CN1229446A - 基材吸湿性处理方法和组合物 - Google Patents
基材吸湿性处理方法和组合物 Download PDFInfo
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Abstract
公开了一种处理诸如无纺织物之类基材的改性组合物和方法,以便赋予诸如吸湿性等耐久性能。组合物包含粘度改进剂,使通常粘稠的处理剂的粘度降低,使它们能在室温下涂布,而对处理的基材所要求的性能没有有害影响。优选处理组合物包括:烷基链中含有8~10个碳原子的烷基多苷,以及诸如乙氧基氢化蓖麻油和山梨糖醇单油酸酯的共混物等表面活性剂。按照本发明用高固体含量处理组合物在室温下处理的无纺织物,按照流出试验测得的耐久性为至少2个循环。本发明的处理组合物是稳定的,并且适于许多常用处理系统。加入烷基多苷的量低至1/20份是有效的。诸如无纺织物之类的处理基材有许多用途,例如,用作个人护理用品的组分、揩布和环保织物等。
Description
本申请书要求1996年9月4日提交的美国临时申请No.60/025621的优先权。
背景
无纺织物及其制造是许多研究工作的课题,结果出现了具有许多用途的各种材料。例如,织物单位重量低的和松散结构的无纺织物,用于个人护理物品,如用作可弃尿布内衬,其可以为皮肤提供干燥接触表面,而且易于把液体输送到吸湿量更大的材料上,这些材料也可以是组成和/或结构不同的无纺织物。厚型无纺织物可以设计成微孔结构,使之适用于过滤、吸温和阻隔应用,例如,消毒物品的包布、揩布,或医用、兽医用或工业应用的防护服。还开发了更厚重的无纺织物,用于消遣、农业和建筑用途。但是,这些只是实际上是无限的无纺织物的类型和应用的几个例子,这是本领域的技术人员总会认识的,他们还会承认新的无纺织物及应用正在不断地发现。现已开发出各种方法和设备来制造具有适于这些应用的所需结构和组合物的无纺织物。这些工艺的实例包括纺粘、熔喷和梳理等,将在下文更详细地叙述。本发明对无纺织物具有通用性,正如本领域技术人员将会明白的那样,它并不受仅作为说明用的特定无纺织物的参考文献或实例的限制。
随着成形就能有效地生产出全部所需性能的无纺织物,并不是总是能够实现的;常常必须对无纺织物进行处理,以便改善或改变其性能,例如,对一种或几种液体的吸湿度、对一种或几种液体的排斥性、静电特性、导电性和柔软性等等。常规处理所包括的步骤是,例如,在处理浴中浸渍无纺织物、用处理组合物对无纺织物进行喷涂,以及用处理组合物印刷无纺织物。出于成本和其他理由,通常希望,使用最少量的处理组合物,产生所希望的具有可接受的均匀度的效果。已知,例如,为除去与处理组合物一起施加的水分而在附加的干燥步骤中加热,能够对无纺织物的强度性能产生有害的影响,并且会增加工艺的成本。所以,需要提供一种用于无纺织物的改进的处理方法和/或组合物,它们应能够有效地并可行地实施所需要的处理,而对所希望的非织造纤维织品的物理性能没有有害的影响,并达到所需要的结果。
还已知,大多数可分散水的常规表面活性剂不易与水形成高固体含量[>10%(重量)]、低粘度(>100cp)、稳定的混合物。所以,另一种要求是提供一种高固体含量的处理浴,该处理浴在整个延续时间范围内均是稳定的,而没有相分离,并且在室温下显示低粘度,这意味着有效地实施表面活性剂处理,从而赋予无纺织物基材诸如耐久的亲水性等特性。
发明概述
本发明的目标在于一种改进的能有效、且可行地处理无纺织物的组合物和方法,以便赋予其诸如耐久吸湿性等一种或多种所需要的性能,并得到改性的无纺织物。该方法和组合物包括至少一种与粘度改进剂相组合的表面活性剂,还包括对无纺织物的一面或两面用纯的或高固体含量的处理组合物进行处理。基本上或完全不必进行干燥,从而不存在其有害影响,并且该方法提供能均匀处理无纺织物的一面或两面达到所需要的程度、而对所得效果,例如:纤维织品吸湿性的耐久性等没有不良影响的手段。按照本发明的方法,将无纺织物引到处理工段,在那里,将优选的溶剂含量约90%以下的处理组合物,借助于涂布、浸渍或喷洒等手段,施加到织物上,其量应能有效地处理与组合物所接触的织物区域。然后,可以使所处理后的织物同侧或对侧经受相似的处理,以及,如果有必要的话,稍加干燥。此外,本发明的方法大大地简化了可能需要的任何清洁步骤。所得到的处理过的无纺织物已被证明能在减少组合物需要量的情况下进行均匀的、耐久的和有效的处理,并且没有或者仅有微小不良影响。所优选的处理剂包括表面活性剂(其本身是一种乙氧基化的蓖麻油和山梨糖醇单油酸酯的混合物),以及粘度改进剂、烷基多苷的组合物。对无纺织物的这些处理,特别应用于个人护理、医疗和其他应用领域,例如,揩布、防护服、涂敷器,及其他希望以高固体含量将组合物施加到基材上的应用。
附图简述
图1是本发明用于在非织造织品基材的一面或两面进行处理工艺的示意图。
图2是表示另一种处理系统的相似示意图。
发明详述
定义
本文所使用的术语“无纺布或织品”意指具有交互铺置的单根纤维或线状物之结构的织品,但不象针织物那样以规则的或可鉴别的方式铺置的结构。它还包括赋予类似于织物性能的经原纤化、多孔化和其它处理形成的泡沫和薄膜。无纺织物或织品现已能由许多方法制成,例如,熔喷法、纺粘法和粘接梳理编织法。无纺织物的单位重量通常以每平方码材料的盎司数(osy)或以每平方米的克数(gsm)表示,纤维有效直径通常以微米表示(注:以osy换算成gsm的方法为osy×33.91)。
本文使用的术语“微纤维”意指平均直径不大于约75微米的小直径纤维,例如,平均直径为约0.5微米~约50微米,或者更具体地说,微纤维的平均直径可以为约2微米~约40微米。另一种常常使用的表示纤维直径的词是旦,其定义是每9000米纤维的克数,其可以按下述方法计算,即,以微米为单位的纤维直径的平方,乘以以克/厘米3为单位的密度,再乘以0.00707。旦数越低说明纤维越细,而旦数越高说明纤维越粗。例如,给定直径为15微米的聚丙烯纤维,可以将其换算为旦数,即,将其平方,所得结果乘以0.89克/厘米3,再乘以0.00707。例如,15微米的聚丙烯纤维的旦数为约1.42(152×0.89×0.00707=1.415)。除美国之外,更常使用的计量单位是“特”,其定义是每1000米纤维的克数。特可以按旦数/9计算出。
本文所使用的术语“纺粘纤维”指的是将熔融热塑性材料以长丝的形式从喷丝板的许多细的、通常为圆形的具有挤出长丝直径的毛细管中挤出,然后直径迅速减小所形成的直径很小的纤维,例如,下列专利所述,Appel等人的美国专利4340563、Dorschner等人的美国专利3692618、Matsuki等人的美国专利3802817、Kinney的美国专利3338992和3341394、Hartmann的美国专利3502763、Levy的美国专利3502538和Dobo等人的美国专利3542615。纺粘纤维经骤冷,在将其置于收集面上时一般是不发粘的。纺粘纤维一般是连续的,平均直径大于7微米,更具体地说,为约10~20微米。
本文所使用的术语“熔喷纤维”意指按如下方法形成的纤维,即,将熔融热塑性材料经许多细的、通常为圆形的喷丝头毛细管挤出,以熔融纤维或丝的形式进入会聚高速气流(例如空气)中,使熔融热塑性材料的丝变细来减少其直径,这样可以达到微纤维直径。此后,高速气流携带熔喷纤维,将其置于收集面上,形成无规分布的熔喷纤维织物。这种方法公开在,例如,Butin的美国专利3849241中。熔喷纤维可以是连续的或不连续的微纤维,其平均直径一般小于10微米,当将其置于收集面上时一般是发粘的。
本文所使用的术语“聚合物”一般包括,但不限于,均聚物,共聚物,例如嵌段、接枝、无规和交替共聚物,三元共聚物等,以及其共混物和改性产品。此外,除非另有专门限制,术语“聚合物”包括该材料的所有可能的几何构型。这些构型包括,但不限于,等规、间规和无规对称性。
本文所使用的术语“机器方向”或MD意指织物生产的长度方向。术语“机器横向”或CD意指织物的宽度方向,即通常指垂直于MD的方向。
本文所使用的术语“单组分”纤维指的是仅使用一种聚合物从一台或多台挤出机中挤出的纤维。这并不意味着要排除用一种加入少量添加剂以着色、抗静电、润滑、亲水等的聚合物生成的纤维。这些添加剂,如着色用的二氧化钛,的存在量一般为5%(重量)以下,更典型的是约2%(重量)。
本文所使用的术语“共轭纤维”指的是用至少两种聚合物从分别的挤出机挤出并且纺在一起形成一根纤维所得的纤维。共轭纤维有时也指多组分或双组分纤维。诸聚合物通常是彼此不同的,但是共轭纤维也可以是单组分纤维。聚合物在共轭纤维的横截面上排列在位置基本不变的不同区域,并且沿着共轭纤维长度方向连续地延伸。这种共轭纤维的结构可以是,例如,皮/芯排列,其中一种聚合物围绕着另一种聚合物,或者可以是并列排列或者为“海岛式”排列。共轭纤维叙述在Kaneko等人的美国专利5108820、Strack等人的美国专利5336552和Pike等人的美国专利5382400中。对于双组分纤维来说,聚合物的存在比例可以为75/25、50/50、25/75或任何其他所要求的比例。
本文所使用的术语“双成分纤维”指的是用至少两种聚合物以共混物形式从同一挤出机挤出的纤维。术语“共混物”的定义如下文所述。双成分纤维中,不同聚合物组分在纤维横断面上的不同区域的位置并不是相对不变的,这些不同的聚合物在纤维的整个长度方向上通常是不连续的,而是通常形成无规地开始和结束的原纤维或原生纤维。双成分纤维有时也称为多成分纤维。这种通用型纤维在,例如,Gessner的美国专利5108827中已有叙述。双组分和双成分纤维还详述在教科书“聚合物共混物和复合材料(Polymer Blends and Composites)”中(Johm A.Manson和Leslie H.Sperling编,1976版权属Plenum出版社,纽约的Plenum出版公司的分部,IBSN 0-306-30831-2,第273~277页)。
本文所使用的术语“共混物”,在应用于聚合物时,意指两种或两种以上聚合物的混合物,而术语“熔合物”意指共混物的子类,其中各组分不混溶,但是已相容。“混溶性物”和“不混溶性物”分别被定义为具有负值和正值混合自由能的共混物。另外,“相容作用”被定义为为了制造熔合物改善不混溶的聚合物共混物的界面性能的过程。
本文所使用的“通过空气粘合”或“TAB”意指一种粘合诸如双组分纤维织物等无纺布的方法,其中被升温至足以使构成织物纤维的聚合物之一熔融的空气强制通过织物。空气速度经常为100~500英尺/分钟,停留时间可以长达6秒钟。聚合物的熔融和再固化而实现粘合。通过空气粘合使可变性受到限制,一般被认为是辅助粘合工序。因为TAB需使至少一种组分熔融才能实现粘合,所以TAB限于诸如双组分织物等具有两种组分的织物,或者含有粘合纤维或粘合粉末的织物。
本文所使用的“热点粘合”包括使织物或无纺布通过加热的轧光机辊和砧辊而被粘合。轧光机辊通常是,但不总是,有某种式样的花纹,如此,整个织物通过其整个表面时并不全部被粘合。这样,为了功能和审美的缘故,开发出轧光机辊的各种花纹。花纹的一个例子是点状,为Hansen Pennings或“H & P”花纹,粘合面积约为30%,每平方英寸约200个粘合点,叙述于Hansen和Pennings的美国专利3855046。H &P花纹具有方形点或针状粘合区,其中每个针点的边尺寸为0.038英寸(0.965mm),针点间隔为0.070英寸(1.778mm),粘合深度为0.023英寸(0.584mm)。所得花纹的粘合面积占约29.5%。另一种典型的点粘合花纹是扩展的Hansen and Pennings或“EHP”粘合花纹,其粘合面积为15%,方形针点边尺寸为0.037英寸(0.94mm),针点间距为0.097英寸(2.464mm),深度为0.039英寸(0.991mm)。另一种称作“714”的典型点粘合花纹具有方形针点粘合面,其中每个针点的边尺寸为0.023英寸,针点间隔为0.062英寸(1.575mm),粘合深度为0.033英寸(0.838mm)。所得花纹粘合面积占约15%。还有另一种普通花纹是C-星形花纹,粘合面积约16.9%。C-星形花纹具有交叉方向的条纹或由闪星隔断的灯芯绒图案。其他普通花纹包括带有重复的和稍稍错位的钻石的钻石图案,和金属丝织造花纹,看上去如所谓“窗纱”一样。一般说,粘合面积百分数为层合织物面积的约10%~约30%。正如本领域众所周知的,点状粘合将层合制品的各层固定在一起,并且通过粘合每层中的丝和/或纤维,赋予各个层的整体性。
本文所使用的术语“个人护理用品”意指尿布、运动裤、吸湿衬裤、成人失禁用品、妇女卫生用品。
本文所使用的术语“耐久吸湿性”或“耐久可湿性”意指经受下述流出试验浸湿至少二次,最好至少三次的能力。
本文所使用的术语“亲水的”意指聚合物材料具有的表面自由能,使聚合物材料能够被含水介质,即水是主要组分的液体介质湿润。即,水介质湿润由表面活性剂浴处理过的无纺织物。例如,表面活性剂浴含有至少10%(重量)表面活性剂或表面活性剂混合物,和不大于约90%的诸如水等溶剂。
试验方法
流出试验(暴露)和洗涤/干燥步骤叙述在Meirowitz等人的美国专利5258221中,在此引入其全部内容供作参考。一般,将普通矩形8英寸×15英寸(约20cm×38cm)的诸如无纺织物之类的纤维织品样品装在由聚丙烯、木浆纤维和/或超吸收材料组成的吸收芯的上面。将所得的试验组合件安放在倾斜表面中心,并在组合件的每一个角用带子固定就位。倾斜表面的角度是45°,而不是该专利所述的30°角。将漏斗置于距试验组合件的底边或较低边缘约7.8英寸(约200mm)处。漏斗阀门置于试验组合件上表面上方约10mm处。在漏斗中放置100ml 35℃的水。打开漏斗阀门分送水约15秒。测量并记录流出的和收集在收集器中的水量(克)。如果在收集设备中所收集的水量小于供与给定类型的纤维织品的量,那么一般认为纤维织品通过修正过的流出试验。例如,在纤维织品是薄型(织物单位重量为0.6盎司/平方码或约20克/平方码)纺粘无纺织品时,所收集的水量应小于20ml。
修改洗涤/干燥操作过程,使用室温下的水(约23℃)500ml,而不是1升。这样,将上述涂布多孔基材的普通矩形样品置于500ml水中。将样品在水中保持1分钟,同时用机械搅拌器以15~20转/分钟进行搅拌。从水中取出样品并将过量水挤回到洗涤水容器中。在空气中干燥一夜,或在80℃烘箱(Blue M型OV-475A-3,产自General Signal,Blue Island,IL)中干燥20分钟,然后,经上述修改的流出试验。重复该过程至所需要的次数。
带条拉伸试验是测定织物经受单向应力时的断裂强度、伸长或应力。该试验是ASTM标准试验法D882(薄塑料片材拉伸性能试验法)的修改方法。
对本发明来说,为测定峰值强度,对标准步骤进行了如下修改:
赋予试验装置的夹紧元件的间隔变化速率,对于所有样品来说,均保持50毫米/分钟。
夹紧元件之间的初始间隔,依所试验样品的类型为1英寸至3英寸。当测试背衬带材时初始间隔为1.5英寸,而当测试外包覆材料和固定环带材料时,初始间隔为3英寸。
按如下方法计算峰值强度;负荷-十字头(Crosshead)位移曲线上的最大负荷除以样品的宽度。
所得结果以断裂时的磅数和断裂之前的伸长百分率表示。数值越高,表示织物强度越大,可伸长性越大。术语“负荷”意指拉伸试验中,使样品断裂或破坏所需要的最大负荷或力,以重量单位表示。术语“应力”或“总能量”意指以重量-长度单位表示的负荷-伸长曲线中的总能量。术语“伸长”意指在拉伸试验中样品长度的增加量。抓式拉伸强度和抓式伸长数值,采用特定织物宽度(通常为4英寸(102mm)),夹具宽度和固定的伸长速率得到。样品比夹具宽,所得的结果代表织物中被夹宽度中纤维的有效强度与相邻纤维所贡献的附加强度之和。样品被夹在3英寸(76mm)长的平行夹具中,例如,Instron Model TM,购自Instron公司(坎顿,华盛顿大街2500号,MA 02021,或Thwing-Albert Model INTELLECT II,购自Thwing-Albert Instrument公司(10960 Dutton Rd.,Phila.,PA 19154))。这几乎可完全模拟实际应用中的织物应力条件。
液体透过时间:该试验按EDANA 150.1-90进行,它是测定涂布到与下面的吸收垫相接触的无纺织物试样表面上的已知体积的液体(模拟尿)通过该无纺织物的时间。一般来说,将50ml滴定管置于环架上,其管尖在漏斗内侧。将由5层特定滤纸(吸收率482%)构成的标准吸收垫置于漏斗下面的丙烯酸类有机玻璃底板上,而无纺织物样品则置于吸收垫的上面。丙烯酸玻璃透过板,25mm厚,重500g,被置于样品上,其在漏斗下有位于中心5mm的腔。在滴定管中装上液体,保持漏斗关闭,使10ml液体流入漏斗。将该10毫升液体排出,并起动计时器,当液体渗入垫中并落到一组电极之下时使之停止,记录所经过的时间。对于每个样品重复该试验5次,每次重复均使用相同的试样,并将所记录的时间平均。
也可以将其他材料与所使用的聚合物共混生产本发明的无纺织物,例如,加入用来增加阻燃的防火剂,用来赋予各层相同的或不同颜色的颜料。也可以使用香料添加剂、气味改善剂、抗菌剂和润滑剂等。纺粘和熔喷热塑性聚合物所用的这些组合是本领域已知的,且常常是内添加剂。如果使用颜料,其加入量一般为该层的5%(重量)以下,同时其他材料的累积量,则可以为25%(重量)以下。
用于制造本发明织物的纤维可以采用本领域已知的熔喷或纺粘工艺等方法生产。这些工艺一般使用挤出机将熔融的热塑性聚合物挤向喷丝板,使聚合物成纤,生产出纤维或较长的纤维。然后,将纤维拉伸,通常采用气流拉伸,置于运动的多孔底板或带上,形成无纺织物。按纺粘工艺和熔喷工艺所生产的纤维是上文所定义的微纤维。
以上概括地讨论了熔喷织品的制法,作为参考。
本发明的织物可以是多层层合制品。多层层合制品的一个例子是下述实施方案,其中一些层是纺粘,而一些层是熔喷,例如纺粘/熔喷/纺粘(SMS)层合制品,正如在Brock等人的美国专利4041203、Collier等人的美国专利5169706、Yahiaoui等人的美国专利5540979和Bornslaeger的美国专利4374888所公开的。这样的层合制品可以通过如下方法制造:在移动的成形带上按顺序放置先是纺粘织物层、然后是熔喷织物层、而最后是另一纺粘层,然后按下述方法粘合该层合制品。或者,可以单独制造各织物层,合并在辊上,再在另一粘合步骤中结合在一起。这类织物的单位重量通常为约0.1~12osy(6~400gsm),或者更具体地说为约0.75~约3osy。
在生产纺粘无纺织物时,通常采用某种方法将其粘合在一起,以便使其具有足够的结构完整性,使之能经受进一步加工为最终产品过程中所受到的严酷作用。能够用许多方法完成粘合,例如:流体缠结(hydroentanglement)、针刺、超声波粘合、粘合剂粘合、缝编、透气粘合和热粘合。
正如以上所指出的,对于处理许多应用领域的无纺织物,其重要参数是吸湿耐久性,或者使用中经受多次浸湿的能力。对用于尿布内衬来说,例如,极其需要在3次或更多次浸湿之后仍保持吸湿性的能力。按照这一标准,一些可行的处理方式证明能达到耐久性,例如使乙氧基化的氢化蓖麻油和山梨糖醇单油酸酯(Ahcovel N-62,可得自ICI公司,也简称为“Ahcovel”)共混物。然而,这种处理物上很粘稠,难以采用常用处理方法于固体含量高的情况下涂布。传统的粘度改性添加剂或表面活性剂的共混物,可以使之粘度下降,但是它们对处理过的织物的耐久性却存在有害的影响,如下文所详述的,参见表3和4。按照本发明,现已发现,使用特定的烷基多苷不仅使其粘度下降,而且能保持理想的耐久性。最好的结果是,烷基多苷是烷基链中具有8~10个碳原子者(例如Glucopon 220UP),其含量为约5%~约80%,最好约5%~约10%(以总组合物重量和烷基多苷组合物的重量为基础计),可以是含水的,例如,含有约40%水。下表1示出了添加Glucopon 220UP对Ahcovel Base N-62的粘度的影响,前者为60%烷基多苷的40%水的溶液(按重量计),可购自Henkel公司(也简称作“Glucopon”)。在每种情况下粘度测定均采用布鲁克菲尔德DV II+粘度计、锭子CP41,在剪切速率为20(1/sec)下,以总固体20%的组合物进行。表1.Glucopon对含有20%固体的Ahcovel的粘度*的影响
*用布鲁克菲尔德DV II+粘度计、锭子CP-41进行测定
处理组合物 | 比率 | 粘度(cp.) | 温度(℃) | 剪切速率(sec.-1) |
AhcovelAhcovelAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/Glucopon | 1120/115/110/15/13/11/1 | 11031504014<12.3<12.3<12.3<12.3 | 2547252525252525 | 2020202020202020 |
对于本发明来说,在使用条件下(优选在室温下),需要粘度达到约100cp以下,这样能够使用高固体含量常用系统和方法,例如WEKO转子阻尼系统(可得自Weko公司)。本领域技术人员很容易推想,可以应用其他涂布机,例如,刷喷涂布机和涂敷印刷涂布机。如上所述,表面活性剂单独不能满足这项要求,而低至1/20份诸如Glucopon 220UP之类的烷基多苷的添加量就会显著地降低其粘度。
相信本发明适用于对各种各样组合物进行粘度降低处理,但是最优选的是与诸如Ahcovel系列表面活性剂组合物的组合,其原因是这种处理具耐久性。然而,在耐久性程度要求不苛刻的地方,唯一必须的是,组合物应含有有效量的混合表面活性剂和粘度调节剂以进行无纺织物的处理。为了决定适用性,可以采用布鲁克菲尔德粘度计进行试验。所优选的组合物是粘度约2000cps或更低者。具体实例包括Triton x-102,购自Union Carbide公司的烷基酚乙氧基化物表面活性剂;Y12488和Y12734,购自OSi的乙氧基化的聚二甲基硅氧烷系列;Masil SF-19,购自PPG的聚乙二醇-接枝三硅氧烷;聚乙二醇单硬脂酸酯、二硬脂酸酯和单月桂酸酯的PEG 200、400和600系列,购自PPG;购自Finetex的GEMTEX SM-33和SC75系列,和磺基丁二酸二烷基酯;以及可溶于水的聚合物,如聚乙烯基吡咯啉酮、聚乙烯醇、乙基羟乙基纤维素、羧甲基纤维素、羟丙基纤维素、淀粉、琼脂,和其他天然水溶性聚合物。粘度改进剂的实例包括Glucopon 220或225,两者均为烷基链中具有8~10个碳原子的烷基多苷,均可购自Henkel公司。所得混合物作为乳液,在使用条件下的粘度为100cp以下,优选,甚至更可取的是50cp以下。
虽然本发明广泛地适用于处理各种无纺织物,但是最有效的,所以也是优选的是具有可高速有效处理性能的无纺织物。这些性能包括织物单位重量,例如5~500gsm;厚度,例如0.2~10毫米,等。
为了使本发明的优点得到最大发挥,优选进行无纺织物和处理组合物的选择,以便该组合物可以借助不多于约80%水(优选)来施用。
参见图1,所述的工艺适用于对运行的织品的一面或双面进行涂布。本领域的技术人员很容易明白,本发明同样地适用于联机处理或单独、脱机处理步骤。织品12,例如纺粘或熔喷无纺织物,在支持辊15下被导向处理区,该处理区包括旋转喷洒头22,以便对织品12的一面14涂布。也可任选使用包括旋转喷洒头(未示出)的处理区18(示出部分剖视图),以便对织品12的反面23涂布,并通过支持辊17,19。每个处理区均接受自贮槽(未示出)供应的处理液30。然后,如果需要,可以使处理过的织品通过烘干筒(未示出)进行干燥,或者采用其他干燥设备来进行,然后在支持辊25下卷绕成卷,或者送至要使用的地方。其它干燥设备包括烘箱透气干燥器、红外干燥器、鼓风机等。
图2表示另一种设备,其采用浸渍和挤干涂布步骤。正如所示,织品100通过导辊102进入浴104,处理时间由导辊106进行控制。借助挤压辊108之间的辊隙排出过量处理组合物,借助收集盘109返回到浴中。烘干筒110排出残留的水分。
也可理解,采用本发明的外涂布表面活性剂进行无纺材料的亲水表面处理方法,不仅可以包括多种表面活性剂,以改善其对含水液体(如尿)的吸湿性,或便于处理其他体液(血、月经液体、粪便等),而且也可包括生物活性化合物和大分子物,这些物质可以对本发明的表面处理提供生物功能特性(例如:抗菌活性、改善气味和皮肤保养等)。
通过如下实例进一步说明本发明,这些实例是本发明的典型,但是其他实例对本领域技术人员来说,也属显而易见,势必包括在权利要求之中。
实施例
实例1~43
高固体含量/低粘度表面活性剂配方
采用低固体含量的浴中的表面活性剂进行无纺材料的亲水处理的多种方法是已知的且常用的。然而,因为溶剂含量高,需要干燥步骤。已知,无纺材料进行表面处理之后,干燥过程所施加的热对其机械性能存在不良影响(表2)。因此,使用高固体含量浴把对干燥设备的需求减至最小或者消除,从而保持织物的固有拉伸强度。高固体含量处理系统的其他显见优点包括:表面活性剂配制、运输和贮存成本较低,节约能量,处理成本较低和处理均匀性较好。本文所使用的“高固体含量”意指固体含量至少约10%,优选该组合物含至少约20%固体。
表2.干燥对0.6osy聚丙烯纺粘织物机械性能影响的数据比较
(KC Test 690-W Tensile)
*织物1:采用高固体含量WEKO工艺用0.9% Ahcovel/Glucopon进行处理,未进行干燥**织物2:采用低固体含量饱和处理法,用0.9% Ahcovel/Glucopon进行处理,在220°F下进行干燥
条带拉伸 条带拉伸 条带拉伸 条带拉伸 条带拉伸 条带拉伸峰值能量 峰值负荷 峰值应力 峰值能量 峰值负荷 峰值应力CD干燥 CD干燥 CD干燥, MD干燥 MD干燥 MD干燥,% % | |
织物1*织物2** | 7.62 7.90 50.66 10.08 12.42 39.445.06 6.24 52.45 6.19 11.42 27.61 |
另一方面,较高固体含量的表面活性剂也有缺点,例如:流变性差、乳液不稳定、胶凝和处理的多变性。关于外涂布表面活性剂进行非织造材料处理的其他复杂问题是,当多次暴露到含水液体时保持吸水性能的耐久性或能力。
因此,本发明的目标是三个方面:1)提供可在室温下使用的低粘度/高固体含量处理组合物,2)提供无干燥要求或将其降到最低限度的高固体含量处理组合物,3)提供能赋予无纺织物耐久吸湿性的处理组合物。
以下步骤是,当使用本发明的高固体含量/低粘度处理组合物时,所使用的典型的通用方法。
无纺织物
一般,14″宽、0.6盎司/平方码(osy)纺粘织物卷,由聚丙烯纤维(约2.2dpf)制造。
表面活性剂配方
一般,所配制的含水处理浴含有0.075%消泡剂(Dow 2210,购自Dow Corning)和20%(重量)表面活性剂制剂(表3)。在室温下充分混合之后,将表面活性剂制剂倒入处理槽中,在室温下继续混合(除非另有要求)(表3)。
表3.无纺织物各种亲水处理的耐久性实验数据和比较
(高固体含量的WEKO工艺)
表3(续)
表3(续)
表3(续)
*对于高固体含量的应用来说,粘度太高
实例# | 编号 | 处理组合物,含20%固体 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | ||
表面活性剂系统 | 比率 | 粘度(cp)20秒-1(T=25℃) | |||||
123456789101112 | C1C2C3C4C5C6C7C8C9D1D2D3 | Ahcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19 | 10∶110∶110∶115∶115∶115∶120∶120∶120∶120∶1∶120∶1∶120∶1∶1 | <12<12<12141414404040808080 | 252525252525252525252525 | 0.30.60.90.30.50.90.30.50.90.30.60.9 | 24624836>10124 |
实例# | 编号 | 处理组合物,含20%固体 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | ||
表面活性剂系统 | 比率 | 粘度(cp)20秒-1(T=25℃) | |||||
131415161718192021222324 | D4D5D6D7D8D9E1E2E3E4E5E6 | Ahcovel/Glucopon/SF l9Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488 | 10∶1∶110∶1∶110∶1∶110∶1∶210∶1∶210∶1∶210∶1∶110∶1∶110∶1∶120∶1∶120∶1∶120∶1∶1 | 282828252525282828858585 | 252525252525252525252525 | 0.30.60.90.30.60.90.30.60.90.30.60.9 | 001000122136 |
实例# | 编号 | 处理组合物,含20%固体 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | |||
表面活性剂系统 | 比率 | 粘度(cp)20秒-1(T=25℃) | ||||||
252627282930313233343536 | E7E8E9A1A2A3B1B2B3G1G1G1 | Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488Ahcovel/Glucopon/Y 12488AhcovelAhcovelAhcovelGlucopon 220UPGlucopon 220UPGlucopon 220UPTriton X-102Triton X-102Triton X-102 | 10∶1∶210∶1∶210∶1∶2111111111 | 353535110311031103<12<12<12120120120 | 150150150232323 | 252525474747252525474747 | 0.30.60.90.30.60.90.30.60.90.30.60.9 | 11224>10001000 |
实例# | 编号 | 处理组合物,含20%固体 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | ||
表面活性剂系统 | 比率 | 粘度(cp)20秒-1(T=25℃) | |||||
37383940414243 | H1H1H1F1F3F4F5 | PEG 400MLPEG 400MLPEG 400MLAhcovel/TL 2119Ahcovel/PEG 400MLAhcovel/Pluronic L 101Ahcovel/Mazawet 77 | 11115∶115∶115∶115∶1 | 404040650*350*>10,000*420* | 252525n/an/an/an/a | 0.30.60.9n/an/an/an/a | 001n/an/an/an/a |
涂布方法
使用WEKO处理器(WEKO,Biel公司,瑞士)涂布本发明的高固体含量低粘度表面活性剂处理组合物。一般的WEKO结构是如图1所示的采用单或双旋转传递体的离心阻尼施加系统。经齿轮泵将表面活性剂制剂泵入WEKO头,经限流管送入阻尼转子。本发明使用的中试WEKO设备装有以约4500rpm速度旋转的6个转子。在旋转转子产生的离心力的作用下,化学品以小滴的形式散布在无纺织物上。
采用不同直径的节流管、头压和浴参数(温度和粘度)控制和调节通过量(克/分钟)。任选把针阀加到头部出口进行通过量精细控制。
干燥
实例1~43中所处理的全部织物均不需任何干燥过程。
增量率
织物的增量率采用Brucker Minispec 120 Pulse NMR(BruckerSpectrospin,Canada,Ltd.)通过低分辨固态核磁共振(NMR)谱进行测定。关于这种分析方法的其他参考资料也可见于:“Wide Line NuclearMagnetic Resonance in Messurement of Finish-on-Fiber of TextileProducts”,J.E.Rodgers,发表在光谱学(Spectroscopy),9(8),40(1994)。
一种优选的表面活性剂处理组合物叙述在实例1~6中。正如表3所示,实例1~6的织物采用相对粘度很低的高固体含量的Ahcovel和Glucopon的比率为10∶1至20∶1的含水乳液进行处理。值得注意的是,举例说,在采用WEKO工艺进行了表面处理之后,所处理过的织物不需任何后干燥工序。在将实例1~6与表3所报告的其他处理进行比较中,不寻常的结果是按照本发明所述的表面活性剂/粘度改性剂进行的处理的耐久性。处理组合物的独特性存在于具有如下特征的同时完成的方法之中,即,1)可在室温下应用的高固体含量、低粘度、稳定的含水乳液;2)不需要进行干燥;3)改进了的按本发明所述流出试验评估的处理耐久性。
表4.采用各种表面活性剂和辅助表面活性剂系统用低固体含量的浴池涂布无纺布
的各种亲水处理的耐久性实验数据及其比较(低固体含量饱和处理)
表4(续)
表4(续)
实例# | 编号 | 处理组合物 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | ||
表面活性剂系统 | 比率 | 浴中固体% | |||||
444546474849505152535455 | E10E10E10E11E11E11E12E12E12E13E13E13 | Ahcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/TL 2119Ahcovel/TL 2119Ahcovel/TL 2199Ahcovel/PEG 400 MLAhcovel/PEG 400 MLAhcovel/PEG 400 MLAhcovel/Pluronic L 101Ahcovel/Pluronic L 101Ahcovel/Pluronic L 101 | 3∶13∶13∶13∶13∶13∶13∶13∶13∶13∶13∶13∶1 | 0.30.60.90.30.60.60.30.60.60.30.60.6 | 252525252525252525252525 | 0.30.60.90.30.60.90.30.60.90.30.60.9 | 236000000112 |
实例# | 编号 | 处理组合物 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | ||
表面活性剂系统 | 比率 | 浴中固体% | |||||
565758596061626364656667 | E14E14E14A4A5A6H2H2H2G3G3G3 | Ahcovel/G 2109Ahcovel/G 2109Ahcovel/G 2109AhcovelAhcovelAhcovelPEG 400MLPEG 400MLPEG 400MLPluronic L 101Pluronic L 101Pluronic L 101 | 3∶13∶13∶1111111111 | 0.30.60.60.30.60.90.30.60.60.30.60.6 | 252525252525252525252525 | 0.30.60.90.30.60.90.30.60.90.30.60.9 | 00124>10001011 |
实例# | 编号 | 处理组合物 | 涂布温度(C) | 增量率(wt%) | 耐久性(循环次数) | ||
表面活性剂系统 | 比率 | 浴中固体% | |||||
686970717273747576 | G4G4G4G5G5G5G6G6G6 | Mazawet 77Mazawet 77Mazawet 77G 2109G 2109G 2109G 1282G 1282G 1282 | 111111111 | 0.30.60.60.30.60.60.30.60.6 | 252525252525252525 | 0.30.60.90.30.60.90.30.60.9 | 000000000 |
流出试验所提供的数据清楚说明,表3中的实例1~11和实例27~29,和表4中的实例44~46、59~61实现了耐久性处理。从流出试验结果可知,仅单独的Ahcovel型表面活性剂以及该表面活性剂与其他表面活性剂的某些复合配方通过了耐久性试验。从耐久性结果(源于流出试验)也表明,增量率和耐久性程度(或流出循环次数)之间的正比关系仅仅存在于Ahcovel型表面活性剂和某些复合配方中,例如Ahcovel/Glucopon、Ahcovel/Glucopon/SF 19和Ahcovel/Glucopon/Y12488。这种相互关系对于其它类型的单一表面活性剂处理和诸如Ahcovel/PEG 400ML、Ahcovel/TL 2119、Ahcovel/G 2109等某些Ahcovel型复合配方来说实质上是不存在的。在后一复合配方中,看来将辅助表面活性剂加到Ahcovel中,对处理的耐久性是有害的。
EDANA液体透过数据提供了关于处理过的织物的液体吸入速率的资料,而且也提供了处理耐久性的资料,上述织物经受10ml盐水的作用5次。在表6中的数据清楚地说明,初始液体吸入时间,对于所有处理过的织物,大致是相同的。性能的差异在于,织物受到多次液体浸湿时。例如:Triton X-102处理的织物的液体吸入时间在循环4次和5次时出现恶化,Ahcovel和Ahcovel/Glucopon、Ahcovel/Glucopon/SF 19,经爱5次盐水作用,性能受到的影响仍较少。所以,EDANA液体透过数据与处理耐久性是一致的,并且结果与流出试验结果一致。
实例44~76
低固体含量饱和处理法
以下步骤是,当使用本发明的低固体含量饱和处理时所使用的典型通用方法。
一般,所制备的含水处理浴含有0.15%消泡剂(Dow 2210,产自Dow Corning)、0.5%己醇,以及按表4所示条件加入需要量的表面活性剂或辅助表面活性剂。在室温下均匀混合之后,将表面活性剂制剂倒入处理工段的槽中(图2)。聚丙烯纺粘纤维(约2.2dpf)制成一般为14″宽、0.6osy织物卷,用表面处理组合物进行处理,如表4所示。在织物经饱和浸渍并在橡胶辊间压轧之后,测定吸液百分率(% WPU),据此决定增量率。% WPU以重量分析法测定,并由下式计算出: 式中,Ww和Wd分别是约12″×12″织物试样的湿重和干重。例如,由0.3%的固体浴处理的织物,测定得100% WPU,其意思应当是织物的增量率达到0.3%。增量率主要由浴的化学品浓度、线速度和压轧压力控制(表5)。表5.低固体含量饱和涂布系统的工艺条件
*±5%
浴浓度(%重量) | WPU*(%) | 目标增量率(%重量) | 线速度(ft/分钟) | 压轧压力(psi) |
0.30.60.9 | 100100100 | 0.30.60.9 | 703516 | 403530 |
在目标增量率验证之后,使所处理的织物经一系列蒸汽加热烘干筒进行干燥(图2)。然后,分批检测处理过的和干燥的织物的耐久性(流出/洗涤/干燥试验)和液体吸入速率(EDANA液体透过时间)。
表6.经各种亲水处理的无纺布的EDANA液体透过时间的实验数据及其比较
(高固体含量的WEKO工艺)
表6(续)
实例# | 处理组合物,20%固体 | 涂布温度(℃) | 增量率(%重量) | EDANA-流体透过时间(秒) | |||
表面活性剂系统 | 比率 | 粘度(cp)在20秒-1下 | 循环 循环 循环 循环 循环1 2 3 4 5 | ||||
25℃ 47℃ | |||||||
123456789101112 | Ahcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/GlucoponAhcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19 | 10∶110∶110∶115∶115∶115∶120∶120∶120∶120∶1∶120∶1∶120∶1∶1 | <12<12<12141414404040808080 | 252525252525252525252525 | 0.30.60.90.30.50.90.30.50.90.30.60.9 | 8.7 8.3 9.6 10.8 11.88.8 9.3 10.7 10.4 12.67.8 7.7 8.1 8.5 9.18.4 8.2 9.1 9.8 10.58.6 7.9 8.1 8.3 8.57.8 8.5 8.4 8.9 10.29.3 10 12.1 13.9 12.18.7 8.9 9.2 8.6 10.87.9 9.1 8.6 10.2 10.17.8 7.9 7.7 8.1 89.17.7 8.1 8.4 7.9 9.27.7 7.6 8.3 8.3 8.7 |
实例# | 处理组合物,20%固体 | 涂布温度(℃) | 增量率(%重量) | EDANA-流体透过时间(秒) | |||
表面活性剂系统 | 比率 | 粘度(cp)在20秒-1下 | 循环 循环 循环 循环 循环1 2 3 4 5 | ||||
25℃ 47℃ | |||||||
131415282930313233343536 | Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19Ahcovel/Glucopon/SF 19AhcovelAhcovelAheovelGlucopon 220UPGlucopon 220UPGlucopon 220UPTriton X-102Triton X-102Triton X-102 | 10∶1∶110∶1∶110∶1∶1111111111 | 282828110311031103<12<12<12120120120 | 150150150232323 | 252525474747252525474747 | 0.30.60.90.30.60.90.30.60.90.30.60.9 | 7.1 8.6 8.5 8.2 9.77.2 7.5 8.3 8.9 10.26.9 7.1 7.9 7.3 9.37.5 7.8 8.8 8.9 11.57.1 7.1 7.2 9.2 10.57.2 7.6 7.4 6.5 9.67.5 8.9 11.5 16.5 17.67.6 9.2 10.9 11.8 12.97.1 8.2 9.7 11.8 12.37.6 11.5 14.9 17.5 16.97.5 9.3 15.6 16.7 14.97.1 9.8 13.7 18.9 17.6 |
实例77
将金属茂聚烯烃泡沫片材(OPCELL LC31泡沫,产自SentinelProducts公司,Hyannis,MA)切割为厚度0.25英寸(约0.6cm)。将泡沫样品用以15∶1重量比共混的Ahcovel/Glucopon的1%溶液和1%Triton X-102饱和处理。然后,将处理过的泡沫在60℃烘箱中干燥30分钟。采用本文已述的EDANA液体透过试验,测定经一次浸湿的处理过的泡沫的液体吸入时间,结果报告于表7。表7.聚烯烃泡沫的液体吸入速率的比较
* 基材太疏水,液体不能透过,吸入时间不能测量。**液体吸入时间仅是对一次浸湿测量的。
样品 | 吸入时间(秒)** |
未处理的LC31泡沫Ahcovel/Glucopon处理的LC31泡沫Triton X-102处理的LC31泡沫未处理的LC33泡沫Ahcovel/Glucopon处理的LC33泡沫Triton X-102处理的LC33泡沫 | *2.95.5*108>200 |
实例78
对不同金属茂聚烯烃泡沫(OPCELL LC33泡沫,产自SentinelProducts公司)实施实例77中所述的相同的处理。按实例77所述测定液体吸入时间,结果示于表7。
采用下述实例进一步叙述本发明。
实例79
实例79中所使用的织物是2.5osy(约85gsm)纺粘无纺织物,其中纤维是并列双组分纤维。以近似等量存在的组分由聚乙烯和聚丙烯组成。将织物切成8英寸×10英寸。将织物样品在3∶1比率的Ahcovel/Glucopon 3%(重量)的溶液中浸渍约30秒。按本文所述,测定的WPU为约200%,因而织物的表面活性剂处理增量率为6%(重量)。测试处理过的织物的吸水性,其方法是横跨织物的宽度放置10个水滴(约0.1ml)。所有10个水滴均立即被吸入织物中,说明所进行的处理赋予织物均匀的高吸水性。未处理的对比织物经相同的水滴试验,结果10个水滴没有一个渗透或吸收到无纺织物中。
实例80
实例80所使用的织物是100gsm梳理机粘合织品(BCW),其中纤维为3dpf,分别由双组分聚乙烯/聚丙烯以皮/芯结构制成。将织物切成8英寸×10英寸。将织物样品浸渍在3∶1比率的3%(重量)Ahcovel/Glucopon的溶液中,历时约30秒。按照本文所述,测定WPU,为约100%,因而,织物的表面活性剂处理增量率为约3%(重量)。检测处理过的织物的吸水性,其方法是横跨织物宽度放置10个水滴(约0.1ml)。所有10个水滴均立即吸收到织物中,说明,所进行的处理赋予BCW织物以均匀的高亲水性。未处理的对比织物(无纺丝整理剂)经同样的水滴试验,结果,10个水滴没有一个渗透或吸收到无纺织物中。
因此,按照本发明,提供了改进的处理方法和制得了具有上述优点的处理过的无纺织物。在以具体实施方案说明本发明的同时,并未将其限制于此,本发明意欲包括出自权利要求广泛范围内的所有同等物。
Claims (31)
1.一种赋予基材耐久性能的稳定的乳液处理组合物,其在约25℃下的粘度为约100cp以下,所述组合物包含粘度改进剂。
2.权利要求1的处理组合物,其中所述粘度改进剂包括烷基多苷。
3.权利要求2的处理组合物,还包含表面活性剂,其固体含量为至少20%(重量)。
4.权利要求2的处理组合物,还包含表面活性剂,其固体含量为20%(重量)以下。
5.权利要求3的处理组合物,其中所述表面活性剂包括乙氧基化氢化蓖麻油和山梨糖醇单油酸酯的共混物。
6.权利要求2的处理组合物,其中所述烷基多苷在烷基链中有8~10个碳原子。
7.权利要求3的处理组合物,其中所述烷基多苷在烷基链中有8~10个碳原子。
8.权利要求5的处理组合物,其中所述烷基多苷在烷基链中有8~10个碳原子。
9.用权利要求2的处理组合物处理的基材。
10.用权利要求6的处理组合物处理的基材。
11.用权利要求7的处理组合物处理的基材。
12.用权利要求8的处理组合物处理的基材。
13.用权利要求2的处理组合物处理的无纺织物。
14.用权利要求6的处理组合物处理的无纺织物。
15.用权利要求7的处理组合物处理的无纺织物。
16.用权利要求8的处理组合物处理的无纺织物。
17.包含权利要求13的无纺织物的个人护理制品。
18.包含权利要求14的无纺织物的个人护理制品。
19.包含权利要求15的无纺织物的人个护理制品。
20.一种处理基材的方法,包括将在约25℃下粘度为100cp以下的处理组合物涂布到基材上的步骤,所述处理组合物包含粘度改进剂和赋予所述基材耐久性能的组分。
21.权利要求20的方法,其中所述涂布步骤使用喷洒设备进行。
22.权利要求21的方法,其中所述喷洒设备包含一个或多个旋转喷洒头。
23.权利要求20的方法,其中所述涂布步骤使用处理浴,所述方法包括干燥步骤。
24.权利要求20的方法,其中所述处理组合物被涂布到所述基材的两面。
25.权利要求21的方法,其中所述处理组合物包括烷基多苷作为粘度改进剂。
26.权利要求25的方法,其中所述基材是无纺织物;所述处理组合物的固体含量至少为约20%(重量),还包含乙氧基氢化蓖麻油和山梨糖醇单油酸酯的共混物。
27.一种按照本发明叙述的流出试验测定的耐久性为至少2次循环,已用处理组合物处理过的无纺织物,所述组合物包含烷基链中含8~10个碳原子的烷基多苷,以及乙氧基化的氢化蓖麻油和山梨糖醇单油酸酯的共混物。
28.权利要求14的无纺织物,包括泡沫物。
29.权利要求15的无纺织物,包括泡沫物。
30.权利要求14的无纺织物,包括薄膜。
31.权利要求15的无纺织物,包括薄膜。
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- 1997-08-11 TR TR1999/00475T patent/TR199900475T2/xx unknown
- 1997-08-11 CN CNB971976422A patent/CN1161512C/zh not_active Expired - Lifetime
- 1997-08-11 BR BR9711663A patent/BR9711663A/pt not_active IP Right Cessation
- 1997-08-11 EP EP19970938257 patent/EP0923658B1/en not_active Expired - Lifetime
- 1997-08-11 PL PL33203197A patent/PL332031A1/xx unknown
- 1997-08-11 AU AU40633/97A patent/AU729628B2/en not_active Expired
- 1997-08-11 KR KR1019997001754A patent/KR100543144B1/ko not_active IP Right Cessation
- 1997-08-11 WO PCT/US1997/014189 patent/WO1998010134A1/en not_active Application Discontinuation
- 1997-09-02 CO CO97050857A patent/CO4930314A1/es unknown
- 1997-09-03 AR ARP970104029 patent/AR009527A1/es active IP Right Grant
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106757894A (zh) * | 2016-11-24 | 2017-05-31 | 杨生勇 | 排水板滤布生产工艺及制得的滤布 |
CN113622082A (zh) * | 2020-05-06 | 2021-11-09 | 深圳陶陶科技有限公司 | 离心纺无纺布制备方法和应用 |
Also Published As
Publication number | Publication date |
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EP0923658B1 (en) | 2003-11-19 |
DE69726289T2 (de) | 2004-08-26 |
KR100543144B1 (ko) | 2006-01-20 |
TR199900475T2 (xx) | 1999-09-21 |
CN1161512C (zh) | 2004-08-11 |
DE69726289D1 (de) | 2003-12-24 |
KR20000068412A (ko) | 2000-11-25 |
PL332031A1 (en) | 1999-08-16 |
EP0923658A1 (en) | 1999-06-23 |
AU729628B2 (en) | 2001-02-08 |
US6028016A (en) | 2000-02-22 |
AR009527A1 (es) | 2000-04-26 |
AU4063397A (en) | 1998-03-26 |
CO4930314A1 (es) | 2000-06-27 |
BR9711663A (pt) | 1999-08-24 |
WO1998010134A1 (en) | 1998-03-12 |
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