維を含む1つ以上の表面領域を持った少なくとも1つの基体を用意し、これにより超疎液性基体を作製する工程、及び該表面領域内のナノ繊維の1つ以上の所定領域をエッチング又は除去することにより超疎液性基体のパターン領域とナノ繊維を含まない裸表面のパターン領域とを作製する工程を含む、表面のパターン化法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項60に記載の方法。
- 複数のナノ繊維を含む1つ以上の表面領域を持った少なくとも1つの基体を用意する工程、及び該少なくとも1つの基体上の1つ以上の領域を1種以上の超疎液性材料で、選択されたパターン状に処理することによりパターン化超疎液性基体を作製する工程を含む、表面のパターン化法。
- 前記ナノ繊維が固体結晶性ナノ繊維を含む請求項62に記載の方法。
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TWI427709B (zh) | 2003-05-05 | 2014-02-21 | Nanosys Inc | 用於增加表面面積之應用的奈米纖維表面 |
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- 2004-04-27 AU AU2004256392A patent/AU2004256392B2/en not_active Ceased
- 2004-04-27 US US10/833,944 patent/US7985475B2/en active Active
- 2004-04-27 WO PCT/US2004/013131 patent/WO2005005679A2/en active Application Filing
- 2004-04-27 EP EP20040775911 patent/EP1618223A2/en not_active Withdrawn
- 2004-04-27 CA CA 2522866 patent/CA2522866A1/en not_active Abandoned
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Cited By (7)
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JP2008526188A (ja) * | 2004-12-31 | 2008-07-24 | ホルム,ペル・ゾンネ | 動物細胞における多剤耐性を逆転させる方法 |
US11369650B2 (en) | 2004-12-31 | 2022-06-28 | Per Sonne Holm | Methods for reversing multiple resistance in animal cells |
JP4855481B2 (ja) * | 2005-12-23 | 2012-01-18 | ボストン サイエンティフィック リミテッド | 紡糸ナノファイバー、医療用具および方法 |
US8455088B2 (en) | 2005-12-23 | 2013-06-04 | Boston Scientific Scimed, Inc. | Spun nanofiber, medical devices, and methods |
KR20190027144A (ko) * | 2017-09-06 | 2019-03-14 | 부산대학교 산학협력단 | 저응착을 위한 표면 패턴 구조를 갖는 초발수 필름 및 이의 제조 방법 |
KR102075763B1 (ko) | 2017-09-06 | 2020-02-10 | 부산대학교 산학협력단 | 저응착을 위한 표면 패턴 구조를 갖는 초발수 필름 및 이의 제조 방법 |
WO2019159792A1 (ja) * | 2018-02-16 | 2019-08-22 | 東レ株式会社 | 樹脂構造体および樹脂構造体の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1618223A2 (en) | 2006-01-25 |
US7985475B2 (en) | 2011-07-26 |
JP4871726B2 (ja) | 2012-02-08 |
WO2005005679A3 (en) | 2005-12-15 |
WO2005005679A2 (en) | 2005-01-20 |
US20110240595A1 (en) | 2011-10-06 |
AU2004256392B2 (en) | 2009-10-01 |
CA2522866A1 (en) | 2005-01-20 |
AU2004256392A1 (en) | 2005-01-20 |
US20050181195A1 (en) | 2005-08-18 |
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