CN101213333A - 弹性、柔软以及点状粘合的具有填料颗粒的无纺织物，其制造方法以及其应用 - Google Patents

弹性、柔软以及点状粘合的具有填料颗粒的无纺织物，其制造方法以及其应用 Download PDF

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CN101213333A
CN101213333A CNA2006800236978A CN200680023697A CN101213333A CN 101213333 A CN101213333 A CN 101213333A CN A2006800236978 A CNA2006800236978 A CN A2006800236978A CN 200680023697 A CN200680023697 A CN 200680023697A CN 101213333 A CN101213333 A CN 101213333A
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fiber
bondedfibre fabric
texturized
monofilament
adhesive
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CN101213333B (zh
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P·格里诺伊斯
H·雷蒂格
O·斯托登迈尔
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Carl Freudenberg KG
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Carl Freudenberg KG
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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Nonwoven Fabrics (AREA)
  • Gloves (AREA)
  • Details Of Garments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

本发明涉及一种弹性无纺织物，所述无纺织物在选定的部位利用具有由填料组成的小颗粒(尤其是潜热储热材料)的粘合剂加固，并在其它部位不进行加固。所述无纺织物的特征是柔软的手感和良好的柔性。所述无纺织物可以用作衬里材料或中间衬层。

Description

弹性、柔软以及点状粘合的具有填料颗粒的无纺织物，其制造方法以及其应用
技术领域
本发明涉及一种特别适合用作衬里材料的无纺织物，一种用于制造所述无纺织物的方法以及所述无纺织物用于制造衬里的应用。
背景技术
设有填料的纺织平面构型物，特别是具有热调节特性的平面构型物是已知的。
EP-A-178372公开了一种褶皱性的多微孔的用于医学用途的多层无纺织物。其中间层由微纤维组成并且在两侧由无纺织物覆盖。各层通过图案式的印刷的粘合剂膏-例如石蜡乳液-相结合。
在EP-A-190788中说明了一种无纺织物，所述无纺织物包含按图案布置的并优选发泡的微球体，并可以用作用于塑料的强化材料。
US-A-5366801或EP-A-611330说明了一种织物的具有粘合剂和分布在其中的微囊的涂层，所述微囊包含潜热储热材料。
由WO-A-02/12607已知一种具有温度调节特性的无纺织物。在该文献中所说明的实施形式中，所述无纺织物用包含分散在其中的微囊包裹的潜热储热材料的粘合剂浸渍。所述具有热调节特性的材料分布在无纺织物的整个内部中。除了整个内部体积由所述材料填充的实施形式，还说明了这样的变型方案，其中，所述材料只存在于纤维的交叉点，而内部空间由空气填充。但在所述的实施形式中，整个无纺织物都用所述材料浸渍。这通过将所形成的无纺织物用粘合剂浸泡来实现。作为初始材料使用无纺织物，即机械稳定的/粘合的材料。
在WO-A-02/59414中说明了一种具有温度调节特性和改善的柔性及透气性的、设有涂层的材料。所述设有涂层的材料由一种基体组成，所述基体在其表面的一部分上设有粘合剂点或包含温度调节材料的粘合剂施加部。所述粘合剂可以施加在表面上或渗入基体的内部空间以及局部或完全地浸透所述基体。在每种情况下，都有一部分的表面没有用粘合剂浸渍。其中说明了不同的设有涂层的基体，例如织物、无纺织物、薄膜、泡沫和纸。
由WO-A-02/95314还已知具有改善的温度调节特性的基体。按照该文献，利用模板(印刷)粒结状地将包含潜热储热材料的聚合物分散液施加到织物表面上。除了金属薄膜和纺织平面物，作为可能的基体，还提到了无纺织物，即机械稳定的材料/粘合的纤维网(Faserflor)。
如果所说明的是纺织平面物，在迄今为止现有技术中使用的基体是这样的构型物，在制造后对所述构型物进行稳定化(粘合、加固)，从而所述构型物可以方便地操作。例如在形成具有机械上还不稳定的面构型的纤维网(形成无纺布)之后，接下来对无纺布进行加固，由此制成无纺织物(例如参见Vliesstoffe，W.Albrecht，H.Fuchs和W.Kittelmann，Wiley-VCH(2000)，第II部分，Herstellungsverfahren für Vliesstoffe，第6章，Vliesverfestigung)。常见的无纺布加固方法是化学方法，如施加粘合剂，或物理方法(机械或热方法)，如针刺、喷气变形、用热空气处理或砑光。所述方法直接在形成无纺布过程之后进行，以使机械上非常不稳定的纤维网转换成可操作的形式。
在本说明书的范围内，无纺织物理解成经加工的层、无纺布或由定向布置或彼此随意定位的纤维组成的纤维网，通过摩擦和/或凝聚和/或粘结进行加固(如ISO 9092或EN 29092中定义的那样)。
已经有过这样的尝试，即，通过借助于圆形筛网模板将膏状的粘合液施加到仍不稳定的纤维网上，从而直接在形成无纺布之后通过模板印刷施加粘合剂(例如参见Vliesstoffe，W.Albrecht，H.Fuchs和W.Kittelmann，Wiley-VCH(2000)，第6.5章，chemische Verfahren，第381页)。目前为止，这种方法在技术上还无法实现，因为通过“粘稠的”粘合剂使纤维网粘合在技术上是有问题的。纤维网松散的纤维倾向于附着在印刷模板上并在短时间内妨碍印刷过程。可以非常强烈地、面状或点状地压缩或压合纤维网，以抑制这种现象，但这样形成的产品特别扁平并且织物特性较少；粘合剂也可以强烈地穿透。
在DE-A-2914617中说明了一种用于均匀和连续地向纺织平面构型物的正面和背面印刷膏状物的方法。根据实施例，通过引导通过梳理形成的纤维网穿过砑光机，并由此进行预加固。接下来，以图案的形式在两侧借助于辊子将粘合剂分散液涂覆到所述纺织平面构型物上，接着进行干燥并在此时使粘合剂交联。
目前为止，通过对无纺织物，即对粘合的、机械稳定的材料，进行后处理来制造具有热调节特性的无纺织物。由于设置在前面的加固步骤，这种无纺织物的弹性和柔软度在一些情况下不能满足期望。
发明内容
由上面所述的现有技术出发，本发明的目的是，提供一种设有填料的无纺织物，所述无纺织物除了高弹性以外，还具有高柔软度。由此可制造具有改善的合体性和穿着舒适性的织物。
本发明的另一个目的是，提供一种改进的用于设有填料的无纺织物的制造方法，在该方法中，可省去设置在前面的无纺布加固步骤，并因此可以用较少的花费制造无纺织物。
本发明涉及一种具有卷曲变形和必要时未卷曲变形的纤维和/或单丝的无纺织物，所述无纺织物在选定的部位利用具有由填料组成的小颗粒的粘合剂加固，并在其它部位不进行加固。
在支承件上进行铺放之后，通过含有填料的粘合剂直接施加在未加固的无纺布即纤维网上并在必要时使其硬化，可以形成一种平面构型物，所述平面构型物在选定的面区域内未加固，即所述平面构型物在所述面区域内没有进行无纺布形成。由于存在未加固的区域，可以改善无纺织物的透过性、弹性和手感。
在本发明中，在制造纤维网时使用可热卷曲变形的纤维或单丝。所述纤维网优选附加地包括为卷曲变形的和不可卷曲变形的或在处理条件下不可卷曲变形的纤维或单丝。
即，根据本发明的无纺织物具有可卷曲变形的纤维和/或单丝，并优选除此以外还具有不可卷曲变形的纤维和/或单丝。
在本说明书的范围内，纤维理解为有限长度的丝线(短纤维)，即具有在分米数量级的长度的丝线。
在本说明书的范围内，单丝理解为具有实践中的无限长度的丝线，即具有在分米数量级以上的长度的丝线。
作为可热卷曲变形的纤维或单丝可采用双组分纤维或单丝，以避免目前由现有技术已知的产品具有的问题。
在无纺织物制造中长期以来就使用双组分纤维或单丝。所述双组分纤维或单丝可以作为皮芯纤维或单丝使用，所述皮芯纤维或单丝具有作为无纺织物面状或点状加固时的粘合纤维的、熔点较低的皮组分(例如参见Vliesstoffe，W.Albrecht，H.Fuchs和W.Kittelmann，Wiley-VCH(2000)，第1.2章，Chemiefasern-Bikomponentfasern，第63页)。
在本发明的无纺织物中，不是由于熔点较低的组分的粘结/结合特性才使用所述双组分纤维或单丝。也可以使用由具有类似熔点的聚合物组分组成的双组分纤维或单丝；所述双组分纤维或单丝例如按并列式的结构或不对称的皮芯结构这样构成，即，在热处理时沿纤维或单丝轴线发生不同的收缩率。代替或附加于双组分纤维或单丝，也可以使用单组分聚合物纤维或单丝，这种纤维或单丝在其制造期间受到在其横截面上不对称的纤维或单丝冷却。
在制造无纺织物时可卷曲变形的纤维或单丝的所使用的比例使得在加载温度时在印刷车间之前出现自然(in situ)收缩。卷曲变形的纤维或单丝使得可以改善纤维网的凝聚力，由此可明显使得无纺织物易于印刷。所述无纺织物附加地获得体积和弹性。在热处理时，这样来选择温度分布，即，使得处理温度低于多组分纤维中熔点或软化点较低的聚合物的熔点或软化点，从而热处理尽管会引发卷曲变形，但不会导致粘结。
通过引发卷曲变形，在根据本发明的无纺织物的制造中，印刷的粘合剂点也可以获得体积和柔软度，因为通过卷曲变形的纤维或单丝不会在纤维阵列中形成压实的点。不需要对粘合剂点进行发泡，但也可以进行发泡。
为了实现特别柔软并且弹性特别高的产品，优选采用包括二维或三维卷曲变形的纤维和/或单丝的无纺织物。
根据本发明使用的纤维网可以由具有不同纤度范围的任意纤维类型组成，例如0.5至10dtex的纤度、优选0.8至6.7dtex的纤度，特别是1.3至3.3dtex。纤维混合物应包含至少5％重量的，优选至少20％重量的卷曲变形的纤维或单丝。所述纤维或单丝可以是异质复合纤维(Heterofilfaser)/双组分纤维。其余的纤维可以是无纺布制造中常见的短纤维或单丝。
根据本发明使用的纤维网可以用不同的无纺布形成技术制造。主要列举梳理、干式铺放的纤维网。也可以使用按纺粘法或熔吹法的直接纤维铺放技术。
特别优选采用由短纤维组成的纤维网。
所使用的纤维网的纤维可以是各向同性或按一优选方向，即各向异性地铺放的。纤维网可以由具有相同或不同纤度的相同的纤维组成。构成纤维网的纤维可以由不同的纤维构成，例如由单组分纤维组成，但也可以由100％的双组分纤维或双组分纤维和单组分纤维的混合物组成。可以采用合成纤维与天然纤维的混合物。
优选采用与聚酯双组分纤维-如聚酯并列式双组分纤维-混合的单组分纤维，如1.7dtex/mm或3.3dtex/mm的聚酯单组分纤维/均聚酯纤维。也可以在混合物中采用例如由3d/1.5”的由PA66组成的聚酰胺纤维。至少5％的异质复合纤维-优选是双组分纤维-的比例是必要的，优选是20％。
根据本发明使用的纤维网可以在无纺织物的制造条件下根据所添加的异质复合纤维的量根据经梳理的纤维网的走向不同进行最多50％的收缩。但所述无纺织物在后面的工步中进行稳定化，并优选变成低收缩的，例如沿机器运行方向(Maschinenrichtung)为-3.0％，而沿横向为-1.5％.
所采用的纤维网通常具有15至210g/m2的单位面积重量。
特别优选采用单位面积重量为35至140g/m2的经梳理的纤维网。
纤维材料的例子有：聚烯烃，优选是聚丙烯或聚丙烯-乙烯共聚物；聚酯；聚酰胺；或聚丙烯腈；以及天然纤维，特别是纤维素纤维、棉纤维、羊毛或其混合物。
包含精细分布的填料的粘合剂可以具有任意的性质，只要所述粘合剂能够在选定的面区域内对纤维网进行加固。
粘合剂的例子有：化学交联的塑料，特别是分散液形式的，例如具有常见的交联基团的丙烯酸己酯或丙烯酸丁酯。但也可以采用包含精细分布的填料的热塑性聚合物。这种聚合物可以用作熔融粘合剂并在这里以这种方式在经处理的区域内对进行纤维的加固。这种类型的热塑性聚合物粘合剂的例子有：聚烯烃粉末，特别是聚乙烯粉末或聚丙烯粉末、优选是熔程＞150°的共聚多酯粉末。粘合剂的其它例子可以在US-A-5366801、WO-A-0212607，WO-A-02/59414和WO-A-02/95314中找到。
可以采用任意精细颗粒的材料作为填料，通过添加所述填料应使所述无纺织物具有希望的特性。
填料的例子有，具有吸附或吸收特性的小颗粒、离子交换剂、矿物填料、加强材料、导电和/或导热的材料/颗粒，以及特别是潜热储热材料。
特别优选采用可膨胀的微囊、活性炭小颗粒、金属小颗粒、由超级吸附性的材料组成的小颗粒。
可以采用本身已知的物质作为特别优选的潜热储热材料。其例子可以在前面提及的文献中看到。
特别优选采用形成微囊的碳氢化合物，特别是形成微囊的石蜡作为潜热储热材料。
在下表中列出了潜热储热材料的例子。
化合物 碳原子数量  熔点(℃)
n-癸烷 10  -32
n-十一烷 11  -26
n-十二烷 12  -11
n-十三烷 13  -5.5
n-十四烷 14  5.9
n-十五烷 15  10.0
n-十六烷 16  18.2
n-十七烷 17  22.0
n-十八烷 18  28.2
n-十九烷 19  32.1
n-二十烷 20  36.8
n-二十一烷 21  40.5
n-二十二烷 22  44.4
n-二十三烷 23  47.6
n-二十四烷 24  50.9
n-二十五烷 25  53.7
n-二十六烷 26  56.4
n-二十七烷 27  59.0
n-二十八烷 28  61.4
n-二十九烷 29  63.4
n-三十烷 30  65.4
n-三十一烷 31  68.0
n-三十二烷 32  70.0
n-三十三烷 33  71.0
n-三十四烷 34  72.9
n-三十六烷 36  76.1
纤维材料和粘合剂以及填料的重量比例在本发明的无纺织物中通常为90∶10至10∶90，优选为50∶50至30∶70。
借助于印刷技术，优选借助于模板印刷在预定的区域内将粘合剂与填料施加到纤维网上。此时，所施加材料的大部分应渗入纤维网中，并尽可能渗透纤维网。也有一些粘合剂留在表面上。但通过点状地施加所述由粘合剂/填料组成的混合物，在制造完成的产品中留下这样的纤维网区域，在所述区域内基本上没有粘合剂/填料。
具有粘合剂/填料的表面覆盖部可以有较宽的范围，通常为面积的20％以上至95％。优选为纤维网面积的35％以上至80％用粘合剂/填料覆盖。
可以按不同的预定图案向纤维网施加粘合剂/填料。所述图案可以由线形、六角形、圆环形或点状的面区域形成。优选是点状图案，如规则或不规则的点状图案。
本发明还涉及一种用于制造上述无纺织物的方法，包括以下步骤：
a)通过按本身已知的方式在一铺放装置上铺放可热卷曲变形的纤维和/或可热卷曲变形的单丝以及必要时铺放不可热卷曲变形的纤维和/或不可热卷曲变形的单丝来制造纤维网，
b)必要时通过加热的辊子对纤维网进行预加固，这样来选择所述辊子的温度，即，引发可卷曲变形的纤维和/或单丝的卷曲变形，
c)按本身已知的方式在纤维网的选定部位施加包含由填料组成的小颗粒的粘合剂，以及
d)加热在步骤c)中经过处理的纤维网，以完全引发可卷曲变形的纤维和/或单丝的卷曲变形，并通过粘合剂和必要时通过粘合剂的交联使纤维网的纤维相结合/粘合。
纤维网的制造可以如上所述用不同的方法来实现。
向纤维网的表面上施加粘合剂/填料同样可以用任意的方法进行。优选采用筛网印刷法，特别是采用圆形筛网印刷模板。
因此，在施加粘合剂时，一种方法优选通过一种圆形筛网印刷模板来实现，所述圆形筛网印刷模板直接在形成未粘合的纤维网之后，必要时在预加固之后作用在纤维网的表面上。
在施加粘合剂/填料之后，通过加热使经这样处理的纤维网稳定化。这可以按本身已知的方式方法进行。
经处理的纤维网优选通过热辊加热，从而可引发纤维网的卷曲变形。
在一个优选的实施形式中，通过梳理纤维和将纤维铺放在支承带上来完成步骤a)。
在另一个优选的实施形式中，通过在没有压力或只有较小压力的情况下使纤维网在加热的辊子之间穿过来完成步骤b)，从而这样的处理对纤维网的厚度没有影响，其中辊子的温度选择成低于形成纤维的材料的、熔点最低的聚合物组分的熔点。
在另一个优选的实施形式中，通过由一模板向纤维网表面的选定部位点状地施加包含由填料组成的小颗粒的粘合剂，优选是潜热储热材料，来完成步骤c)。
根据本发明的无纺织物可以用于各种不同的领域，例如用作衬里材料或中间衬层。应用的例子有：用于服装、床上用品，手套或鞋中。所述无纺织物特别是用作衬里材料。
所述应用同样是本发明的内容。
具体实施方式
下面的实施例在不限制本发明的情况下说明了本发明。
实施例
在梳理机上制造由40％的3.0dtex/60mm的聚酯并列式双组分纤维、30％的3.3dtex/60mm的聚酯单组分纤维和30％的1.7dtex/38mm的聚酯单组分纤维的混合物组成的纤维网。在没有压力的情况下引导经梳理的纤维网在两个具有125℃温度的加热辊之间穿过。用旋转筛网印刷模板将由软的丙烯酸酯粘合剂和mPCM潜热储热材料按1∶2的比例的40％的混合物按点状图案的形式施加到纤维网上。施加量为90g/m2。印刷的面积为82.5％。在施加之后，通过多带干燥机在150℃下对经印刷的纤维网进行干燥，并使粘合剂交联。这种产品称为“40％双组分，点状”。
下面的表格示出了所形成的无纺织物根据可卷曲变形的双组分纤维的量和种类的弹性特性。
这里“CVT，全面”表示整个面积用粘合剂/mPCM浸渍的纤维网。
“100％双组分，点状”是根据本发明的无纺织物，所述无纺织物与上述“40％双组分，点状”类似地制造，其中改变之处在于，使用了100％的双组分纤维。
HZK表示最高拉力；HZD表示断裂拉伸率。在不同的拉伸值下测量弹性模量。测量与EN 29073-3类似地进行。
在拉伸率较低时，弹性模量越低，材料越易于拉伸。
表格
重量(g/m2)     HZK纵向(N/5cm)     HZD纵向(％)   5％弹性模量(N/5cm)   10％弹性模量(N/5cm)   15％弹性模量(N/5cm)   20％弹性模量(N/5cm)
 CVT，全面 140 54 34 17.4 28.2 36.4 49.4
 100％双组分，点状 130 14 58 2.2 5.6 8.5 11.9
 40％双组分，点状 140 13 48 3.0 5.9 8.4 10.8
重量(g/m2)     HZK纵向(N/5cm)     HZD纵向(％)   5％弹性模量(N/5cm)   10％弹性模量(N/5cm)   15％弹性模量(N/5cm)   20％弹性模量(N/5cm)
CVT，全面 140 55 75 4.1 8.5 12 18.1
100％双组分，点状 130 38 76 0.3 1.1 2.7 8.1
40％双组分，点状 140 31 69 0.6 2.1 4.2 9.7

Claims (19)

1.一种弹性无纺织物，具有卷曲变形的纤维和/或卷曲变形的单丝和必要时具有未卷曲变形的纤维和/或未卷曲变形的单丝，所述无纺织物在选定的部位利用具有由填料组成的小颗粒的粘合剂加固，并在其它部位不进行加固。
2.根据权利要求1所述的无纺织物，其特征在于，所述无纺织物具有卷曲变形的纤维和/或单丝，并且除此以外还具有未卷曲变形的纤维和/或单丝。
3.根据权利要求1所述的无纺织物，其特征在于，所述无纺织物具有至少20％重量的卷曲变形的纤维和/或卷曲变形的单丝。
4.根据权利要求1所述的无纺织物，其特征在于，所述无纺织物是短纤维无纺织物。
5.根据权利要求1所述的无纺织物，其特征在于，所述无纺织物包含卷曲变形的双组分纤维。
6.根据权利要求1所述的无纺织物，其特征在于，所述无纺织物除了卷曲变形的聚酯双组分纤维以外还包含未卷曲变形的聚酯单组分纤维，并且必要时还包含未卷曲变形的聚酰胺纤维。
7.根据权利要求1所述的无纺织物，其特征在于，所述无纺织物包含二维和/或三维地卷曲变形的纤维。
8.根据权利要求1所述的无纺织物辆，其特征在于，所述粘合剂包含化学交联的塑料。
9.根据权利要求1所述的无纺织物，其特征在于，所述粘合剂包含热塑性聚合物，所述聚合物通过熔融粘结使纤维网的纤维相结合。
10.根据权利要求1所述的无纺织物，其特征在于，采用具有吸附或吸收特性的小颗粒、离子交换剂、矿物填料、加强材料、导电和/或导热的材料/颗粒，以及特别是潜热储热材料作为填料。。
11.根据权利要求10所述的无纺织物，其特征在于，采用可膨胀的微囊、活性炭小颗粒、金属小颗粒、由超级吸附的材料组成的小颗粒作为填料。
12.根据权利要求10所述的无纺织物，其特征在于，所述潜热储热材料是微囊包裹的碳氢化合物。
13.根据权利要求1所述的无纺织物，其特征在于，包含填料的粘合剂按穿透纤维网的规则或不规则的点图案的形式施加。
14.用于制造根据权利要求1所述的无纺织物的方法，包括以下措施：
a)通过按本身已知的方式在一铺放装置上铺放可热卷曲变形的纤维和/或可热卷曲变形的单丝以及必要时铺放不可热卷曲变形的纤维和/或不可热卷曲变形的单丝来制造纤维网，
b)必要时通过加热的辊子对纤维网进行预加固，这样来选择所述辊子的温度，即，引发可卷曲变形的纤维和/或单丝的卷曲变形，
c)按本身已知的方式在纤维网的选定部位施加包含由填料组成的小颗粒的粘合剂，以及
d)加热在步骤c)中经过处理的纤维网，以完全引发可卷曲变形的纤维和/或单丝的卷曲变形，并通过粘合剂和必要时通过粘合剂的交联使纤维网的纤维相结合。
15.根据权利要求14所述的方法，其特征在于，通过梳理纤维和将纤维铺放在支承带上来完成步骤a)。
16.根据权利要求14所述的方法，其特征在于，通过在没有压力或只有较小压力的情况下使纤维网在加热的辊子之间穿过来完成步骤b)，从而这样的处理对纤维网的厚度没有影响，其中辊子的温度选择成低于形成纤维的材料的、熔点最低的聚合物组分的熔点。
17.根据权利要求14所述的方法，其特征在于，通过由一模板向纤维网表面的选定部位点状地施加包含由填料组成的小颗粒的粘合剂，优选是潜热储热材料，来完成步骤c)。
18.根据权利要求17所述的方法，其特征在于，通过一种圆形筛网印刷模板来实现施加粘合剂，所述圆形筛网印刷模板直接在形成未粘合的纤维网之后，必要时在预加固之后作用在纤维网的表面上。
19.根据权利要求1的无纺织物的应用，其中，该无纺织物用作衬里材料或中间衬层，特别是用于服装、床上用品，手套或鞋中。
CN2006800236978A 2005-06-28 2006-04-28 弹性、柔软以及点状粘合的具有填料颗粒的无纺织物，其制造方法以及其应用 Expired - Fee Related CN101213333B (zh)

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CN112064194A (zh) * 2019-12-06 2020-12-11 长春博超汽车零部件股份有限公司 纤维毡、纤维板及其制备装置和方法

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US20090100565A1 (en) 2009-04-23
JP4779014B2 (ja) 2011-09-21
EP1937886B1 (de) 2012-10-10
CN101213333B (zh) 2012-05-23
KR101052376B1 (ko) 2011-07-28
TWI322205B (en) 2010-03-21
DE102005030484A1 (de) 2007-01-04
KR101172600B1 (ko) 2012-08-08
KR20080022214A (ko) 2008-03-10
US8114794B2 (en) 2012-02-14
EP1937886A1 (de) 2008-07-02
JP2008546927A (ja) 2008-12-25
KR20100101700A (ko) 2010-09-17
PL1937886T3 (pl) 2013-02-28

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