CN102482820B - 具有连续玻璃纤维的织物芯 - Google Patents
具有连续玻璃纤维的织物芯 Download PDFInfo
- Publication number
- CN102482820B CN102482820B CN201080037012.1A CN201080037012A CN102482820B CN 102482820 B CN102482820 B CN 102482820B CN 201080037012 A CN201080037012 A CN 201080037012A CN 102482820 B CN102482820 B CN 102482820B
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- China
- Prior art keywords
- glass strands
- continuous glass
- internal layer
- reinforcing components
- molded reinforcing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Abstract
根据本发明的芯包括由连续玻璃纤维的碎条制成的厚而透气性良好的内层(2),该内层(2)被两个外层(3,4)覆盖,这两个外层由具有热熔性表面的纤维段组成。该组件通过将具有热熔性表面的纤维段(3b,4b)刺入来进行固定,所述段沿其长度的一部分刺入内层(2)中并且附着到连续玻璃纤维(2a)上。
Description
技术领域
本发明涉及用作加强产品的凝聚且柔性的织物芯(骨架),该加强产品用于复合材料制品-即用于通过加强纤维加强的基于树脂(聚酯或其他树脂)的制品。
背景技术
已经公知许多由一层或更多层联接在一起的纤维制成的凝聚的织物芯加强结构。该织物芯通常呈包装在卷筒中的柔性垫纱的形式,该垫纱因此能够被输运并在它被用于生产复合材料产品的地点处理。
为了生产复合材料制品,流程通常如下:切出一块具有合适的表面积的织物芯并且将其安置在模具中,然后将树脂引入模具以包围该织物芯。在聚合之后,树脂和嵌件形成机械上牢固的结构。
机械强度特性仅在树脂在组成嵌件的纤维之间充分渗透而不留下任何无树脂的区域的条件下并且在它充分附着到纤维上的条件下获得。还需要纤维占据充分的容积并且均匀地占据待生产的复合材料制品的容积,特别是通过当该制品不平坦时与该制品的形状一致来进行。
最后需要纤维本身具有使得它们能够形成有效的加强嵌件的足够的机械强度。
已经提出各种加强织物芯结构。
因此,文献EP 0 395 548记载了两层式织物加强件的使用,所述织物加强件例如由玻璃纤维制成并分别定位在一中心层的一侧,该中心层由基于具有永久卷曲的合成纤维、例如已进行组织化处理的长40至70mm的聚酯纤维的垫纱制成。这些织物加强件层通过缝合/编织联接到该中心层。
文献EP 0 694 643记载了两个织物加强层的使用,这两个织物加强层各自定位在为所述材料提供厚度的中心层的一侧,所述层通过缝合/编织互相连接,并且抵靠其中一个外表面设置粘合或缝合上的合成纤维网。
缝合/编织技术相对缓慢,并且这样生产的织物芯具有不均匀的可变形性并且在它们的表面处存在外观缺陷。
为了提高生产率并减少源自编织操作的缺陷,WO 2008/139423 A1最近提出基于纤维的织物芯的生产,该织物芯包括厚而通气的内层和定位在该内层的每侧上的外层,该内层基于已经受使它们永久卷曲的处理的合成纤维的90mm部分,所述外层包括具有热熔性表面的纤维部分,所述具有热熔性表面的纤维部分中的至少一些在它们的长度的一部分上穿过内层并且部分地互相附着且附着到内层的合成纤维上。
此结构的益处是它给织物加强件提供了大的柔性和良好的可变形性,以使得它们能够符合复杂模具的形状,卷曲的合成纤维确保了内层维持充分的容积以便树脂在后续的模制操作期间的正确渗透。
可将50mm的裁切玻璃纤维引入外层。然而,对于某些应用,希望进一步提供复合材料制品的机械特性,特别是其屈服或弯曲强度。
根据文献WO 98/42495 A1中记载的另一种公知技术,利用通过聚合粘结剂结合在一起的连续的玻璃线股来生产模制的加强产品。
这种包含连续的玻璃线股的加强产品能用于利用注射模制来生产复合材料产品。
直径通常为5μm至24μm的单个玻璃长丝的集合称为线股。线股通常包括约40个长丝。线股的集合称为粗纱。粗纱通常包含约50个线股。
为了允许注射模制,希望使用充分通气的加强产品,特别是对于给定重量的线股具有或维持足够膨松的加强产品。
文献WO 98/42495 A1教导了一种由取自卷筒或“纱架”的连续线股的层形成的加强产品。粗纱是由绕卷筒轴线或多或少粘在一起的基本线股组成的卷绕的粗纱组件。在该文献中,来自粗纱的线股在其上被喷射可聚合的液体粘合剂的同时通过空气射流或轧辊膨胀,然后将以垫纱的形式随机安放在支承件上。
此技术的缺点是仍需存在粘合剂以在它在注射模制步骤前进行处理时给加强产品提供凝聚性。其结果是玻璃纤维的量保持相对低并且粘合剂易于降低树脂在注射模制步骤期间渗透的能力。
此外,该公知技术设计成用于生产有限尺寸的片材,并且不适合例如能够容易地切割成选定形状的元件的连续生产。
发明内容
本发明所解决的问题是显著提高利用基于纤维的模制加强件生产的复合材料制品的机械强度,同时在模制前维持该模制加强件所呈现的凝聚性(紧密性,黏合性,连贯性,一致性,cohérence)、柔性和可变形特性,并且确保模制加强件维持令人满意的体积以及维持与树脂在模制时的透入和压印有关的良好特性。
另外,本发明提出在需要的情况下提高通过利用模制加强件模制而生产的复合材料制品的表面的均匀度。
优选地,本发明还寻求允许将加强产品作为连续条带生产,该连续条带能够作为卷筒进行包装(打包),并且能够进行切割或裁切而不存在边缘被损坏或磨损的风险。
为了实现这些和其他目的,本发明提供一种由基于纤维(以纤维为基础)的垫纱(纱层,纤维片层,nappe)制成的模制加强件,包括:
-基于纤维的厚而通气(充气,透气,通风)的内层,
-定位在该内层的每一侧上的外层,
-所述外层包括具有热熔性(可热熔)表面的纤维部分,
-具有热熔性表面的纤维部分中的至少一些在它们的长度的一部分上刺入该内层,并且部分地互相附着(粘附,紧贴)以及附着到该内层的纤维上,
-其中该内层包括以数种厚度并以随机定向延伸的连续玻璃线股型的纤维。
以随机定向并以数种厚度放置的玻璃线股的连续性质利用它们良好的弹性效应来给内层提供在模制时促使树脂渗透的充分厚且通气的性质。内层的连续玻璃线股因此使得可以显著改善通过模制这种加强件而生产的复合材料制品的机械特性。外层-该外层的一些纤维部分刺入并附着到内层的纤维上-可以在已制造模制加强件之后但在该加强件被使用之前暂时将内层的连续玻璃线股足够牢固地保持在一起。
同时,带有刺入并附着的纤维的外层允许仅使用少量的玻璃以外的材料-即在使玻璃在模制加强件中的相对比例最大化的同时-来将连续玻璃线股保持在一起。
外层可以特别薄,呈例如克重(基重,grammage)为约25至30g/m2的纤维的网(覆盖物,voile)的形式。
为了从内层中的玻璃线股的弹性效应受益,重要的是这些线股形成环圈和交织(交叉,交错),以使大部分玻璃线股均在它们的长度的数个部分上抵靠相邻厚度的其它线股,这些接触点之间的中间部分保持自由和弹性柔性,从而给内层提供被弹性压缩的能力。该效果自然可以通过长线股例如超过1米长的线股来获得。然而,已发现,通过被裁切为较短长度例如约20到40cm之间的长度的线股仍出乎意料地获得了此效果。
在说明书和权利要求中,玻璃线股因此在它们的长度超过约20cm时被认为是“连续的”。
在第一实施例中,连续玻璃线股是长度大于约20cm的线股部分。
20至40cm的线股的优点是更容易在将它们放置到合成纤维的网上的步骤中使用:将卷绕成卷筒的长的连续玻璃线股放置到连续移动的支承件上使得,为了避免线股的任何扭转,必须与卷筒轴线成直角旋转卷筒,并且在每个卷筒结束时停止该移动;相反,将玻璃线股部分放置到移动的支承件上是容易的并且能够以完全不中断的方式执行。
呈随机定向放置的玻璃线股部分需具有充分的数量,以便形成数种线股厚度并因此在垫纱或模制加强件的表面上构成连续网格(maillage)。
这种连续网格还使得更容易获得随后通过模制该模制加强件而生产的复合材料制品的良好的机械强度。已估算,在相同条件下,根据本发明的具有20cm玻璃线股的模制加强件所提供的机械强度比具有5cm长的玻璃线股的模制加强件所提供的机械强度高20%。
根据另一实施例,连续玻璃线股的形式为由长的连续玻璃线股形成的至少一个膨胀粗纱(mèche),该粗纱来自卷筒或“纱架”。
这种膨胀粗纱的布置还有利于弹性效应给内层提供满意的厚度和通气性质以允许树脂渗透。
连续玻璃线股的粗纱可有利地具有介于约2400与4800tex(特)之间的支数。
连续玻璃线股可有利地由单位(单体)直径介于约14μm与约17μm之间的长丝(单丝)的组件形成。
作为替换或附加,连续玻璃线股可具有约40至80tex的单位支数。
为了提高通过包覆成型根据本发明的模制加强件而生产的复合材料制品的表面的均匀度,有利地可在内层与至少一个外层之间设置基于裁切的玻璃纤维的中间层。
根据一个有利的实施例,根据本发明的模制加强件可具有介于400与1800g/m2之间的克重。这是模制加强件的厚度与其在模制前的变形能力之间的良好折衷。
根据另一方面,本发明提供一种制造这种模制加强件的方法,包括以下步骤:
a)提供具有热熔性表面的化学纤维的第一网,
b)将连续玻璃线股全部以随机定向和数种厚度放置在具有热熔性表面的化学纤维的第一网上,以形成连续玻璃线股的内层,
c)将具有热熔性表面的化学纤维的第二网放在连续玻璃线股的层上,
d)执行双面的轻针刺操作,以使每个网中具有热熔性表面的纤维部分刺入内层,
e)将整个组件加热到足够高的温度,以使具有热熔性表面的纤维软化并且使它们呈粘性,
f)冷轧该组件。
根据第一可能性,在步骤b)期间,将连续玻璃线股以长的连续玻璃线股的一个或多个膨胀粗纱的形式放置。
优选地,在步骤b)期间,将连续玻璃线股以长度超过约20cm的玻璃线股部分的形式放置。
附图说明
本发明的其他目的、特征和优点将会从下文结合附图对特定实施例的描述而显现,在附图中:
-图1是根据本发明第一实施例的模制加强件的纵向剖面的示意图;
-图2是由连续玻璃线股形成的粗纱在进行膨胀处理时的示意性透视图;
-图3是连续玻璃线股的透视图;
-图4是图1中的模制加强件在制造过程中的纵向剖面的示意图;和
-图5是根据本发明第二实施例的模制加强件的纵向剖面的示意图。
具体实施方式
在图1所示的第一实施例中,根据本发明的模制加强件1包括三层纤维,即一个内层2以及布置在该内层2各侧的两个外层3和4。
内层2包括呈随机定向并呈几种厚度延伸的连续玻璃线股2a。这意味着在内层2中,连续玻璃线股2a在内层2的总体平面内相继采取所有可能的定向,从而形成环圈。连续玻璃线股2a例如在沿其长度的数个部分处还搁在内层2中的相邻连续玻璃线股上。由于环圈例如图1中的环圈2c、2d和2e的存在,接触点沿数个方向延伸。接触点之间的连续玻璃线股的中间部分保持有弹力的柔性并且赋予内层2通气的结构和被弹性压缩的能力。
外层3和4均包含具有热熔性表面的纤维部分3a和4a。
具有热熔性表面的纤维部分3a和4a可由具有足够低的熔点和能附着到内层2的连续玻璃线股2a上的良好特性的任何材料制成。
作为替换,具有热熔性表面的纤维部分3a和4a可为双组分化学纤维,包括由聚酰胺、聚酯或聚丙烯制成的中央芯和由共聚多酯、聚乙烯或具有低于中央芯的熔点的任何其它材料制成的外皮。利用由聚酯制成的中央芯和由共聚多酯制成的外皮,或者由聚丙烯制成的中央芯和由聚乙烯制成的外皮,可实现良好的结果。可以以共轴双组分纤维的形式使用其他成对材料:聚丙烯和共聚聚丙烯,聚丙烯和乙烯醋酸乙烯酯。
由于双组分纤维的中央芯具有高于外皮的熔点,所以避免了在模制加强件1的制造期间意外地完全熔化具有热熔性表面的纤维部分3a和4a的风险。
还有效地限制了下述风险:热熔性纤维部分3a和4a因为在进行加热以制造模制嵌件1的步骤期间的过度或不受控的加热而完全熔化,从而通过其组成材料在加强层2的上、下表面上的扩散蔓延而形成均匀层或树脂不能透过的层。双组分纤维的芯不会被破坏(或者仅很少地被破坏)并且因此维持了外层3和4。
此外,使用具有外皮和中央芯的热熔性表面的双组分纤维意味着能够减少模制加强件1的聚烯烃含量。这是有利的,因为树脂与聚烯烃不是特别兼容的。
内层3和4内的具有热熔性表面的纤维部分3a和4a中的至少一些-例如图1中的刺入部分3b和4b-在它们的长度的一部分上刺入内层2并且部分地互相附着以及附着于内层2的连续玻璃线股2a。
纤维的刺入部分3b和4b均匀地分布在模制加强件1的表面上并且为整个组件提供附着性,而同时维持了模制加强件1的可变形性和柔性特性。刺入部分的表面密度可为例如每平方厘米模制加强件1的表面积(刺入)5至10个部分。
在实践中,根据第一实施例,在内层2中,连续玻璃线股2a可有利地作为长的连续玻璃线股的至少一个膨胀粗纱分布。作为实例,图2示出这种粗纱5或大致互相平行的成束线股。首先,在该粗纱中,连续玻璃线股2a互相接触。随着粗纱5膨胀,线股互相散开,而同时保持基本平行或者保持在不是特别发散的方向上。
作为替换,可优选利用至少约20cm长的玻璃线股部分的交织形成内层2。由于它们的交织和随机定向,连续玻璃线股在模制加强件1的表面上形成连续网格。
将有利地选择由长丝20a的组件形成的连续玻璃线股2a(图3),该长丝的单位直径介于约14μm与约17μm之间。通过组装约50个玻璃长丝,连续玻璃线股的单位支数的范围例如可在40与80tex之间。
连续玻璃线股2a事实上由足以使它们不会在根据本发明处理和使用期间断裂的量的长丝组成,应指出,通常保持在它们离开制造模具时的尺寸的单个长丝单独以这种方式处理和使用时过于脆弱。
根据本发明的模制加强件1能以作为长卷筒被包装的连续条带的形式生产。
例如,生产用于构成外层3的具有热熔性表面的纤维的第一网,将连续玻璃线股2a的部分或连续玻璃线股2a的一个或多个膨胀粗纱连续放置在该第一网3上,使它们具有随机定向以便产生具有数种厚度的内层2。
连续放置连续玻璃线股2a粗纱的操作可以如文献WO 98/42495 A1中所述那样执行,除了随后在本身在连续输送机上移动的第一网上完成纤维的放置以外。
连续放置连续玻璃线股2a的部分的操作可以通过允许它们从裁切工位的出口随机落下而以用于线股部分的通常公知的方式执行。
用于构成第二外层4的具有热熔性表面的纤维的第二网叠置在由此生产的连续玻璃线股2a的该内层2上。
对由此获得的整个组件进行双面轻针刺操作,该轻针刺操作使每个网中具有热熔表面的纤维部分3a和4a的至少一些(3b,4b)刺入内层2,将整个组件加热到足够高的温度,以使具有热熔性表面的纤维的热熔性部分3b、4b软化并且确保它们附着到内层2的连续玻璃线股2a上。
图4示意性地图示了轻针刺操作并且示出了用于预针刺的针8,该针8驱动纤维的刺入部分3b和4b以使它们刺入内层2。
所执行的轻针刺操作例如实现每平方厘米约5至10个穿孔的穿孔密度。这应当与通常实现至少10倍高的密度的针刺方法相比较。轻针刺操作使得可在根据本发明的模制加强件的制造期间实现高产量。
所执行的轻针刺操作足以确保粗制模制加强件在被传递到下一工位时维持充分的附着性,但不足以给模制加强件1提供永久附着性,并且该加强件仍然不能从针刺机输出以用作加强产品。
在轻针刺操作之后执行的加热操作使外层3和4中的纤维的刺入部分3b、4b的热熔性表面层软化,以使它们呈粘性。已通过轻针刺操作的针8驱动的纤维的刺入部分3b、4b附着到内层2的连续玻璃线股2a上。在冷却之后,模制加强件1的各个层2、3和4因此通过纤维的经针刺并结合的刺入部分3b、4b联接在一起。模制加强件1则是凝聚的并且可被输运。对加热进行调节以使具有热熔性表面的纤维部分3a、4a软化并且使它们呈粘性,但不使它们熔化。
现在参见图5,其中示意性地示出根据本发明的模制加强件的第二实施例。
该第二实施例与图1的第一实施例的不同之处在于内层2与相应的外层3和4之间附加地存在两个中间层9和10。各中间层9或10基于大致平行于加强件的平均平面呈随机定向分布的裁切玻璃纤维。
这些中间层9和10既具有提供机械加强的效果,又具有使内层2的表面平滑的效果。这因此产生表面更平滑的模制加强件,从而使得通过模制该模制加强件而生产的复合材料制品可具有良好的表面光洁度。
同样存在将层2、3、4、9和10结合在一起的纤维的刺入部分3b、4b。
示例1
I)在常规梳理机上形成具有热熔性表面的化学纤维的第一网。化学纤维的一部分由双组分纤维制成,该双组分纤维具有聚酯中央芯和由共聚多酯制成的热熔性外皮。由共聚多酯制成的热熔性外皮具有约110℃的熔点。
双组分化学纤维具有介于约2但尼尔与约4但尼尔之间的单一支数。
II)在常规梳理机上形成与第一网类似的具有热熔性表面的化学纤维的第二网。
III)将连续玻璃线股的一个或多个膨胀粗纱放置在具有热熔性表面的纤维的第一网上,以使都以数种厚度随机定向。连续玻璃线股由具有约15μm的单未直径的40个长丝的组件形成,所述线股具有约50tex的单位支数。
IV)将第二网放在内层2的相对侧上。
V)使用传送带将由此产生的粗制模制加强件引入针刺机。针穿孔的密度为10/cm2。针刺入的深度为12mm。带的行进速度为20m/分钟。
VI)在轻针刺操作之后,以20m/分钟的行进速度将粗制模制加强件引入包括12米长的加热部的通气炉(four àair traversant)。该通气炉的温度为约120℃。
VII)在离开通气炉时,将模制加强件1冷轧至约4至5mm的最终厚度。
该模制加强件的克重为1200g/m2。
该克重能够介于约400与1800g/m2之间。
示例2
使用与以上示例1中相同的步骤生产模制加强件,唯一的区别在于:在步骤III)中,在具有热熔性表面的纤维的第一网上放置的是长20cm并且支数为50tex的玻璃线股部分-每个玻璃线股都由具有约15μm的单位直径的40个长丝形成,数量与示例1中相同,以便获得相同的克重。
在此步骤完成时,发现玻璃线股的层的厚度为约10至15cm(在针刺之前)。该厚度与通过直径相同但长5cm的玻璃线股的部分的交织获得的3或4cm的厚度相比较。这证实了当玻璃线股的长度超过约20cm时玻璃线股所提供的弹性和通气效果。
本发明并不局限于所明确描述的实施例,而且包括被包含在随后的权利要求的范围之内的实施例的变型和概括。
Claims (11)
1.一种由基于纤维的垫纱制成的模制加强件,包括:
-基于纤维的厚且通气的内层(2),
-定位在所述内层(2)的每一侧上的外层(3,4),
-所述外层(3,4)包括具有热熔性表面的纤维部分(3a,4a),
-所述具有热熔性表面的纤维部分(3a,4a)中的至少一些(3b,4b)在它们的长度的一部分上刺入所述内层(2),并且部分地互相附着以及附着到所述内层(2)的纤维上,
其特征在于,所述内层(2)包括连续玻璃线股(2a)型的纤维,该连续玻璃线股是长度超过20cm的线股部分,并且该连续玻璃线股处于数种厚度并以随机定向延伸,这些连续玻璃线股形成环圈和交织,以使大部分连续玻璃线股均在它们的长度的数个部分上抵靠相邻厚度的其它连续玻璃线股,这些连续玻璃线股的接触点之间的中间部分保持自由和弹性柔性,从而给内层提供被弹性压缩的能力。
2.如权利要求1所述的模制加强件,其特征在于,在该内层(2)中,连续玻璃线股(2a)沿所述垫纱的表面形成连续网格。
3.如权利要求1所述的模制加强件,其特征在于,该连续玻璃线股(2a)呈至少一个长的连续玻璃线股的膨胀粗纱(5)的形式,该膨胀粗纱是由连续玻璃线股的集合形成的。
4.如权利要求3所述的模制加强件,其特征在于,该连续玻璃线股的膨胀粗纱(5)具有2400至4800tex的支数。
5.如权利要求1至4中任一项所述的模制加强件,其特征在于,该连续玻璃线股(2a)由单位直径在14μm与17μm之间的范围内的长丝的组件形成。
6.如权利要求1至4中任一项所述的模制加强件,其特征在于,该连续玻璃线股(2a)具有40至80tex的单位支数。
7.如权利要求1至4中任一项所述的模制加强件,其特征在于,该模制加强件还在该内层(2)与至少一个外层(3,4)之间包括基于裁切的玻璃线股的中间层(9,10)。
8.如权利要求1至4中任一项所述的模制加强件,其特征在于,该模制加强件具有介于400与1800g/m2之间的克重。
9.如权利要求1至4中任一项所述的模制加强件,其特征在于,所述模制加强件呈包装成卷筒的连续条带的形式。
10.一种制造如权利要求1至4中任一项所述的模制加强件的方法,包括以下步骤:
a)提供具有热熔性表面的化学纤维的第一网(3),
b)将连续玻璃线股全部以随机定向并以数种厚度放置在该具有热熔性表面的化学纤维的第一网(3)上,以形成连续玻璃线股的内层(2),其中,将所述连续玻璃线股以长度大于20cm的玻璃线股部分的形式放置,并使所述连续玻璃线股形成环圈和交织,以使大部分连续玻璃线股均在它们的长度的数个部分上抵靠相邻厚度的其它连续玻璃线股,这些连续玻璃线股的接触点之间的中间部分保持自由和弹性柔性,从而给内层提供被弹性压缩的能力,
c)在该连续玻璃线股的内层(2)上放置具有热熔性表面的化学纤维的第二网(4),
d)执行双面轻针刺操作,以使每个网(3,4)中的具有热熔性表面的纤维部分(3b,4b)刺入该内层(2),
e)将整个组件加热到足够高的温度,以使具有热熔性表面的纤维软化并使它们呈粘性,
f)冷轧该组件。
11.如权利要求10所述的方法,其特征在于,在步骤b)期间,将所述连续玻璃线股以一个或更多长的连续玻璃线股的膨胀粗纱的形式放置。
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CN104708860A (zh) * | 2015-04-08 | 2015-06-17 | 常州众杰复合材料有限公司 | 一种网格夹芯缝编复合织物及其应用 |
CN111032326B (zh) * | 2017-06-14 | 2022-04-19 | Php纤维有限公司 | 条形复合材料 |
CN107512062A (zh) * | 2017-08-14 | 2017-12-26 | 华信博伟(安徽)车辆部件有限公司 | 一种天窗遮阳板及其制备方法 |
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CN111648035B (zh) * | 2020-06-13 | 2023-10-27 | 郑西双 | Es纤维芯材制品及其制备方法 |
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CN1242736A (zh) * | 1996-12-31 | 2000-01-26 | 欧文斯-康宁玻璃纤维西班牙有限公司 | 具有由玻璃纤维和薄棉纸制成的薄层的复合材料织物 |
CN1784303A (zh) * | 2003-05-05 | 2006-06-07 | 奎德兰特塑料合成股份公司 | 无纺布复合件 |
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Publication number | Publication date |
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WO2011021133A1 (fr) | 2011-02-24 |
EP2467524A1 (fr) | 2012-06-27 |
BR112012003545A2 (pt) | 2016-03-08 |
JP2013502333A (ja) | 2013-01-24 |
US20120148815A1 (en) | 2012-06-14 |
JP5719364B2 (ja) | 2015-05-20 |
MX2012002000A (es) | 2012-09-12 |
FR2949238B1 (fr) | 2011-09-09 |
IL218098A0 (en) | 2012-04-30 |
KR20120094903A (ko) | 2012-08-27 |
MY183998A (en) | 2021-03-17 |
AU2010286073A1 (en) | 2012-03-15 |
CA2771742A1 (fr) | 2011-02-24 |
CN102482820A (zh) | 2012-05-30 |
FR2949238A1 (fr) | 2011-02-25 |
EP2467524B1 (fr) | 2015-11-25 |
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