CN102883694A - 高柔性的有吸附能力的层合体及其制造方法 - Google Patents

高柔性的有吸附能力的层合体及其制造方法 Download PDF

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Publication number
CN102883694A
CN102883694A CN2011800164824A CN201180016482A CN102883694A CN 102883694 A CN102883694 A CN 102883694A CN 2011800164824 A CN2011800164824 A CN 2011800164824A CN 201180016482 A CN201180016482 A CN 201180016482A CN 102883694 A CN102883694 A CN 102883694A
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China
Prior art keywords
flexible pipe
core body
elastic
molding core
web material
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Granted
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CN2011800164824A
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CN102883694B (zh
Inventor
W·芬斯克
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Evonik Super Absorbent Co ltd
Evonik Operations GmbH
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Evonik Industries AG
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Abstract

本发明涉及一种用于连续制造柔韧的有吸附能力的幅面材料的方法，该幅面材料包含两个外层，其中至少一个外层是由纺织材料制成的，在两个外层之间加入至少两个处于预应力下的弹性的中间层，其由倾斜于制造方向相互反向设置的纱线或带构成，通过所述纱线或带，幅面材料在中间层松弛时基本上横向于其制造方向缩短和变成皱褶的并且在弹性的中间层的自由空间中引入粉末状的或纤维状的嵌入物，其具有相对于液体例如尿、血、水或汗的吸收特性或再吸收特性，例如释放医疗物质、化妆物质或用于产生热/冷。

Description

高柔性的有吸附能力的层合体及其制造方法
技术领域
本发明涉及一种纺织的有吸附能力的材料，其能够在至少一个坐标方向上伸展以产生空间用于由于吸取待吸收的液体而引起的体积增大，这种有吸附能力的材料特别是与一次性物品（例如婴儿尿布、尿失禁产品、卫生巾）相关联地需要的，或者在用于包装和食品技术中的吸收性物品的领域中是需要的。该功能在传统上通过由纸浆、超吸收性颗粒或纤维和由合成无纺布材料、纸浆或棉构成的液体分布层构成的合适的组合产品满足。
出于对于地球的自然资源的可持续性的责任的和对使用自然资源的后果的小心对待，需要将原料和包装材料的消耗以及用于制造和销售的原料保持尽可能少。为了制造卫生用品，其首先意味着初级能量消耗、纸浆、输送体积、包装膜和包装硬纸板以及废料体积的减小。
特别是在婴儿尿布的范围内，不仅由文献而且由工业产品已知多种多样的项目，其追求通过吸水性的聚合物（超吸收体）颗粒部分地或完全地替代纤维素或者说纸浆的吸收性。从而在技术上、经济上和生态上期望的是，例如将现代的婴儿尿布或用于成人的尿失禁产品完全转变成无纸浆的吸收垫，以便将使用一次性物品对气候变化的影响保持尽可能低。
背景技术
两种完全不同的途径追求由婴儿尿布、尿失禁产品、卫生巾中减少或去除纸浆：
1.通过使用可伸展的或可膨胀的热塑性体作为在超吸收体的颗粒之间的粘合剂来替代纸浆，这种粘合剂在超吸收体膨胀时保持粘附、参与膨胀运动并且即使在潮湿状态下也确保基质的完整性。
2.将多个离散的超吸收体部分引入到两个或多个载体层之间，其中超吸收体通过液体吸取而膨胀导致的体积增大替代地通过在超吸收体引入到层合体中时一个或多个载体层的弹性、一个或多个载体层的皱褶或拉伸，或者通过各单个载体层的彼此之间的合适连接实现，使得由于超吸收体的膨胀引起的破裂应力可能导致这种连接的针对性的局部开裂。
在EP 724418中描述了一种层合体的制造，其由两个外层构成，它们之中至少一个层是亲水的并且借助于对水灵敏的粘附剂彼此胶合，从而在隔离的非胶合的部分中可以点状地引入超吸收体，其在膨胀状态下特别是断裂开胶合并且达到层合体的对于膨胀体积所需要的体积增大。在此不利的是，在膨胀状态下仅可以达到层合体的最小的完整性。
由US20020102392同样已知一种用于制造吸收性的层合体的方法，其具有整合的超吸收体部分和弹性特性。在此在两个外层（它们之中一个在纵向方向上借助于成型辊被形成褶皱）之间且横向于制造方向经由真空系统定位各个超吸收体部分并且获得在纵向方向上可伸展的层合体，其中可以通过使用弹性的薄膜或无纺布材料提高弹性和皱褶。
由US20020115969已知另外一种用于制造层合体的方法。在此描述一种具有各单幅面超吸收体的、纵向连续的层合体的制造，超吸收体借助于热胶这样安装到两个外层之间，使得横向于制造方向分别存在由超吸收体覆盖的区域条和无超吸收体的区域条。
在WO 2004071539和WO 2004071363中描述了层合体的制造，该层合体包含两个外层和点状地整合的超吸收体部分。借助于有纹理的真空辊将第一外层用于构成凹部，该凹部利用超吸收体和纤维材料填充并且与第二外层连接。可比较的产品长久以来也用作在手术和患者保护方面的垫子。
发明内容
超吸收体在液体吸取期间经历了2500-5000%的重量增加。随之而来的体积增大必须通过包围的载体材料的合适的柔韧性承受。这在传统的纸浆/超吸收体的吸收垫的情况下原则上不是问题，因为纸浆在所有三维上可以实现伸展。在所谓的超吸收体-层合体中（其中超吸收体颗粒或超吸收体/纤维混合物借助于粘结剂或借助于热被固定在两个或多个无纺布层、薄膜成或纸巾层或类似物之间），层合体的外层必须实现该功能，通过伸展或通过几何柔韧性。然而在此必须任何时候都确保超吸收体的埋入，而不会出现其中一个外层的断裂或导致层合体的撕裂。此外期望的是，该层合体不仅在垂直于其制造平面的方向上，而且在该平面本身中也是可弹性伸展的，以便不仅使得超吸收体由于液体吸取导致的体积增大变得容易，而且在与另外的上述的卫生用品的其它元件的组合，不损害卫生用品的柔韧性和与相应的身体轮廓的适配能力。
因此，本发明的目的在于提供一种制造方法，其可以以高的生产能力和由此便宜地连续制造有吸附能力的纺织的幅面材料，其中最终产品不仅具有面状弹性的特性以最佳适配使用者的身体轮廓，而且具有体积弹性的特性以用于接纳较大的液体量。
上述目的根据本发明如此实现，通过将超吸收体和一个或多个单纱线、单条或带构成的弹性的中间层引入到如此制造的层合体的两个外层之间，该层合体基本上可横向于制造方向伸展并且在松弛状态下是有褶皱的，并且该弹性的中间层以缝合的覆盖层的形式包围各单个由超吸收体构成的部分并且为层合体在接纳液体时的垂直于制造平面的和在制造平面中的扩展提供空间。为了用于应用在现代的超薄的和弹性的卫生用品的领域中，此外重要的是，如此制造的层合体是完全弹性的和可伸展的并且不仅在干燥的状态下而且在潮湿的状态下与身体轮廓完美适配。
通过层合体的皮肤侧的表面或者说层合体的被待吸收的液体碰到的那一侧上的如此获得的褶皱和纹理并且与相应的亲水的和有转移能力的外层相结合，有利地确保了不仅在非干燥的状态而且在潮湿的状态下出色的液体引导。如此制造的层合体即使在膨胀的状态下在弹性的层的胶合的区域内也总是在垂直于其制造平面的方向上是可透水的，而不会由于超吸收体的膨胀而被阻止，从而即使在背向皮肤的一侧上液体转移效率也通过表面的纹理和相应的外层的选择而确保并且皮肤侧的外层在润湿/皮肤湿度方面可以被优化。
根据本发明，首先第一外部的纺织层20的前端部被施加在细长的杆状的或管状的成型芯体5的端部部段上并且在围绕成型芯体的进给运动时折叠成软管状封闭的形状。
在成型芯体上的进给运动的进一步的进程中，通过成型芯体的横截面的缩小，软管的圆周相应地缩短，使得过剩的材料通过位于软管外部的导轨或导棒8引导到成型芯体的合适的凹部中，紧接着通过两个或多个环形包围成型芯体的且成对反向被驱动的供给装置11和14由在圆周方向上隔开距离的多个单引导部17将多组弹性纱线或条50和53松动地抽出并且在没有或仅仅具有由摩擦引起的较小的应力的情况下在成型芯体上的进给过程中围绕第一外部的材料层放置。在弹性的纱线或条的十字形对称包围第一外部的材料幅面的软管的平面图案32上线状地涂覆粘合剂29，其基本上润湿和包裹露出的弹性的纱线。在进给运动的进一步进程中，通过成型芯体的横截面的加大，第一外部的材料幅面的软管被绷紧并且因此与弹性的纱线接触并且最后变成扁平的形状。在该扁平的软管的两侧，借助于一对牵拉或压紧辊38将第二外部的材料层32的两个单幅面连接到第一外部的材料幅面20和设有粘合剂29的弹性纱线17的露出的表面上。在该连接期间，在第一外部的材料幅面的软管的两侧在该材料幅面和供给的第二外部的材料幅面之间加入各单轨迹（Spur）的超吸收体47。最后，如此形成的软管沿着纵向分割成多个单幅面并且其横跨地卷绕到单辊上或存放在箱子中。
通过折叠成第一材料幅面的软管和通过第一外部的材料幅面的张开产生软管的圆周弹性，同时弹性的平面图案32扩展，那么相对于可比较的基于预紧的纱线或带的用于弹性软管的卷绕方法（例如WO03041627或DE 102004026070），通过去除对纱线的单引导的驱动装置显著减小复杂度并且得到与层合体的可横向伸展性成比例实现的生产量的提高，因为根据本发明生产速度通过环形的供给装置的极限转速限定。此外用于粘合剂29的涂覆或加设系统的宽度同等减小。
因为在将弹性的纱线或条施加到第一外部的材料幅面的软管上之后，这些纱线或条仅仅点状地接触并且否则露出，所以螺旋形或回纹形地施加的粘合剂被强制通过弹性纱线的平面图案、优选将其包裹并且在第一外部的材料幅面的软管的张开之后基本上围绕纱线定向，由此产生与平面图案32对应的胶图（图4），其基于弹性的纱线的包裹在成型芯体上的进给运动的进一步进程中将该纱线不仅与第一外部的材料幅面而且与第二外部的材料幅面粘接。
证明有利的是，成型芯体5相应于图2a由引导材料幅面20的引导牵条35和在引导牵条之间设置的存储牵条38（图2a）构成，在成型芯体的缩小期间通过相应的导轨8将材料幅面20的软管的过剩的材料压入所述存储牵条38中（图2b）。
第一外部的材料层一旦被压入存储牵条中可以轻易通过负压、通过压缩空气或通过静电加荷被保持在紧密贴靠在成型芯体的引导和存储牵条上的位置上并且低摩擦地经由成型芯体拉动。
在加设弹性的中间层和粘合剂之后，成型芯体的张开有利地如此实现，即成对对置的引导牵条在成型芯体的进一步分布中在其横向于成型芯体的纵向轴线的伸展方向上连续地加宽，另外一对引导牵条以相同的量在宽度上减小，从而第一外层的软管连续地由存储牵条中拉出并且经由引导牵条的顶端被绷紧地拉动并且因此与被胶粘的弹性层处于面状接触（图2c），最后在进给运动的进一步进程中通过引导牵条的进一步的同步的成对的扩宽或宽度减小在基本上相同的圆周长度的情况下变成扁平的状态（图2d）。
有利地成型芯体5以其纵向方向这样垂直地设置，使得牵拉辊56位于成型芯体5的下端部上（图1）。
超吸收体47的供给根据本发明以单独的体积连续或重量计量的连续的单幅面或轨迹实现，其或者间歇性地通过脉动的压缩空气或活塞被加入到平面图案的无胶的区域内或者间歇性地与平面图案32相符合地横向于第一外部的材料幅面的软管的行进方向被转向。为了简单的应用，足够的是将这些单轨迹慢慢流入，其中符合目的地平面图案的每个盒子供给两个单幅面。
可以有利的和符合目的的是，第一外部的材料幅面20的软管在输入到牵拉辊56中之前在横向方向上通过引导牵条的宽度的减小而被松弛，从而其在输入第二外部的材料幅面44时具有轻微的波纹度，由此在平面图案26的未被胶合的区域内形成小的凹处，其使得超吸收体33的放置变得容易。
在本发明的进一步发展中通过合适控制该波纹度，第一和第二外部的材料幅面的材料宽度相互之间的比例可以被如此控制，使得制造的层合体在第一外层这一侧上相对于第二外层那一侧具有较高程度的波纹度。由此在各单个卡带的相同的膨胀体积时，外层20和44的相应的昂贵的材料的最少化是可能的。
附图说明
下面借助附图详细阐述本发明，附图示出在制造面状弹性（area-elastic）的有吸附能力的幅面材料时如何实施本发明的方法。
附图示出：
图1可用于实施根据本发明的方法的装置的主要功能元件的示意的侧视图；
图2a由引导及存储牵条构成的成型芯体的构造；
图2b由引导及存储牵条构成的成型芯体以及在成型芯体的缩小部的区域内的导轨的构造；
图2c在成型芯体张开的区域内的成型芯体构造；
图2d在成型芯体完全张开之后的成型芯体构造；
图3单引导部在一个供给装置中的布置，该供给装置在根据图1和2的装置中设置用于施加多组未张紧的或稍微张紧的纱线或绞纱；
图4在使用两个根据图3的被反向驱动的供给装置的情况下得到的弹性的纱线或绞纱和施加的粘合剂在以根据本发明的方式制造的幅面材料中的平面图案；
图5a在使用两个根据图3的被反向驱动的供给装置的情况下得到的弹性的纱线或绞纱和点状施加的粉末状的填充材料在以根据本发明的方式制造的幅面材料中的平面图案；
图5b在使用两个根据图3的被反向驱动的供给装置的情况下得到的弹性的纱线或绞纱和连续地以各离散的单幅面形式供给的粉末状的填充材料在以根据本发明的方式制造的幅面材料中的平面图案；
图5c在使用两个根据图3的被反向驱动的供给装置的情况下得到的弹性的纱线或绞纱和连续地以各离散的单幅面形式供给的、横向于制造方向间歇性地被转向的粉末状的填充材料在以根据本发明的方式制造的幅面材料中的平面图案；
图6根据本发明制造的层合体的示意图，其中第一材料幅面的软管和整合的弹性的中间层在引入超吸收体和与第二外层连接之前横向于制造方向松弛；
图7a成型芯体的横截面的细节示意图，其中使用两个分别在各两个引导牵条之间的存储牵条并且通过对导轨的定位来控制第一外层的逐段式的引入；
图7b根据图7a制造的弹性的幅面材料的弹性纱线的平面图案的平面的松弛状态。
具体实施方式
在图1中简化和显著示意示出的用于实施本发明的方法的装置2具有一个细长的具有正方形横截面的成型芯体5，其通过两个在纵向方向上彼此隔开的供给装置11和14包围。这些供给装置在通过箭头a和b示出的方向上被反向地旋转驱动。在这些环形的供给装置上分别设置在圆周方向上彼此隔开布置的、用于弹性的纱线、条或绞纱的单引导部17，经由单引导部，弹性的元件从其络筒机上抽出并且朝向成型芯体5引导。
一个第一纺织层20优选在幅面应力受控的情况下从一个被可旋转支承和驱动的材料辊26输送并且经由成型凸肩6被折叠成矩形横截面的软管并且被置于在该例子中通过多个牵条35、38构成的成型芯体5的前端部上（图2a）。有利地由此第一纺织层20在构成软管时的重叠通过施加粘合剂、焊接或机械俘获而固定。
如此构成的软管接下来经由在其横截面上逐渐缩小的成型芯体如此引导，使得软管仅仅在成型芯体的宽度缩短的引导牵条35的端部上引导并且位于之间的软管材料借助于导轨或引导金属丝8被导入到通过在引导牵条之间设置的存储牵条38形成的自由空间中（图2b）。
在其圆周上缩短的软管紧接着通过两个反向旋转的供给装置11和14引导。在这些供给装置中由静止的滚子或卷筒的分别在圆周方向上间隔开的单引导部17抽出各单个弹性的纱线、条或绞纱并且放置到第一外部的材料层20的软管上。通过两个供给装置11、14的旋转运动和第一材料层20的进给运动的重叠，得到弹性的元件50、53的反向-对角的图案，其与第一材料层仅仅在成型芯体5的导轨35的尖端上接触，否则露出，图3。
在成型芯体5上进一步的进给过程中在弹性的纱线50、53上涂敷粘合剂优选作为螺旋或回纹纱线的帘子，其在碰撞到弹性纱线50和53的露出的反向-对角的图案上时被纱线转向并且优选润湿和包裹弹性的纱线、特别是纱线50和53的交叉点，图4。
在成型芯体5上进一步的进给过程中成型芯体的横截面如此张开，使得分别有两个对置的引导牵条的宽度相应地扩大并且互补的一对引导牵条的宽度相应地减小，使得首先保留在成型芯体5的存储牵条38中的第一层20的材料被连续地松开并且第一材料层20的软管经由导轨35的端部被绷紧地张紧（图2c）。由此第一材料幅面20的软管与弹性元件17的和施加在弹性元件上的粘合剂的图案面状接触。引导牵条35的成对扩宽和随之而来的互补的引导牵条的缩小的过程在第一材料幅面20的软管经由成型芯体5的进一步的进给过程中相应继续，使得最后第一材料幅面20的软管仅仅经由成型芯体5的两个引导牵条35的端部引导并且因此几乎是平面的。
在进一步的进给过程中如此成型的且变成扁平形状的软管被导入一个装置中，其是两个被反向驱动的牵拉元件（在此是两个辊子或滚子56的形式），该牵拉元件提供牵拉，用于将第一外层20从材料辊26上抽出并且经由成型芯体输送所有材料。
经由牵拉辊56，在材料幅面20两侧由两个彼此隔开距离的被旋转驱动的材料辊41分别将第二外层44的一个单幅面优选以幅面应力受控的方式地抽出和输送，该单幅面与第一材料层20和弹性的平面图案32经由粘合剂29面状连接。
在通过牵拉单元56将第一材料幅面20的扁平的软管与第二材料幅面44的被供给的平面的幅面结合后，在软管的两侧垂直地这样引入超吸收体47，使得相应地与平面图案32相协调的、单独地在体积或重量方面与第一材料幅面20的软管的牵拉速度相协调的单幅面或者说单轨迹连续地慢慢流入，由此得到根据图5b的产品图案。替代地，这些轨迹间歇地或振荡地横向于行进方向地与平面图案32相对应地被机械地或气动地转向（根据图5c的产品图案），或者这些轨迹通过脉动的或间歇性的压缩空气、机械活塞或输送装置的机械转向部被横向于第一材料幅面20的软管的行进方向转向到该软管的通过平面图案32构成的无粘合剂的区域的中心上（图5a的产品图案）。
在粘合剂有利地通过牵拉辊56的压紧力粘合之后并且在两个外层20和44通过嵌入到它们之间的弹性元件50、53彼此连接之后，其中在两个外层之间包围埋入的吸水性的聚合物（超吸收体47），在进一步的进给运动的过程中如此形成的多层的软管沿着纵向被分割成多个单幅面，这些幅面可选择地横跨地卷绕到辊子上或放置在盒子中或被盘绕。
在根据本发明的在此描述的方法的进一步发展中，由第一纺织层20和弹性的元件32的平面图案构成的扁平的软管的宽度在张开到图2d的扁平状态下通过导轨35的宽度的缩小如此松弛和变成皱褶的，使得在与本来基本上扁平的第二外层44连接之后得到一个弹性的有吸附能力的幅面材料。该幅面材料在通过第一纺织层构成的外侧上与在通过第二外层形成的一侧上相比具有程度较高的褶度，图6。
在根据本发明的在此描述的方法的进一步发展中可以期望的和符合目的的是，如此制成的平面的层合体横向于其制造方向配备外层的不同的褶度和因此不同的膨胀体积的各部分，这通过控制超吸收体横向于层合体的制造方向的分布导致吸收能力的有利的横向分布。在图7a中示例地示出，在此情况下如何利用每个引导牵条对38的两个存储牵条38通过在牵拉方向的横向方向上通过导轨8的合适布置在成型芯体5的相应成型的存储部分中嵌入第一外层20的由于成型芯体5的缩小而过剩的幅面材料的不同幅面宽度。如果现在在成型芯体5的张开运动和进给运动的进一步进程中，首先通过存储牵条38在其尖端上的扩宽，材料幅面20与弹性的层50、53的粘合剂29接触，并且紧接着成型芯体5的张开按照附图2b-d继续，并且与超吸收体和第二外层44的组合结束，那么最后得到沿纵向分割的幅面材料，其在松弛的平面的状态下具有外层的褶的在横向方向上条状的变化和因此吸收能力的相应变化，图7b。
可以符合目的的是，替代导轨8，通过来自的引导芯体的负压达到将第一纺织层压入到存储牵条的自由空间中的功能，这通过第一材料幅面20相对于成型芯体的牵条35、38的静电加荷或者通过将压缩空气施加在第一材料层20的软管的外侧上达到。
此外有意义和符合目的的是，图2a和2b的相应四个引导和存储牵条的功能通过相应较高数量的牵条达到，以便特别是在成型芯体5缩小时在第一材料层20的大的幅面宽度时或在高的存储需要时达到良好的材料引导。
即使当各超吸收体部分在原本彼此胶合的幅面材料（其由两个外部的材料幅面20和44以及嵌入的弹性层50和53构成）的无胶的区域内的隔离对于超吸收体47在应用时吸收液体时的膨胀效果和体积加大是有利的，也可以有意义的是，第二外层44在与第一外层20组合之前面状地或以纵向条的形式利用附加的薄层粘合剂润湿，以便尽可能面状地固定超吸收体，由此在液体吸收之前防止该材料的可能的结块并且改善如此制造的层合体的手感。
附图标记清单
2 整体装置
5 成型芯体
6 第一纺织层的成型凸肩
8 第一纺织层的引导部
11 第一供给装置
14 第二供给装置
17 弹性纱线的单引导装置
20 第一纺织层
23 成型凸肩
26 第一纺织层的材料辊
29 粘合剂
32 弹性纱线的平面图案
35 成型芯体的引导牵条
38 成型芯体的存储牵条
41 第二纺织层的材料辊
44 第二纺织层
47 超吸收体
50 第一中间层的单纱线
53 第二中间层的单纱线
56 牵拉装置

Claims (10)

1.用于制造柔韧的有吸附能力的幅面材料的方法，该幅面材料包含两个外部的纺织层，在它们之间加入两个处于预应力下的弹性的中间层并且加入多个由超吸收性的颗粒构成的部分，该幅面材料如此制造：一个纺织的外层经由一个细长的成型芯体折叠成软管，该软管通过该成型芯体的横截面的缩小而尺寸减小并且利用多组尽可能未张紧的弹性的纱线或带互相反向地以软管加强件的形式进行缠绕，在这些弹性元件组上施加粘合剂并且其通过经由成型芯体的张开在张紧状态下与第一外层的软管处于接触，两者一起在软管在成型芯体上的进给运动的进一步进程中变成扁平的形状并且在间歇性地或连续地供给多个单轨迹的超吸收体的情况下与第二外层的两个幅面连接并且在纵向上被分割成横向弹性的各个单幅面。
2.如权利要求1所述的方法，其特征在于，两个外层中之一是薄膜。
3.如权利要求2所述的方法，其特征在于，薄膜是可透过水蒸气的。
4.如上述权利要求1-3所述的方法，其特征在于，替代超吸收体，加入其它的功能性的颗粒。
5.如权利要求4所述的方法，其特征在于，替代所述颗粒，加入成团的、糊状的或纤维形式的功能性材料。
6.如上述权利要求1-5所述的方法，其特征在于，至少一个所述外层是不透水的，然而在与粘合剂相结合的情况下变成透水的。
7.如上述权利要求1-5所述的方法，其特征在于，至少一个所述外层是不透水的，在两个外层连接期间通过机械压力或穿孔变成点状透水的。
8.如上述权利要求1-7所述的方法，其特征在于，第一材料层在利用被加设的弹性层的预应力的情况下在与第二外层连接之前这样在其横向方向上松弛和缩短，使得与第二外部的材料幅面结合时如此形成的幅面材料在通过第一外层形成的幅面侧上具有程度提高的褶皱。
9.如上述权利要求1-8所述的方法，其特征在于，在第二外层的面向超吸收体的一侧上在干燥状态下涂覆附加的粘合剂以用于将超吸收体面状固定。
10.弹性的、柔韧的和有吸附能力的或有再吸附能力的幅面材料，其按照权利要求1-9制成。
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US9056033B2 (en) 2015-06-16
AU2011234939A1 (en) 2012-10-18
RU2012145726A (ru) 2014-05-10
EP2553156A2 (de) 2013-02-06
ZA201207294B (en) 2013-06-26
DE112011101100A5 (de) 2013-04-04
JP5967074B2 (ja) 2016-08-10
JP5917485B2 (ja) 2016-05-18
WO2011120504A2 (de) 2011-10-06
MX2012011297A (es) 2013-02-15
MA34177B1 (fr) 2013-04-03
EP2552372A2 (de) 2013-02-06
JP2013528507A (ja) 2013-07-11

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