CN1080343C - 受控滞后的复合弹性材料和个人护理制品 - Google Patents
受控滞后的复合弹性材料和个人护理制品 Download PDFInfo
- Publication number
- CN1080343C CN1080343C CN96199531A CN96199531A CN1080343C CN 1080343 C CN1080343 C CN 1080343C CN 96199531 A CN96199531 A CN 96199531A CN 96199531 A CN96199531 A CN 96199531A CN 1080343 C CN1080343 C CN 1080343C
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- Prior art keywords
- layer
- fiber
- polymer
- block copolymer
- styrene
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- Expired - Lifetime
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Abstract
本发明提供一种多层材料,它是由弹性薄膜,纤维,或纤维网构成,其中至少一层是由弹性聚烯烃构成。并且至少一附加层是选自包括下述种类的弹性体构成,即聚氨基甲酸酯,共聚醚酯,聚酰胺聚醚嵌段共聚物,乙烯乙酸乙烯酯(EVA),和具有一般结构式为A-B-A’,A-B-A-B或A-B的嵌段共聚物,如共聚(苯乙烯/乙烯-丁烯),(聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯),和聚(苯乙烯/乙烯-丁烯/苯乙烯)。这种材料还包括至少一可收缩纤维网,使其连接弹性纤维网。并且可制成个人护理制品,传染病控制制品。复盖层或服装。
Description
发明背景
用挤压出的热塑性树脂来形成纤维,薄膜和纤维网已有数年,对于这种应用的最普通的热塑性材料是聚烯烃,尤其是聚丙烯,但是每一种材料相对最终产品所希望的特性,各具有其特有的优点和缺点。
无纺织物是可由这样的聚合物制成的一典型产品,其可用于广泛的应用范围,例如个人护理产品象尿布,妇女卫生制品和失禁产品,传染控制制品,外衣和其它制品。使用于这些用途的无纺织物常常为叠层的形式,其具有数层熔喷无纺织物和纺粘无纺织物,如纺粘/熔喷/纺粘(SMS)叠层,SMMS叠层以及甚至叠层具有6层或更多层。
用于制造纤维,薄膜和纤维网的一种特殊所希望的热塑性聚合物是弹性的。用于生产这些产品的组合物的一实例已揭示在授予Wisneski等人的US 4,663,220中,其中纤维是由一种A-B-A′嵌段共聚物的聚合物生产的,而“A”和“A′”各为一种包括苯乙烯部分的热塑性端基封闭,“B”为弹性聚(乙烯-丁烯)中嵌段,和聚烯烃处理助剂。
虽然至此聚烯烃如聚乙烯和聚丙烯为非弹性的,但在聚合物和催化剂技术中新研制出一种称之为金属茂聚合物的材料。通过金属茂方法生产的聚合物具有不同于通过传统的齐格勒-纳塔和其它系统生产的聚合物的一些特点,所述的聚合物的某些聚合物可以是弹性的。基于弹性聚烯烃的金属茂具有不同于已知弹性体的拉伸和回缩特性。
本发明人现已发现了一种多层层压制品,其中一些层是由弹性聚烯烃制成的,该弹性聚烯烃是通过金属茂处理而生产的,一些层是通过传统的弹性体而制造的,使其让最终产品的拉伸和回缩特性满足非常高的程度要求。据信在纤维产品之前仅仅混合不同的弹性体是一种很好的方法,其原因为:第一,混合物,类似化学反应,是不可预料的,而实际上结果是增加了织物的所希望的特性,第二,某些聚合物是不能混合的,或是不能制成一种混合物。
本发明的一个目的是提供具有至少一弹性聚烯烃层和至少一其它弹性聚合物层的层压制品,以便于由这样的层压制品生产的材料的特性能得以良好的控制。
发明概述
本发明提供的多层层压制品是由数层弹性薄膜纤维、或纤维网而构成,其中至少一层是由弹性聚烯烃组成,而至少一附加层是选自包括下列所述的种类的弹性体组成:聚氨基甲酸酯、共聚醚酯、聚酰胺聚醚嵌段共聚物、乙烯乙酸乙烯酯(EVA),和通式为A-B-A′或A-B的嵌段共聚物,例如象共聚(苯乙烯/乙烯-丁烯), (聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯,和聚(苯乙烯/乙烯-丁烯/苯乙烯)。这样的层压制品可制成个人护理制品,控制传染制品,覆盖层或外衣。定义
在本申请中所使用的术语“织物或纤维网”是指具有一种被相互放置的各个纤维或线的结构的纤维网,但并不是一种可易识别的方式如一种针织织物。无纺织物或纤维网是由许多工艺方法而形成的,例如,熔喷工艺方法,纺粘工艺方法,和粘合梳理纤维网工艺方法。无纺织物的基重通常表示成盎司/平方码(osy),或克/平方米(gsm),纤维直径一般表示成微米,(注osy换算成gsm是33.91乘以osy)。在此所使用的术语“微纤维”是指具有平均直径不大于75微米的小直径纤维,例如平均直径为0.5微米至50微米,尤其是微纤维可具有2微米至40微米的平均直径。用于表示纤维直径的另一常用单位是旦尼尔,其被定义为纤维每9000米长的克数。例如,在给定微米表示的一种聚丙烯纤维的直径可以通过用0.00629乘其平方的结果转换成旦尼尔,这样,15微米的聚丙烯纤维约为1.42旦尼尔(152×0.00629=1.415)。
在此使用的术语“纺粘纤维”表示较小直径的纤维,它是通过把熔融的热塑性材料以长丝的形式从一纺丝板的许多细小的,通常是圆形毛细管中挤出并使挤出的长丝的直径迅速减小而形成的,这种方式,例如在下述专利中被揭示,Appel等人的US 4,340,563,Dorschner等人的3,692,618,Matsuki等人的US 3,802,817,Kinney的US 3,338,992和US 3,341,394,Hartman的US 3,502,763以及Dobo等人的US3,542,615。纺粘纤维当其放置到收集表面时通常是不堆积的。纺粘纤维一般是连续的并且平均直径是大于7微米,尤其是在10到20微米之间。
在此使用的术语“熔喷纤维”是指由下述方式形成的纤维,把熔融热塑性材料挤压通过一些细的、通常为圆形的模压毛细孔成为熔融纱线或长丝而进入到成会聚的高速气流(如空气)中,该气流使熔融热塑性材料的长丝变细以减少其直径,并使其达到微纤维直径。随后,熔喷纤维被高速气流传输并被放置在收集表面上以形成一种熔喷纤维随机分配的纤维网。这种工艺方法已被揭示,例如US 3,849,241。熔喷纤维是微纤维,它是连续的或非连续的,平均直径一般小于10微米,并且当放置到收集表面时通常是堆积的。
在此使用的术语“聚合物”通常包括下列材料,但并不限制于此,均聚物,共聚物,例如嵌段、接枝、无规和交变共聚物,三元共聚物等和其混合物和变体。此外,除非有另外说明限定,术语“聚合物”将包括材料所有可能的几何构形。这些构形包括全同立构,间同立构和无规对称,但并限制于此。
在此使用的术语“机器方向”或MD意思是织物在其生产方向上的织物长度方向。术语“横向机器方向”或CD意思是织物的宽度方向,即通常垂直于MD的方向。
在此使用的术语“单组分”纤维表示仅使用一种聚合物一种或多种挤压形成的纤维。这不意味着把所形成的纤维从为了着色,抗静电性,润滑,亲水性等而已添加的少量添加剂的一种聚合物中排除。这些添加剂,例如用于着色的二氧化钛,一般是少于5%(重量),并一般多于2%(重量)。
在此使用的术语“共轭纤维”表示是由至少两种聚合物从分离的挤压机挤出但被一起纺制以形成一根纤维所制成的纤维。共轭纤维有时还表示多组分或双组分纤维。这些聚合物一般相互是有区别的,纵然共轭纤维可以是多组分纤维。所述的聚合物在共轭纤维的横截面上是以基本不变布置的明显区域而排列的,并且是沿共轭纤维的长度方向连续地延伸。例如这样的一种共轭纤维的构形可以是皮/芯型排列的,其中一种聚合物由另一种聚合物围绕,或者可以是并列排列的,或者可以是“海岛”(天星状)型排列的。一些共轭纤维在Kaneko等人的US 5,108,820,Strack等人的US 5,336,552,Pike等人的US 5,382,400中报道。对于两种组分的纤维,其聚合物的比例为75/25,50/50,25/75,或者任何其它所希望的比例。
在此使用的术语“双成分(复合)纤维”表示由至少两种聚合物,以一种混合物的形式,从相同的挤压机挤出而形成的纤维。术语“混合物”在后面被限定。双成分纤维在纤维的横截面区域上没有其各聚合物组分相对恒定布置明显区域的排列,并且各聚合物沿着纤维的整个长度是不连续的,而通常所形成的纤维或原纤维自始至终是随机的。双成分纤维有时也表示多成分纤维。一般典型的这类纤维已被揭示,例如,Gessner的US 5,108,827。共轭和双成分纤维也揭示在John A.Manson和Leslie H.Sperling的教科书聚合物混合物和组合中,Plenum Press1976版,New York,IBSN 0-306-30831-2 Plenum PublishingCorporation的部分273-277页。
在此使用的术语“混合物”意味着两种或多种聚合物的混合物,而术语“合金(alloy)”意味着混合物的一个子类,其中组分是不混溶的,但已经过相容处理。“混溶性”和“不混溶性”定义为混合物分别有负值和正值的混合自由能。此外,“相容处理”定义为为了制造一种合金对不溶混聚合物混合物进行的界面改性的工艺过程。
在此使用的术语“压辊”表示在纤维网之上和之下的装置或一些辊,其用来压紧如以预粘合或者初粘合的刚刚制出的纺粘纤维网形式的纤维网,以便为进一步的加工工艺而给其以足够的完整性,但相对于另外的粘合工艺如TAB热粘合,水力缠绕和超声波粘合不是强有力的粘合。压辊轻微地挤压纤维网,以便增加其自粘和其完整性。压辊完成这种功能是非常适宜的,但是它还有一些缺点。缺点之一是压辊实际上压实了纤维网,从而引起织物的松密度或膨松性降低,这对于使用要求来说是不希望有的。第二个并且是更为严重的缺点是织物有时会缠绕在一个或两辊上,为了清理辊从而引起织物生产线停机,在停机期间生产率明显降低。压辊第三个缺点是如果在纤维网成形中产生微小的缺陷,例如聚合物的一落下物形成到纤维网上,压辊可迫使落下物进入到有孔的传送带上,而大部分纤维是形成到其传送带上,这样会引起传送带的不完善并将损坏该传送带。
在此使用的术语“热空气刮刀”或HAK的意思是一种预处理或最初处理刚刚制出的纤维的工艺技术,以便为进一步加工工艺而给其足够的完整性,但相对于另外的粘合工艺如热粘合,水力缠绕和超声波粘合而言,它不是强有力的粘合。热空气刮刀是一种装置,该装置聚焦一加热的空气流,其空气流有非常高的流速,流速一般为1000~10000英尺/分(fpm)(305~3050米/分),该空气流在纤维网成形之后立刻射向无纺纤维网。对于用于纺粘法的普通热塑性聚合物来说,空气温度一般为200至500°F(93至290℃)。通过至少一个宽度为1/8至1英寸(3至25mm),尤其是3/8英寸(9.4mm)的狭缝来整理并引导HAK所聚焦的空气流,其狭缝是作为朝着纤维网的加热空气的出口,而狭缝是在纤维网的整个宽度之上,基本为机器横向方向布置的。在其它的实施例中,也可有一些相互靠近的或以微小间隙分离安置的狭缝。至少一个狭缝是较好的,但不必要是连续的,例如它可由一些具有小间距的孔组成。HAK具有一封闭的空间,以用来在加热空气从狭缝引出之前,配置和贮装加热空气。HAK的封闭空间压力最好为1.0至12.0英寸水柱(2至22mmHg),并HAK位于成形线材之上0.25至10英寸,最好为0.75至3.0英寸(19至76mm)。在一特殊实施例中,对于横向方向流动的HAK的封闭空间的横截面面积(即机器方向上的封闭空间横截面面积)至少是整个狭缝出口面积的两倍。由于纺粘聚合物形成在其上的有孔线材一般是以高速率移动,纤维网的任何特殊部分受到由热空气刮刀排出的空气作用的时间小于十分之一秒,与具有非常长的停留时间的穿透空气粘合工艺相比其时间一般为百分之一秒。HAK工艺过程具有至少空气温度、空气速度和HAK封闭空间距纤维网的距离的大范围的可变性和可控性。
在此使用的穿透空气粘合或“TAB”,表示粘合无纺共轭纤维的一种工艺方法,其中足以加热至使其制造的纤维网的其中之一的聚合物纤维熔融的空气被迫使通过纤维网。空气速度为每分钟100至500英尺,并且停留时间可仅为6秒。聚合物的熔融和再固化构成了粘合。穿透空气粘合通常被认为第二步粘合过程。由TAB要求至少一种组分熔融来完成粘合,这就限定纤维网至少具有两种组分如共轭纤维或其包括一种粘合剂。
在此使用的术语“缝编”表示例如根据Strack等人的US 4,891,957或Carey,Jr的US 4,631,933为一种材料的缝合。
在此使用的“超声粘合”意为把织物在集声器与砧辊之间通过所完成的一种工艺过程,如在Bornslaeger的US 4,374,888中的说明。
在此使用的“热点粘结”是涉及把织物或将被粘合纤维的纤维网,在加热的轧光辊与砧辊之间通过。轧光辊通常以某种方式制有花纹,但未必总是,以便整个织物不会横跨其轧光辊的整个表面被粘合,而砧辊通常是平整的。因此,由于功能具有美观效果的原因已研制出了轧光辊的各种图案。一种图案花纹的实例是具有一些点,并且是HansenPennings或“H&P”图案花纹,其具有30%的粘合区域及200粘合点/平方英寸,如在Hansen和Pennings的US 3,855,046中被报告。H&P图案花纹具有方点或针粘合区域,其中每一针侧向尺寸0.038英寸(0.965mm),针之间的间距0.070英寸(1.778mm),粘合深度0.023英寸(0.584mm)。所得到的图案花纹具有29.5%的粘合区域。另一典型的点粘合图案花纹是扩展的Hansen Pennings或“EHP”粘合图案花纹,其产生有15%的粘合区域,方针具有侧向尺寸0.037英寸(0.94mm),针距0.097英寸(2.464mm),粘合深度0.039英寸(0.991mm)。另一典型的设计为“714”的点粘合图案花纹具有方针粘合区域,其中每针具有侧向尺寸0.023英寸,针间的间距0.062英寸(1.575mm),粘合深度0.033英寸(0.838mm)。所获得的图案花纹具有约15%的粘合区域。而另一普通图案花纹是C-Star图案,其具有16.9%的粘合区域。C-Star图案花纹具有一横向条纹或由突出的星状物断开的“条绒”图案。其它一些普通的图案花纹包括具有重复的和稍微不重合方块的方块图案花纹,它约有16%的粘合区域,和一种线材织的图案花纹,如名称联想象一种窗网,其约有19%的粘合区域。一般,粘合区域百分比为织物层状纤维网的面积的10%至30%不等。正如本领域已知的,点状粘合把各层固定在一起,并且通过每层中的粘合长丝和/或纤维把完整性赋予给每个层。
在此使用的语术“粘合窗”是指用于把无纺织物粘合在一起,成功完成这种粘合的轧光辊的温度范围。对于纺粘聚丙烯,粘合窗一般为270°F至310°F(132℃至154℃)。若低于270°F,聚丙烯不能足以被熔融和粘合,高于310°F,聚丙烯将过度熔融并可附着到轧光辊上。聚乙烯具有更窄的粘合窗。
在此使用的术语“回缩”,表示当通过偏压力的施加时,其材料随之拉伸,偏压力结束时,被拉伸的材料的收缩。例如,如果具有松驰的未加偏压的长度为1英寸的材料通过拉伸到1.5英寸而伸长50%,那么材料将具有一拉伸长度,该拉伸长度是其松驰长度的150%。在偏压和拉伸力解除之后,如果该样品受拉伸的材料收缩,它回缩到长度为11英寸,那么材料将回缩其伸长的80%(0.4英寸)。
在此使用的术语“颈缩”或可交换的“颈向拉伸”,表示通常在机器方向上延长无纺织物的一种方法,以控制的方式减少其宽度从而达到所希望的数量值。受控拉伸可发生在冷却,室温或较高温度下,并且是限制在要求断裂织物的延长范围内在拉伸方向上的整个尺寸的一个增量,在多数情况下,约为1.2至1.4倍。当被松驰时,纤维网朝着其原尺寸收缩。例如,这种工艺方法揭示在Meitner和Notheis的US4,443,513和Morman的US 4,965,122,US 4,981,747和US 5,114,781中。
在此使用的术语“弹性的”和“弹性体的”为把纤维、薄膜或织物意指在施加一偏压力时的一种材料是可拉伸的,使被拉伸的偏压力长度是其松驰的未拉伸长度的150%或1.5倍,并且在拉伸偏压力解除时,其将回缩至少延长的50%。
在此使用的术语“复合弹性材料”表示一种弹性材料,它可以是一种多组分材料或多层材料。例如,一种多层材料可具有至少一弹性层,该弹性层至少在两位置处相连于至少一个可收缩层,以致可收缩层在连接弹性层的位置之间被收缩。这样一种复合弹性材料可拉伸达到这样的程度,以至在粘合位置之间收缩的非弹性体材料使弹性材料延长。例如,一种类型的多层复合弹性材料由Vander Wielen等人的US 4,720,415所揭示,其全部内容可引为参考,其中可使用由多排挤压机生产的相同聚合物的多层材料。其它一些复合弹性材料被揭示下列专利中Kieffer等人的US 4,789,699,Taylor的US 4,781,966,Morman的US 4,657,802和US 4,652,487以及Morman等人的US 4,655,760和US 4,692,371。一种复合弹性材料也可为这样一种形式,其中可收缩纤维网是一种被颈缩的可颈缩的材料,然后连接到一弹性片材上,如揭示在Morman的US5,226,992,US 4,981,747,US 4,965,122和US 5,336,545中。
在此使用的术语“衣服”意指任何类型的非医用有关的可穿的服装。它包括工业工作服,衣裤相连的工作服,内衣,裤子,衬衫,夹克,手套,短袜等等。
在此使用的术语“传染控制制品”意指医用有关产品,例如外科用的长衫和帘布,面具,头部覆盖物象膨松皱裥领巾帽,外科用的帽子和护罩,鞋袜象鞋覆盖物,靴套和拖鞋,绷带,杀菌包装物,擦试物,服装象实验室外套,工作服,围裙和夹克,病人床上用品,拉伸器和摇篮片材等等。
在此使用的术语“个人护理制品”意指尿布,运动裤,吸收性内衣,成人不能自制制品,和妇女卫生制品。
在此使用的术语“保护性覆盖物“意指用于交通工具如汽车,卡车,船,飞机,摩托车,自行车,高尔夫车等的覆盖物,用于常常放置在层外的装置的覆盖物,所述的装置如格栅,场地和公园设备(割草机,旋转式舵柄等),和草坪设施,以及地板覆盖物,桌布和野餐地面覆盖物。试验方法
熔体流动速率:熔体流动速率(MFR)是聚合物粘度的数值。MFR可表示为根据测量循环时间在特殊负载或切变速率下来于一已知尺寸毛细管的材料的重量,并且例如根据ASTM测试1238-90b以规定温度和负载测量的克数/10分钟。
循环试验:循环试验是使用一个可由Sintech Incorporated ofStoughton.MA获得的Sintech 2计算机材料测试系统而完成的。
在对于停止试验的延长或拉伸中,一个3英寸×6英寸(76mm×152mm)样品(长尺寸为机器方向),放置在Sintech 2机器的夹爪内,夹爪之间的间隙为50mm。然后样品被一个2000克的止动负载以500mm/min的十字头速度牵拉。相对于在2000克未拉伸长度的以百分比形式的延长率是拉伸到停止值的拉伸量。
以停止试验条件下的延长率也得到了以截距形式的延长值。截距延长值是在负载上转折点的拉伸百分比与拉伸百分比图的比值。数值为75%的截距延长率用于测定样品在循环试验中被拉伸的最大百分比。
在循环试验中,一种材料相对于75%截距延长率被认为固定延长5次,并且使其回到它的原始尺寸,如果能这样进行的话。获得的测量结果为伸长负载、滞后损失和回复负载。这就可用来设计一种最终结果的表示图,例如在图1,2和3中,y轴是负载,x轴是延长率。该图产生一个曲线,它具有一区域,在其之下称为“总能量吸收”或“TEA”。对于一样品各种循环的TEA曲线比率是与材料、基重和样品宽度无关的值,其能与其样品比较。
附图简述
图1表示了控制的复合弹性层压制品的TEA曲线。图2表示了实例1的复合弹性层压制品的TEA曲线。图3表示了实例2的复合弹性层压制品的TEA曲线。Y轴表示以克为单位的负载,X轴为以百分比为计的延长率。图4表示了适合于复合弹性材料生产的一平行排列的制造工艺方法的示意图。
发明详述
热塑性聚合物在薄膜、纤维和纤维网的产品中是十分有益的,所述的产品供例如个人护理物品,传染控制制品,服装和防护性覆盖物等各种产品之用。在一些应用中,理想的是,薄膜、纤维和纤维网是弹性的,以便由薄膜,纤维和纤维网制成的产品可适合客体,或以便可进行稍微的拉伸而无受到损坏。
弹性聚合物在过去已用于这些应用之中,但是其弹性聚合物对于工艺是有些困难的。在Wisneski的US 4,663,220中揭示了一种通过添加一种聚烯烃,尤其是聚乙烯处理剂改善弹性聚合物特性的方法。此外,这些产品具有一个拉伸和收缩特征的特殊范围。
本申请人已生产出一种具有至少一层由新种类聚合物制成的层压制品,其在使用之前具有不同的拉伸和收缩特征。该层压制品具有一些特别有用的特性,此外其结构致使使用者让薄膜、纤维和纤维网层压制品的特性满足其准确要求。
新种类的聚合物是有关“金属茂”聚合物或根据金属茂工艺技术生产的这种聚合物。金属茂工艺技术通常使用一种金属茂催化剂,它是通过一种辅助催化剂而被活化,即被电离。
金属茂催化剂包括双(正丁基环戊二烯基)二氯化钛,双(正丁基环戊二烯基)二氯化锆,双(环戊二烯基)氯化钪,双(茚基)氯化锆,双(甲基环戊二烯基)二氯化钛,双(甲基环戊二烯基)二氯化锆,二茂钴,环戊二烯基三氯化钛,二茂铁,二氯化二茂铪,异丙基(环戊二烯基,-1-芴基)二氯化锆,二氯化二茂钼,二茂镍,二氯化二茂铌,二茂钌,二氯化二茂钛,氢氯化二茂锆,氯化二茂锆等等。这些化合物的一更详细表包括在Rosen等人并转让给Dow化学公司的US 5,374,696中。这些化合物还揭示在Stevens等人并转让给Dow的US 5,064,802中。
金属茂工艺技术,和一些特殊的催化剂和催化剂基础系统是一些专利的主题。Kaminsky等人的US 4,542,199描述了一种方法,其中辅助催化剂象甲基铝氧烷(MAO)加入到甲苯中,加入通式是(环戊二烯基)2MeRHal的金属茂,其中Me是过渡金属,Hal是卤素,R是双戊二烯基或C1至C6烷基,然后加入乙烯以形成聚乙烯。LaPointe等人的并转让给Dow化学公司的USP 5,189,192描述了一种通过金属中心氧化而制备加聚催化剂的工艺方法。Exxon Chemical Patents,Inc的US 5,352,749描述了一种在流化床中聚合单体的方法。US 5,349,100描述了手性金属茂化合物和通过对映选择氢化物转移产生手性中心的制备方法。
辅助催化剂是一些如甲基铝氧烷(MAO)的材料,甲基铝氧烷是最普遍的,另外还有烷基铝,含硼的化合物,如三(五氟苯基)硼,四(五氟苯基)硼锂,和二甲基苯胺四(五氟苯基)硼。由于处理和产品污染问题,因此正在对其它的辅助催化剂系统或最大限度减少或者甚至省去烷基铝的可能性不断地进行研究。需要强调的是金属茂催化剂被活化或电离成正离子形式以用来与将被聚合的单体反应。
使用金属茂催化剂生产聚合物具有能制得非常窄小的分子量范围的极好优点。图1表示了对于齐格勒-纳塔催化剂与金属茂型催化剂比较的一典型分子量分布情况,其金属茂催化剂给出了较窄的曲线。聚合度分布性数量(Mw/Mn)低于4甚至低2对于金属茂生产聚合物来说是可能的。当与其它类似于齐格勒-纳塔催化剂生产的聚合物比较,这些聚合物具有窄的短的链支化分布。
当使用立体定向金属茂催化剂时,则有可能利用金属茂催化剂系统来控制聚合物非常接近的全同立构规整度。事实上,已生产的聚合物具有超过99%的全同立构规整度。还有可能的是利用该系统,可生产高间同立构聚丙烯。
控制聚合物的全同立构规整度还能结果形成这样的聚合物产品,其含有全同立构嵌段和交变在聚合物链的整个长度上的无规立构材料的嵌段。这种结构根据无规立构部分产生一种弹性聚合物。这种聚合物合成由K.B.Wagne在杂志“科学”,267卷(1995.1.13)P.191的文章中讨论。在讨论Coates和Waymouth的工作成果中,Wanger解释道,催化剂在立体化学构型间振荡,产生一种具有连接到无规立构中心的延伸长度上的全同立构立构中心的延伸长度的聚合物链。全同立构支配减少从而产生弹性。Geoffrey W.Coates和Roberr M.Waymouth在相同的出版物第217页发表了一篇题名为“振荡立构规正控制:对于热塑性弹性聚丙烯合成的战略”,该文章论述了他们的工作,其中他们在有甲基铝氧烷(MAO)的情况下,使用了双(2-苯茚基)二氯化锆,并且在反应器中改变压力和温度,振荡在全同立构与无规立构之间的聚合物形式。
金属茂聚合物的商品化产品受到一定限制。但却是在发展的。这些聚合物可由Exxon Chemical company of Baytown,Texas在基于聚丙烯的聚合物的EXXPOL和ACHIEVETM,和基于聚丙烯的聚合物的EXACT和EXCEEDTM的商品名下获得。Dow Chemical Company of Midland,Michigan具有在名为ENGAGE下获得的商品聚合物。这些材料被认为是利用非立体定向金属茂催化剂而生产的。Exxon通常认为他们的金属茂催化剂技术为“单位置(single site)”催化剂,而Dow认为是在名为INSITE下的“限制几何结构”,以区别于传统的具有多反应位置的齐格勒-纳塔催化剂。其它一些生产者例如Fina Oil,BASF,Amoco,Hoechst和Mobil在该领域也是很积极的,并相信在未来十年根据该技术生产的聚合物的利用率将会增长。尤其在本发明情况中,弹性聚烯烃如聚丙烯和聚乙烯是非常适用的。
有关基于金属茂的弹性聚合物,Kaminsky等人的US 5,204,429描述了一种工艺方法,它可使用一种催化剂由环烯和线形烯生产弹性共聚物,其催化剂是立体刚性手性金属茂过渡金属化合物和铝氧烷。聚合反应是在一种惰性溶剂如脂族的或环脂族烃例如甲苯中完成的。使用待聚合的单体作为溶剂,反应也可会出现气相。Lai等人的转让给DowChemical的US 5,278,272和US 5,272,236以及名为“显著弹性的线形烯族烃聚合物”描述了聚合物具有特殊的弹性特性。Dow也大批的生产一系列商品名“ENGAGE”下的弹性聚烯烃。
用于本发明的其它一些弹性热塑性聚合物可由一些嵌段共聚物制成,例如聚氨基甲酸酯,共聚醚酯,聚酰胺聚醚嵌段共聚物,乙烯乙酸乙烯酯(EVA),具有通常结构式为A-B-A′,A-B-A-B,或A-B的嵌段共聚物,象共聚(苯乙烯/乙烯-丁烯),(聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯),聚(苯乙烯/乙烯-丁烯/苯乙烯),等等。
有用的弹性树脂包括具有一般结构为A-B-A′,或A-B的嵌段共聚物,而A和A′各是一种热塑性聚合物端基封闭,它含有苯乙烯的一部分,例如聚(乙烯芳烃),而B是一种弹性聚合物的中嵌段,例如共轭二烯系或低链烯聚合物。A-B-A′型嵌段共聚物对A和A′嵌段可具有不同的或相同的热塑性嵌段聚合物,而该嵌段共聚物意指包括线性的,支化和径向嵌段共聚物。关于这一点,径向嵌段共聚物可表示为(A-B)m-X,其中X是多宫能团的原子或分子,而每个(A-B)m-是由X以A为端基封闭的方式扩散。在径向嵌段共聚物中,X可以是有机或无机的多宫能团原子或分子,而m是具有相同值的存在于X的原本官能团的整数,它通常至少是3,一般是4或5,但不限于这些。这样,在本发明中,所述的“嵌段共聚物”,尤其是“A-B-A′”和“A-B”嵌段共聚物意指包括具有如上述似橡胶的嵌段和热塑性嵌段的所有嵌段共聚物,它们能被挤出(如被熔喷纺制),并且不限制嵌段数量。例如,弹性无纺纤维网可由弹性(聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯)嵌段共聚物构成。这些弹性共聚物的商品化实例是例如称为KRATON材料,它们可由Shell ChemicalCompany of Houston,Texas获得。KRATON嵌段共聚物可得到一些不同的配方,它们数量确定在US 4,663,220中,在此引为参考。
由弹性A-B-A′-B′四嵌段共聚物组成的聚合物也可尤其用于本发明中,这样的聚合物描述在Taylor等人的US 5,332,613中。在这样的聚合物中,A是热塑性聚合物嵌段,B是实际与聚(乙烯-丙烯)单体单元氢化合的异戊间二烯单体单元。这样的四嵌段共聚物的一个实例是苯乙烯-聚(乙烯-丙烯)-苯乙烯-聚(乙烯-丙烯)或SEPSEP弹性嵌段共聚物,可由Shell Chemical Company of Houston,Texas,商品名称KRATONG-1657下获得。
热塑性共聚多酯弹性体包括具有下列一般结构式的共聚醚酯
其中“G”是选自下述所构成的组合:聚(氧乙烯)-α,ω-二醇,聚(氧丙烯)-α,ω-二醇,聚(四亚甲基)-α,ω-二醇,而“a”,“m”和“n”是正整数。这些材料当根据ASTM D-638测量时通常具有约600%~750%的断裂伸长率,当票据ASTM D-2117测量时具有约350°F~400°F(176-205℃)的熔点。
这样的共聚多酯材料的商品化实例例如称为ARNITEL,从前可从Akzo Plastics of Arnhem,Holland获得DSM of Sittard,Holland获得,或称为HYTREL,它们可从E.I.DuPont de Nemours ofWilmington,Delaware获得。由聚酯弹性材料形成的弹性无纺纤维网被揭示在例如,Morman等人的US 4,741,949中,在此可引用参考。
可被使用的其它实例的弹性材料包括例如聚氨基甲酸酯弹性材料,它们可在商标ESTANE下从B.F.Goodrich & Co.或MORTHANE从Morton Thiokol Corp.获得,聚酰胺聚醚嵌段共聚物,例如称为PEBAX,可从Atochem Inc.Polymers Division(RILSAN),of GlenRock,New Jersey获得,和聚酯弹性材料,例如可在商品名HYTREL下从E.I.DuPont De Nemours & Company获得。
弹性聚合物还包括乙烯和至少一个乙烯系单体的共聚物,其乙烯系单体例如醋酸乙烯酯,不饱和的脂族单羧酸,和这样单羧酸的酯类。这些弹性共聚物和由其弹性共聚物形成的弹性无纺纤维网例如揭示在US4,803,117中。
还有可能的是与弹性体混合的其它材料用于生产根据本发明的层材,例如碳氟化合物化学产品以增强化学抵抗性,这些都教授在US5,178,931中,例如用于增加抗燃的阻燃剂和/或色料使各层具有相同或不同颜色。用于纺粘和熔喷热塑性聚合物的阻燃剂和色料是已知技术并且是内部添加剂。如果使用的话,色料通常用量少于层材重量的5%,而其它材料累积量少于25%(重量)。
由本发明层压制品制造的产品也可受到有关的处理,使其适用更专门功能。这些有关处理和其适用的方法是已知技术,并且包括例如抗乙醇处理,抗静电处理和类似处理,其通过喷射,浸渍等方式而实施的。应用Zelec抗静电剂(可从E.I.DuPont,Wilmington,Delaware获得)是该有关处理的一个实例。
当本发明的层压制品是以无纺纤维网的形式时,它们可通过本领域已知的熔喷或纺粘工艺技术而生产。这些工艺技术通常使用一挤压机以把熔融的热塑性聚合物提供到一纺丝板处,在该处聚合物被纤维化从而产生纤维,该纤维可以是短的或较长的。这些纤维随后通常由空气拉伸,并放置在一个移动的成形垫或带上以形成无纺纤维网。以纺粘和熔喷工艺技术生产的这些纤维是一些如上定义的微纤维。
纺粘无纺织物通常以某种方式被预先或首先粘合,如它们的生产是为了给予它们足够的结构完整性,以便经受住对成品的严厉的进一步加工。这种预粘合可通过压辊或通过热空气刮刀来完成,辅助粘合能以如下方式实现,水力缠绕,针刺,超声波粘合,粘合剂粘合,缝编粘合,空气中粘合和热熔粘合。
多层熔喷织物可通过针刺法,超声波粘合法,粘合剂连接法,热熔粘合法及挤压涂覆法而被粘合的。
多层层压制品的一个实施例是一种实施方案,其中某些层是纺粘的,某些是熔喷的,例如一种纺粘/熔喷/纺粘(SMS)层压制品揭示在Brock等人的US 4,041,203,Collier等人的US 5,169,706,和Bornslaeger的US 4,374,888中,其整个内容在此可引为参考。这种层压制品是通过按顺序首先把纺粘织物层放置到一移动的成型带上,然后放置一熔喷织物层及至少另一纺粘层,并且随后以上述方式粘合该层压制品而制成的。另外,织物层可分别制成,将它们收集在一些辊上,并在一个单独粘合步骤中而结合在一起,该内容揭示在US 4,720,415中,在此其全部内容可引为参考。这样的多层层压制品通常具有的基重为0.1~12osy(6至400gsm),尤其是0.75~3osy。
本发明的复合弹性材料具有至少一弹性聚烯烃层与至少一其它类型的弹性聚合物层和一可收缩的纤维网。该纤维网连接到弹性纤维网上。这是可实现的,在弹性纤维网被拉伸时候和/或而可收缩纤维网是被颈缩。弹性聚烯烃最好由金属茂工艺方法制成。有可能是两个可收缩纤维网;在弹性层的每侧上有一该纤维网,也有可能是多层弹性层。弹性层材可以用下列方式排列,例如,弹性聚烯烃材料在中间,在弹性聚烯烃材料的各侧上有其它类型的聚合物弹性层,并且最后一可收缩粘合到各其它弹性层上。层压制品可具有在中间的弹性聚烯烃层、每侧上的其它弹性层、然后在其它弹性层每侧上的附加弹性聚烯烃层以及最后的可收缩层作为外层。层的数量和排列仅受设备和设想的限制。
本发明的可收缩纤维网可以是聚烯烃,例如聚丙烯的纺粘纤维网,或可以是其它适宜材料,它没有如上限定的弹性特征。
图4表示了一种用于把拉伸粘合弹性和可收缩纤维网制成层压制品的连续制造一列式工艺方法示意图,其中两个可收缩纤维网位于由两弹性聚合物构成的一可拉伸纤维网的各相对侧上。在图中,弹性聚合物由各熔喷纺丝装置1被放置到一成形线2上,而制成一弹性纤维网3,成形线2以某第一速度如层材放置速度而移动。弹性纤维网3向前移动并通过粘合辊6、7,在这种情况下,在此处弹性纤维网3与从贮辊上退绕的两个可收缩纤维网4、5结合在一起。所示的粘合辊6、7是由一个有图案花纹的轧光辊6和一个光滑砧辊7组成,但是如上所述的其它方法和装置在此也可使用。纤维网3,4,5以与成形线2的辊和各贮辊相关的箭头所示的方向运行。弹性纤维网3是通过下述方式而拉伸到所希望的数量值,即粘合辊6、7以大于成形线2的速度转动,产生一个粘合辊/成形线的速度比。辊6、7之间的压力把可收缩纤维网4,5粘合到弹性纤维网3上,从而形成一种复合弹性材料8。随后复合弹性材料8被卷绕到卷绕筒9上。
本发明人获得的是这样一种层压制品,即其中至少一层最好是由聚合度分布性小于4的弹性聚烯烃制成的,至少一层其它弹性聚合物层,还有一层非弹性可收缩纤维网,使得由这种层压制品制成的产品的一些弹性特性,如滞后性,可精确得到控制。尤其是具有一弹性聚烯烃层与一弹性聚(苯乙烯/乙烯-丁烯/苯乙烯)嵌段共聚物层和在各侧上的一可收缩聚丙烯纤维网的层压制品,形成有非常良好的混合拉伸和回缩特征。
为了说明根据本发明层压制品的优点,给出下列的实例和对比例。请注意,用于生产这些层压制品的工艺条件被给在表1中。
对比例
使用作为可收缩纤维网的0.4osy(13.6gsm)聚丙烯纺粘外层和Shell’s KratonG-2755聚(苯乙烯/乙烯-丁烯/苯乙烯)或SEBS树脂的一弹性熔喷内层,来制成复合弹性材料的两样品。当弹性熔喷层用如表所示的粘合/线比拉伸时,外层被热熔粘合,以生产出具有13%粘合区域图案花纹的层压制品。
实例1
使用作为可收缩纤维网的0.4osy(13.6gsm)聚丙烯纺粘外层和具有在190℃和2160gm负载下熔流指数为30g/m的Dow’s ENGAGE58200.02金属茂聚合物的一熔喷内层来制成复合弹性材料的3个样品。当弹性熔喷层用如表中所示的粘合/线比拉伸时,外层热熔粘合以生产出具有13%粘合区域案图花纹的层压制品。
实例2
使用作为可收缩纤维网的0.4osy(13.6gsm)聚丙烯纺粘外层和Shell’s KratonG-2755聚合物的一熔喷内层以及Dow’s ENGAE58200.02聚合物的一个第二内层来制成复合弹性材料的两样品。当弹性熔喷内层采用如表中所示的粘合/线比拉伸时,外层热熔粘合以生产出具有13%粘合区域案图花纹的层压制品。
对比例和实例根据上述的循环测试方法在“试验方法”下测试拉伸特性,其结果公布在表1中。在表中,缩写EXT指“拉伸”,RET指“回缩”,STS指“停止拉伸”,MB指“熔喷”,BW指“基重”。
层压制品基重GSM | 拉至停止时的伸长率% | 循环 1EXT TEA | 循环 1RET TEA | 循环 5EXT TEA | 循 环5 /1EXT/TEA比 | 截 流处 负载,g | 循环伸长率% | 30%伸长 率的 负载,g | 40% 时伸 长 率的 负载,g | 循环伸长时的负载,g | 熔融温度,F | 空气度,F | 粘合/线比 | 粘合温度,F(set) | |
实例2 | 64 | 86.9 | 30.5 | 20.4 | 21.7 | 0.7115 | 854 | 60 | 420 | 515 | 680 | 455 | 491 | 2.9 | 135 |
实例2 | 56 | 111.3 | 44.5 | 28.1 | 30.8 | 0.6921 | 927 | 80 | 368 | 461 | 735 | 455 | 491 | 3.8 | 135 |
实例1 | 65 | 83.3 | 30.9 | 20.2 | 20.3 | 0.6570 | 871 | 60 | 415 | 527 | 730 | 466 | 477 | 4.2 | 145 |
实例1 | 70 | 74.2 | 27.2 | 16.4 | 16.7 | 0.6139 | 813 | 60 | 356 | 462 | 681 | 431 | 438 | 2.8 | 170 |
实例1 | 65 | 90 | 28.9 | 17.6 | 17.9 | 0.6194 | 774 | 60 | 378 | 497 | 725 | 401 | 438 | 4.2 | 170 |
对比例 | 47 | 151.4 | 30.7 | 20 | 21.2 | 0.6906 | 957 | 60 | 436 | 513 | 618 | -500 | 474 | 3.2 | 130 |
对比例 | 47 | 151.4 | 49.9 | 29.3 | 31.8 | 0.6373 | 957 | 80 | 460 | 535 | 716 | -500 | 474 | 4.5 | 130 |
该表表示出在层压制品中,通过提供弹性聚烯烃和非聚烯烃弹性体的层材,良好的拉伸控制和回缩特性是可能的,并且有可能制造一种比其它层压制品具有或多或少拉伸和更好或更差回缩的层压制品。这种控制使由本发明的层压制品制成的产品的使用者能更精确地让其产品满足服务对象的需要,由于产品将提供所要求的拉伸,而且正是所要求的,这也可使费用降低。例如,生产一种具有一弹性聚烯烃层与在其各侧上的弹性聚氨基甲酸酯层的层压制品,将提供一种比具有一弹性聚烯烃层和在其各侧上的弹性SEBS的层压制品有不同拉伸和回缩特征的层压制品。把弹性聚烯烃层放在弹性聚醚酯各侧上将提供与上述两种具有不同滞后现象的层压制品。
尽管本发明的少数实施例已在上面详细描述,在本领域的技术人员将很容易理解,根据这些实施例一些改进是可能做到的,而实质上不会脱离本发明的新型教导和优点。因此,所有改进都打算包括本发明及随后的权利要求范围内。
在权利要求中,方法加上功能的权利要求是用来覆盖在此所描述的为完成列举功能的结构,不仅包括结构上的等同物,而且包括等同的结构。因此,尽管钉和螺钉可能结构不等同,因为钉使用一圆柱形表面与木质部分固定在一起,而螺钉使用一螺旋面与木质部分固定在一起,在紧固木质部分场合中,钉与螺钉可为等同结构。
Claims (17)
1.一种受控滞后复合弹性材料,包括一层弹性金属茂聚烯烃层的第一层,并且它连接至少一层另外的层,这另外的层是由弹性聚合物构成,它选自包括下列所述的种类:聚氨基甲酸酯,共聚醚酯,聚酰胺聚醚嵌段共聚物,乙烯乙酸乙烯酯(EVA),和通式为A-B-A′,A-B-A-B,或A-B的嵌段共聚物,上述层还连接一第三层,该层是一种可收缩纤维网。
2.根据权利要求1的材料,其中所述的聚烯烃具有少于4的聚合度分布性。
3.根据权利要求1的材料,其中所述的第三层在连接时是颈缩拉伸的。
4.根据权利要求1的材料,其中所述的第一层和所述的一层另外的层在连接于所述的可收缩纤维网时是被拉伸的。
5.根据权利要求1的材料,其中所述的层是通过选自包括下列所述种类的方法而被连接在一起的:针刺法,粘合剂粘合,热熔粘合,和挤压涂覆。
6.根据权利要求1的材料,其中所述的第一层和所述的一层另外的层是薄膜。
7.根据权利要求1的材料,其中所述的至少一层另外的层是一种由纤维构成的纤维网,该纤维是选自包括下列种类的聚合物,聚氨基甲酸酯,共聚醚酯,聚酰胺聚醚嵌段共聚物,乙烯乙酸乙烯酯(EVA),共聚(苯乙烯/乙烯-丁烯),(聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯),和聚(苯乙烯/乙烯-丁烯/苯乙烯)。
8.根据权利要求1的材料,其中所述的第一层是一种由具有聚合度分散性少于4的弹性聚烯烃所构成的微细纤维的熔喷纤维网,而所述的至少另外一层是由聚(苯乙烯/乙烯-丁烯/苯乙烯)构成的熔喷纤维网。
9.一种个人护理制品,选自包括下述种类:尿布,运动裤,吸收性内衣,成人不能自制产品,和妇女卫生制品,该个人护理制品由权利要求8所述熔喷纤维网材料构成。
10.根据权利要求9的个人护理制品,它是一种尿布。
11.根据权利要求9的个人护理制品,它是一种吸收性内衣。
12.根据权利要求9的个人护理制品,它是一种成人不能自制产品。
13.根据权利要求9的个人护理制品,它是一种妇女卫生制品。
14.一种受控滞后复合弹性材料,它包括由平均直径小于10微米的纤维构成的金属茂聚烯烃层的第一层,并且它连接一层平均直径小于10微米的纤维构成的第二层,其由选自包括下列种类的弹性聚合物,聚氨基甲酸酯,共聚醚酯,聚酰胺聚醚嵌段共聚物,乙烯乙酸乙烯酯(EVA),和通式为A-B-A′,A-B-A-B,或A-B的嵌段共聚物,上述两层还连接一第三层,该层是由平均直径大于7微米的纤维构成的可收缩纤维网。
15.根据权利要求14的材料,其中所述的第一层和第二层是在连接其第三层时被拉伸的。
16.根据权利要求14的材料,其中它还包括连接到第一层的平均直径大于7微米的纤维构成的另一可收缩纤维网。
17.根据权利要求14的材料,它还包括由平均直径小于10微米纤维构成的第四层,其纤维由选自包括下列种类的弹性聚合物构成:聚氨基甲酸酯,共聚醚酯,聚酰胺聚醚嵌段共聚物,乙烯乙酸乙烯酯(EVA),和通式为A-B-A′,A-B-A-B,或A-B的嵌段共聚物,其连接第一层,并且具有平均直径大于7微米的纤维构成的可收缩的第五层连接于所述的第4层上,其中第一,第二和第四层在连接时被拉伸。
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CN108950861A (zh) * | 2018-08-10 | 2018-12-07 | 苏州多瑈新材料科技有限公司 | 一种双向弹性纤维材料的成型方法 |
CN112127007B (zh) * | 2020-08-28 | 2022-09-02 | 武汉纺织大学 | 聚氨酯-尼龙6嵌段共聚物及其制备方法和聚氨酯-尼龙6弹性纤维 |
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- 1996-10-18 WO PCT/US1996/016780 patent/WO1997020091A1/en active IP Right Grant
- 1996-10-18 EP EP96939481A patent/EP0861343B2/en not_active Expired - Lifetime
- 1996-10-18 BR BR9611716A patent/BR9611716A/pt not_active IP Right Cessation
- 1996-10-18 KR KR10-1998-0703569A patent/KR100401431B1/ko not_active IP Right Cessation
- 1996-10-18 CN CN96199531A patent/CN1080343C/zh not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
EP0861343B2 (en) | 2009-03-18 |
EP0861343B1 (en) | 2001-12-12 |
AU698002B2 (en) | 1998-10-22 |
AU7664496A (en) | 1997-06-19 |
US5709921A (en) | 1998-01-20 |
DE69617997D1 (de) | 2002-01-24 |
KR19990067547A (ko) | 1999-08-25 |
CN1207146A (zh) | 1999-02-03 |
CA2235386A1 (en) | 1997-06-05 |
KR100401431B1 (ko) | 2003-11-15 |
EP0861343A1 (en) | 1998-09-02 |
DE69617997T3 (de) | 2009-09-24 |
MX9803715A (es) | 1998-09-30 |
WO1997020091A1 (en) | 1997-06-05 |
BR9611716A (pt) | 1999-02-23 |
DE69617997T2 (de) | 2002-08-01 |
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