CN101854820B - 具有排流层的可透气衣服 - Google Patents
具有排流层的可透气衣服 Download PDFInfo
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- CN101854820B CN101854820B CN2008801160053A CN200880116005A CN101854820B CN 101854820 B CN101854820 B CN 101854820B CN 2008801160053 A CN2008801160053 A CN 2008801160053A CN 200880116005 A CN200880116005 A CN 200880116005A CN 101854820 B CN101854820 B CN 101854820B
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Abstract
本发明公开了包括位于外织物层和内织物层之间的可透气的复合织物的衣服。该可透气的复合织物包括两个纳米纤维网层和设置在它们之间的多孔的排流层。
Description
发明领域
本发明涉及包含可透气的复合织物和任选的包封该复合织物的内织物层和外织物层的衣服，所述复合织物由两个纳米纤维网层和它们之间的排流层构成。
发明背景
长期以来，人们希望使衣服能够不易受到流体例如雨水、血液和油的透湿，尤其是在高压点或高压区域诸如肘部和裤的座区。
众所周知，向衣服中加入可透气并且防水的膜可在赋予衣服透气性的同时使衣服防水，从而让使用者感觉更加舒适。例如膨胀的聚四氟乙烯(ePTFE)膜已被用于该应用中。
随着时间的推移，以身体油脂和流出物形式的污垢可堵塞薄膜中的孔，从而严重影响膜的性能。人们曾尝试通过向所述膜涂覆允许水蒸汽通过的聚合物以便对该膜进行保护，但这会导致衣服的透气性下降。因此，需要在使用寿命和舒适性之间进行权衡。
期望提供具有改善的透湿抗性(尤其是在高压区域)而不会不利地影响衣服的透气性的衣服。
发明概述
本发明涉及一种衣服，该衣服包括可透气的复合织物、外织物层和内织物层，所述可透气的复合织物包括两个纳米纤维网层和设置在它们之间的多孔的排流层。
发明详述
术语“纳米纤维层”、“纳米纤维网层”、“纳米纤维网”和“纳米网层”在本文中可互换使用，其是指包含纳米纤维的非织造材料。
如本文所用，术语“纳米纤维”是指具有小于约1000nm，甚至小于约800nm，甚至介于约50nm和500nm之间，并且甚至介于约100和400nm之间的数均直径的纤维。就非圆形横截面的纳米纤维而言，如本文所用，术语“直径”是指最大的横截面尺寸。
术语“非织造材料”是指包括多根无规分布的纤维的纤维网。纤维通常可以彼此结合，或者可以不结合。纤维可以是短纤维或连续纤维。纤维可包含一种材料或多种材料，也可以是不同纤维的组合，或者是分别包含不同材料的类似纤维的组合。
所谓“衣服”是指由使用者穿着以覆盖或保护使用者身体的某些部位免受气候或体外环境中的其他因素影响的任何物品。例如外套、夹克、裤子、帽子、手套、鞋子、袜子、和衬衫均被认为是符合该定义的衣服。
当术语“外”被用于描述层的位置时，其是指衣服的背向穿着者的表面。术语“内”是指面向使用者的衣服的一侧。
术语“压延”是指使纤维网穿过两个辊之间的辊隙的工艺。辊可以彼此接触，或者可以在辊表面之间有固定的或可变的间隙。“无图案的”辊是指在能够制造它们的过程中具有平滑表面的辊。当纤维网通过辊隙时，没有点或图案使得可在纤维网上特意生成图案，这不同于点粘合辊。
术语“稀松布”、“基底”和“支撑层”可互换使用，其是指任何平面结构；纳米网可与所述结构结合、粘附或层压。有利的是，可用于本发明的稀松布层为纺粘非织造层，但也可由非织造纤维的梳理纤维网等制成。
可用于本发明的衣服的复合织物的纳米纤维网层可通过静电纺纱诸如传统的静电纺纱或电吹法来生产，并且在某些情况下可通过熔喷法来生产。传统的静电纺纱是在全文并入本文中的美国专利4,127,706中所述的技术，其中向聚合物溶液施加高电压以生成纳米纤维和非织造垫。然而，静电纺纱法中的总生产能力太低，因此无法商业化生产基重较大的纳米网。
电吹法在PCT专利公布WO 03/080905中有所公开，其全文以引用方式并入本文。将包含聚合物和溶剂的聚合物溶液流从储罐送至喷丝头内的一系列纺丝喷嘴中，向喷丝头施加高电压，聚合物溶液经喷丝头排出。同时，任选地加热的压缩空气由空气喷嘴排出，该空气喷嘴设置在纺丝喷嘴的侧面或周边。通常向下引导空气以形成吹气流，吹气流包裹住新排出的聚合物溶液并使其向前，并且有助于形成纤维网，纤维网被收集在真空室上方的接地多孔收集带上。电吹法使得可在相对短的时间周期内形成商用尺寸和数量的纳米纤维网，其基重超过约1gsm，甚至高达约40gsm或更高。
对于可用来制备本发明的纳米网的聚合物材料并没有特别限制，所述聚合物材料包括加聚物和缩聚物材料诸如聚缩醛、聚酰胺、聚酯、聚烯烃、纤维素醚和纤维素酯、聚亚烷基硫、聚亚芳基氧、聚砜、改性聚砜聚合物、以及它们的混合物。这些种类中优选的材料包括交联和非交联形式的、不同水解程度(87％至99.5％)的聚(氯乙烯)、聚甲基丙烯酸甲酯(和其他丙烯酸类树脂)、聚苯乙烯、和它们的共聚物(包括ABA型封端共聚物)、聚(偏二氟乙烯)、聚(偏二氯乙烯)、聚乙烯醇。优选的加聚物往往是玻璃状的(Tg大于室温)。聚氯乙烯和聚甲基丙烯酸甲酯、聚苯乙烯聚合物的组合物或合金或低结晶度的聚偏氟乙烯和聚乙烯醇材料便是如此。一类优选的聚酰胺缩聚物为尼龙材料，例如尼龙-6、尼龙-6，6、尼龙6，6-6，10等。当通过熔喷法形成本发明的聚合物纳米纤维网时，可使用能够熔喷形成纳米纤维的任何热塑性聚合物，包括聚烯烃，例如聚乙烯、聚丙烯和聚丁烯；聚酯，例如聚对苯二甲酸乙二醇酯；以及聚酰胺，例如上述尼龙聚合物。纳米网可由相同的聚合物形成，或者纳米网可各自由不同的聚合物形成。
可能有利的是，向上述多种聚合物中加入本领域已知的增塑剂以降低纤维聚合物的Tg。在本文中Tg被定义为聚合物经历从玻璃态向橡胶态转变时的温度。适合的增塑剂取决于将被静电纺纱或电吹的聚合物，并且取决于纳米纤维网具体的最终应用。例如，尼龙聚合物可用水或甚至用静电纺纱或电吹工艺中的残余溶剂来增塑。可用于降低聚合物Tg的本领域已知的其他增塑剂包括但不限于脂族二元醇类、芳族磺胺类、邻苯二甲酸酯类。邻苯二甲酸酯类包括但不限于选自下列的那些：邻苯二甲酸二丁酯、邻苯二甲酸二己酯、邻苯二甲酸二环己酯、邻苯二甲酸二辛酯、邻苯二甲酸二异癸酯、邻苯二甲酸双十一酯、邻苯二甲酸双十二酯、以及邻苯二甲酸二苯酯等。“Handbook of Plasticizers”(增塑剂手册)(GeorgeWypych编辑，2004Chemtec Publishing)公开了可用于本发明的其他聚合物/增塑剂组合，该文献以引用方式并入本文。
本发明的初生纳米纤维网可被压延以赋予本发明织物所需的物理特性，如提交于2006年9月20日的共同未决的美国专利申请11/523,827中所公开，该专利申请全文以引用方式并入本文。可将初生纳米网喂送到两个无图案辊之间的辊隙中，其中一个辊是无图案的软辊，一个辊是无图案的硬辊，并且将硬辊的温度保持在Tg和Tom之间的温度，其中Tom在本文中被定义为聚合物开始熔融的温度，使得纳米网的纳米纤维在穿过压延辊隙时处于塑性状态。辊的组成和硬度可以变化以生成织物的所需最终使用特性。一个辊可以是硬金属例如不锈钢，另一个辊可以是软金属或聚合物涂覆的辊或硬度小于Rockwell B 70的复合材料辊。纤维网在两个辊之间的辊隙中的停留时间由纤维网的线速度控制，所述线速度优选介于约1m/min和约50m/min之间，并且两辊之间的占有面积为纤维网与双辊同时接触时的纵向距离。该占有面积受施加在两辊之间的辊隙处的压力所控制，并通常以辊的每线性横向尺寸上的力来测定，所述占有面积优选介于约1mm和约30mm之间。
此外，纳米纤维网还可被拉伸，任选地被同时加热至纳米纤维聚合物的Tg和最低Tom之间的温度。拉伸可以在将纤维网喂入压延辊中之前和/或之后进行，可以在纵向或横向上进行，或在两个方向上同时进行。
纳米纤维网还可包括抗静电剂、抗微生物剂、加工添加剂、着色剂等。
根据本发明的可透气的复合织物包括设置在所述两个纳米纤维层之间的排流层。排流层通过如下方式防止经受力或压力的流体诸如受驱动的雨水、被肘部、座区等处的压缩挤进的流体发生流体透湿：减小流体穿透外纳米网的压力，使得内纳米网经受显著减小的流体压力。排流层为柔性结构，所述柔性结构具有足以允许流体快速穿过排流层并远离压缩区域的厚度和平均孔径，所述流体已透过了内纳米纤维网层或外纳米纤维网层并且接触到了排流层。排流层的平均孔径可在排流层的任一侧面上均大于内纳米纤维网层和外纳米纤维网层的平均孔径。排流层的厚度可与纳米纤维网层的较厚者一样厚，并且有利地厚于纳米纤维网层的较厚者。当排流层为疏水性时，较大的孔径和孔隙率是优选的以有利于流体的排泄。排流层的材料可为非吸收性的和多孔的，以便在流体透入到排流层上的情况下，流体不太可能完全润湿排流层和/或透入到另一个纳米纤维网层上。所谓“多孔的”是指该层在20mm水标下具有至少0.05立方米/分钟/平方米(m3/min/m2)的透气率。可使用在20mm水标下具有200m3/min/m2的透气率或更大透气率的层。
作为另外一种选择，排流层的材料可为吸收性的并且具有高芯吸速率，以便在流体透入到排流层上的情况下，流体将被快速传送而远离透入点。
排流层可选自纺粘非织造材料、梳理非织造材料、针刺非织造材料、气流成网非织造材料、湿法成网非织造材料、射流喷网非织造材料、纺粘-熔喷-纺粘非织造材料、织造织物、编织织物、熔喷非织造材料、三维织网、纳米纤维层、它们的组合等。可将排流层任选地质构化或绉纹化以在引流层中产生沟道，所述沟道引导并有利于流体穿过排流层并远离压缩区域。如果排流层包括纳米纤维层，则可有利地提供对纳米纤维层的亲水性处理以增大排流层的芯吸速率。
在用于形成纳米纤维网的方法中，排流层可用作收集基底，通过将排流层布置在纳米纤维网收集器上来收集和组合在基底上所纺成的纳米纤维网。可将所得组合的纤维网/排流层用于本发明的衣服的复合织物。
由所述两个纳米纤维网层和它们之间的排流层形成的复合织物为可透气的，并且可具有介于约0.5CFM/ft2(0.15m3/min/m2)和约25CFM/ft2(7.6m3/min/m2)之间的透气率以及至少约500g/m2/24hr的湿汽透过率。
排流层和纳米网可任选地彼此结合。所有三个层可同时通过点结合或超声波结合而彼此结合，或者所述三个层中的仅两个层可结合。例如，排流层可结合到相邻的纳米纤维网层上。作为另外一种选择，纳米纤维网层可以如下方式彼此结合：结合区域的图案限定纳米网之间的空隙或空间，其中纳米网未结合。排流层可设置在该空隙中，而不连结到纳米网上。合适的结合技术的实例包括粘合剂结合、热结合诸如点结合、和超声波结合，然而也可利用本领域的技术人员已知的任何用于结合的方法。
为了改善复合织物和包括复合织物的衣服的抗流体透湿性，可用本领域已知的含氟化合物来处理纳米纤维网层中的至少一个，优选地处理最外面的纳米纤维网层，以改善所述层的流体排斥性并且使纳米纤维网层成为疏水性的和疏油性的。
在粘合剂结合的情形中，所用的粘合剂可为多种粘合剂中的任何粘合剂，包括分散体和合成胶乳。优选地，与复合织物中所用的纤维的耐化学品特性和耐热特性相比，粘合剂应当具有类似的或更好的耐化学品特性和耐热特性。可能的粘合剂体系包括以下共聚物的含水阴离子分散体：丁二烯丙烯腈共聚物；基于丙烯酸酯、乙烯基和偏二氯乙烯聚合物的共聚物和通过乳液聚合作用制备的共聚物；苯乙烯-丁二烯共聚物；以及丁二烯、苯乙烯和乙烯基吡啶的三元共聚物。
可使用不同的方法将纳米网以粘合剂方式结合到排流层上。例如，可首先将纳米网在所需区域中涂布上粘合剂，然后将排流层放置成接触涂布过的纳米网上的粘合剂。施加足够的热和压力以使粘合剂流进纳米网和排流层的一些孔中。如果粘合剂是可交联的，则粘合剂会由于受热而发生交联，因而导致纳米网和排流层的机械连结。在一个优选的实施方案中，纳米网和排流层使用合适的层压技术来结合，诸如使材料在足以熔融粘合剂的温度下穿过辊隙。咬送辊中的一个在其表面上可具有凸起图案以在层压体中产生点结合图案。
复合织物在衣服中位于外织物层和内织物层之间。有许多种天然织物和合成织物是已知的并且可用作外织物层和内织物层。通常，设计用作耐用外衣的衣服由相对疏松织造的织物构成，该织物由具有相对低强度或韧度的天然和/或合成纤维(例如尼龙、棉、聚酯、聚丙烯酸类、聚丙烯等)制成，每种纤维可具有小于约8克/旦尼尔(gpd)，更典型小于约5gpd，以及在某些情况下小于约3gpd的拉伸强度或韧度。此类材料可具有多种有益特性，例如可染性、透气性、亮度、舒适度、以及在某些情况下的耐磨性。
可使用不同的编织结构和不同的编织密度来形成几种可供选择的织造织物，作为本发明的组成。编织结构例如平纹结构、增强平纹结构(具有双或多经线和/或纬纱)、斜纹结构、增强斜纹结构(具有双或多经线和/或纬纱)、缎面结构、增强缎面结构(具有双或多经线和/或纬纱)均可使用。拉伸织造织物、格子布、多臂织物和提花织物也适用于本发明。
作为另外一种选择，可将非织造织物用作外织物层和任选的内织物层。非织造片材的实例包括纺粘纤维网、熔喷纤维网、多方向多层的梳理成网纤维网、气流法纤维网、湿法纤网、射流喷网法纤维网和包括一种以上的非织造片材的复合纤维网。合适的纺粘纤维网包括聚烯烃纤维，尤其是聚乙烯或聚丙烯。聚烯烃纤维可包含微量的其它共聚单体单元。如本文所用，术语“纺粘纤维网”是指由长丝形成的非织造纤维网，所述长丝被挤出、拉伸和沉积在连续的收集表面上。结合可通过若干种方法中的任何方法来实现，包括点结合或图案结合、压延或使非织造织物在高压下穿过饱和蒸汽室。合适的纺粘聚烯烃薄片材料的一个实例为以商品名
得自E.I.du Pont de Nemours and Company的闪纺聚乙烯。
可通过任何已知的方法例如以粘合剂方式、以热方式、使用超声波场或通过溶剂结合，将复合织物在其表面的一部分上结合到内织物层和/或外织物层上。可任选地使用一种或多种粘合剂将复合织物结合到内层和/或外层织物上。一种合适的粘合剂是热塑性粘合剂。在一些加热和冷却循环中，该粘合剂在加热后软化，然后在冷却后硬化。这种热塑性粘合剂的一个实例为热熔性粘合剂。在一个实施方案中，纳米纤维网使用聚合物粘合剂的溶液例如聚氨酯粘合性地结合，然后使溶剂蒸发。在另一个实施方案中，当纳米纤维网直接静电纺纱至织物上时，纺成纳米纤维网的溶剂用于实现溶剂结合。
Claims (22)
1.包括可透气的复合织物、外织物层和内织物层的衣服，所述可透气的复合织物包括两个纳米纤维网层和设置在它们之间的多孔的排流层。
2.权利要求1的衣服，其中通过粘合剂结合、热结合、超声波结合、溶剂结合或它们的任何组合，将所述排流层结合到一个或两个纳米纤维网层上。
3.权利要求1的衣服，其中所述复合织物结合到所述外织物层和内织物层中的至少一个上。
4.权利要求1的衣服，其中所述排流层选自纺粘非织造材料、梳理非织造材料、针刺非织造材料、气流成网非织造材料、湿法成网非织造材料、射流喷网非织造材料、纺粘-熔喷-纺粘非织造材料、织造织物、编织织物、熔喷非织造材料、三维织网、纳米纤维层以及它们的组合。
5.权利要求4的衣服，其中将所述排流层质构化或绉纹化以利于流体从其中穿过。
6.权利要求1的衣服，其中所述可透气的复合织物具有介于0.15m3/min/m2和7.6m3/min/m2之间的透气率以及至少500g/m2/日的湿汽透过率。
7.权利要求1的衣服，其中将最外面的纳米纤维网层用含氟化合物进行处理。
8.权利要求1的衣服，其中所述排流层的平均孔径至少与所述纳米纤维网层中的一个的平均孔径一样大，并且所述排流层至少与所述纳米纤维网层的较厚者一样厚。
9.权利要求1的衣服，其中所述排流层为非吸收性的。
10.权利要求1的衣服，其中所述排流层为吸收性的。
11.权利要求1的衣服，其中所述外织物层和内织物层为织造织物，所述织造织物包括选自下列的纤维：尼龙、棉、聚酯、聚丙烯酸类、聚丙烯、以及它们的组合。
12.权利要求1的衣服，其中所述纳米纤维网层以限定它们之间的空隙的图案彼此结合，并且所述排流层在所述空隙内以不连结方式设置在所述纳米纤维网层之间。
13.权利要求1的衣服，其中所述纳米纤维网层通过直接静电纺纱或电吹到所述排流层的表面上来制备，并且所述纳米纤维网层和所述排流层通过源自所述静电纺纱法或电吹法的残余溶剂彼此结合。
14.权利要求1的衣服，其中所述纳米纤维网层包括聚合物的纳米纤维，所述聚合物选自聚缩醛、聚酰胺、聚酯、纤维素醚、纤维素酯、聚亚烷基硫、聚亚芳基氧、聚砜、改性的聚砜聚合物以及它们的混合物。
15.权利要求1的衣服，其中所述纳米纤维网层包括聚合物的纳米纤维，所述聚合物选自下列交联和非交联形式的聚合物：聚(氯乙烯)、聚甲基丙烯酸甲酯、聚苯乙烯、以及它们的共聚物、聚(偏二氟乙烯)、聚(偏二氯乙烯)、聚乙烯醇。
16.权利要求1的衣服，其中所述纳米纤维网层包括聚合物的纳米纤维，所述聚合物选自尼龙6、尼龙6，6、和尼龙6，6-6，10。
17.权利要求1的衣服，其中所述两个纳米纤维网层中的每一个包含不同的聚合物。
18.权利要求1的衣服，其中所述纳米纤维网层为压延过的。
19.权利要求1的衣服，其中所述复合织物为压延过的。
20.权利要求1的衣服，其中将所述复合织物在接触所述内织物层和外织物层时进行压延。
21.权利要求1的衣服，其中所述纳米纤维网层中的至少一个为疏油性的或疏水性的。
22.权利要求1的衣服，其中所述外织物层和内织物层为非织造织物。
Applications Claiming Priority (4)
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| US282007P | 2007-11-13 | 2007-11-13 | |
| US61/002820 | 2007-11-13 | ||
| US61/002,820 | 2007-11-13 | ||
| PCT/US2008/003213 WO2009064311A1 (en) | 2007-11-13 | 2008-03-11 | Breathable garment having a fluid drainage layer |
Publications (2)
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| CN101854820A CN101854820A (zh) | 2010-10-06 |
| CN101854820B true CN101854820B (zh) | 2013-06-19 |
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| CN2008801160053A Active CN101854820B (zh) | 2007-11-13 | 2008-03-11 | 具有排流层的可透气衣服 |
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| EP (1) | EP2207440B1 (zh) |
| JP (1) | JP5336504B2 (zh) |
| KR (1) | KR101460838B1 (zh) |
| CN (1) | CN101854820B (zh) |
| AT (1) | ATE524079T1 (zh) |
| BR (1) | BRPI0817404A2 (zh) |
| WO (1) | WO2009064311A1 (zh) |
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| BRPI0719410A2 (pt) * | 2006-12-15 | 2017-10-31 | Freudenberg Nonwovens India Pvt Ltd | um sistema para aumento de entrada de massa de ar |
| WO2009064311A1 (en) | 2007-11-13 | 2009-05-22 | E. I. Du Pont De Nemours And Company | Breathable garment having a fluid drainage layer |
| CN104888620B (zh) * | 2008-10-07 | 2017-09-15 | 纽约州立大学研究基金会 | 高通量高效率纳米纤维膜及其制备方法 |
| WO2010060090A1 (en) * | 2008-11-24 | 2010-05-27 | Georgia Tech Research Corporation | Systems and methods to affect anatomical structures |
| US20100292664A1 (en) * | 2009-05-13 | 2010-11-18 | E. I. Du Pont De Nemours And Company | Garment having a fluid drainage layer |
| WO2011040718A2 (ko) * | 2009-09-30 | 2011-04-07 | 주식회사 아모메디 | 웨스턴 블롯용 나노섬유 멤브레인 및 그 제조방법 |
| EP2850230A4 (en) * | 2012-05-16 | 2016-01-13 | Univ North Carolina State | APPARATUS AND METHOD FOR PRODUCING NANO FIBERS FROM DISPLACED SOLUTIONS UNDER CONTINUOUS RIVER |
| EP2959509B1 (en) | 2013-02-14 | 2018-05-23 | Nanopareil, Llc | Electrospun hybrid nanofibre felt, method for making the same, and method for purifying biomolecules |
| DE102013008391A1 (de) * | 2013-04-23 | 2014-10-23 | Mann + Hummel Gmbh | Filtermedium, insbesondere Luftfiltermedium, sowie Filterelement, insbesondere Luftfilterelement, mit einem Filtermedium |
| US10201198B2 (en) * | 2014-12-23 | 2019-02-12 | Profit Royal Pharmaceutical Limited | Protective masks with coating comprising different electrospun fibers interweaved with each other, formulations forming the same, and method of producing thereof |
| CA3026497C (en) * | 2016-06-10 | 2023-09-19 | Ascend Performance Materials Operations Llc | Solution-spun polyamide nanofiber nonwovens |
| CN114161783A (zh) | 2017-04-26 | 2022-03-11 | 博爱（中国）膨化芯材有限公司 | 一种热复合速渗导流材料及其应用 |
| BR102017017992B1 (pt) * | 2017-08-22 | 2023-04-18 | Ec Brand Com Imp Exp De Vest Ltda | Forro multicamada de vestuário |
| US10519349B2 (en) | 2017-09-18 | 2019-12-31 | Bemis Associates, Inc. | Systems and methods for forming and using an adhesive tape |
| CN108004628B (zh) * | 2018-01-05 | 2021-04-02 | 东华大学 | 一种带有纳米纤维防粘连机构用于制备纳米纤维/短纤混纺纱的装置及方法 |
| US20210015684A1 (en) * | 2019-07-15 | 2021-01-21 | Patricia Kayanga Nakabugo | Bamboo And Nonwoven Disposable Garments |
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- 2008-03-11 CN CN2008801160053A patent/CN101854820B/zh active Active
- 2008-03-11 US US12/075,388 patent/US8241729B2/en active Active
- 2008-03-11 EP EP20080726706 patent/EP2207440B1/en active Active
- 2008-03-11 KR KR1020107012733A patent/KR101460838B1/ko active IP Right Grant
- 2008-03-11 BR BRPI0817404A patent/BRPI0817404A2/pt not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| ATE524079T1 (de) | 2011-09-15 |
| US20090123700A1 (en) | 2009-05-14 |
| BRPI0817404A2 (pt) | 2018-06-12 |
| CN101854820A (zh) | 2010-10-06 |
| JP2011503383A (ja) | 2011-01-27 |
| EP2207440A1 (en) | 2010-07-21 |
| KR20100100862A (ko) | 2010-09-15 |
| JP5336504B2 (ja) | 2013-11-06 |
| US8241729B2 (en) | 2012-08-14 |
| WO2009064311A1 (en) | 2009-05-22 |
| EP2207440B1 (en) | 2011-09-14 |
| KR101460838B1 (ko) | 2014-11-12 |
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