CN1100666C - 包含填料膜和连续膜的可透气层压制品 - Google Patents
包含填料膜和连续膜的可透气层压制品 Download PDFInfo
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Abstract
一种可透气的多层膜层压制品(20),包括粘合到连续膜(16,26)上的微孔填料膜(22)。在该膜层压制品的一个表面或2个表面上可以粘贴诸如纤维网之类的支承层。
Description
发明领域
本发明涉及包含填料膜和可拉伸的连续膜的可透气多层膜层压制品。此外,本发明还涉及制造这种层压制品的方法。
发明背景
本发明涉及包含至少一层微孔膜和一层可拉伸的连续膜的可透气层压制品及制造这种层压制品的方法。这类材料尤其在限制使用和用可弃物品领域中有各种用途。
传统上,在限制使用或用可弃物品中通常用膜来提供阻挡性能。所谓限制使用或用可弃,是指产品和/或部件只用少数几次或可能只用一次就丢弃。这类产品包括,但不限于例如手术帘布和手术衣,用可弃工作服例如衣裤相连的工作服和实验室用的外套,以及个人护理吸收产品例如尿布、运动短裤、失禁服装、卫生巾、绷带和包装材料。在个人护理吸收产品例如婴儿尿布和成人失禁产品中,用膜作为外罩,其目的是防止人体废液污染衣服、被褥及使用的周围环境的其它方面、在包括医院服装的防护服方面,用膜来防止穿戴者和病人之间的微生物交叉交换。在包装领域,用膜来让H2O和O2通过,但不让微生物通过。
采用膜层压法可生产出不透性的,但在外观和质地上又有点象布的材料。用可弃尿布上的外罩就是其中的一个例子。在这方面,可参考1989年4月4日颁布的共同转让的美国专利4,818,600和1988年2月16日颁布的美国专利4,725,473。手术衣和手术帘布是另一些例子。在这方面,可参见1983年4月5日颁布的美国专利4,379,102。
在这类层压制品中使用膜的主要目的是提供隔液性能。也需要可透气的这类层压制品,以便使它们具有透过水蒸气的能力。由这种可透气和/或微孔膜的层压制品做成的衣服穿着起来更舒适,因为减少了衣服下面水蒸气的浓度和皮肤的水合作用。但是,在可透气膜中孔的尺寸不能太大,尤其在防护服应用方面,例如工业用或医用服装,化学液体的渗透对穿着者来说存在着污染的危险。此外,有微孔的膜能让化学蒸气和/或病毒通过从而降低防护服的效果。
获得可透气微孔膜的常用方法是将含有填料的热塑性薄膜进行拉伸。在拉伸过程中通过填料颗粒产生微孔。薄膜通常在牵伸工艺之前进行加热,以使其塑性和展性更大些。这种牵伸或拉伸也使膜中的分子结构发生取向,使其在拉伸方向的强度和耐用性增加。由于拉伸所产生的分子取向对于改善耐用性来说是有利的。
膜可以在机器方向和/或横截机器方向上被拉伸。在横截方向上拉伸膜是特别复杂的,因为必须在膜的边缘施加力量,使膜伸长。通常使用拉幅框架。相反,在机器方向上拉伸膜是比较容易的。只需在膜处于加热和塑性状态时增加2辊之间的牵引比或速度比就够了。然而,对于单向拉伸的薄膜,即机器方向或横向拉伸的薄膜,存在耐用性问题。单向拉伸引起分子在拉伸方向上取向。这就导致沿拉伸方向容易撕裂或开裂的薄膜。例如,沿机器方向取向的膜具有沿机器方向开裂或撕裂的倾向。同时,在机器方向上膜的抗拉特性急剧增加,而横向上的抗拉强度则大大低于机器方向上的抗拉强度。
单向拉伸取向膜的这些耐用性问题是众所周知的。通常可用两种方法来消除由于这种高度各向异性强度特性所引起的产品耐用性问题。第一种方法是在机器方向和横向两个方向上对膜进行拉伸定向。经过双轴拉伸的薄膜具有更加平衡的强度性能。第二种方法是将一层沿机器方向取向的薄膜与一层沿横向取向的薄膜结合成一种层压制品。这种方法费时、尺寸有限,而且成本高。因此需要一种使用低成本材料制成的单向拉伸、重量轻、可透气的薄膜层压制品,以及提供这种透气性、阻挡性和使用耐久性均理想的层压制品的方法。
此外,为了避免产生太大的孔,通常需要精确控制拉伸工艺,因为,如前所述,不希望的大孔的形成会使膜的水压头值降低到不可接受的低水平,从而引起液体、产生气味的微生物的泄漏。因此需要一种可透气的柔性层压制品,以及提供具有透气性阻挡性能且适应性和舒适性均理想的层压制品的方法。
发明简述
本发明涉及包含一层取向填料膜和至少一层连续膜的多层膜层压制品。填料膜包含聚合物树脂和填料,填料含量至少为所述聚合物树脂体积的10%。较好地,填料膜含有约25~约50%(体积)的填料。连续的弹性膜在拉伸之前粘合到填料膜上。弹性膜是水蒸气可透过的,但对引起气味的微生物而言,多半是不可透过的。连续的弹性膜较好是连续粘合或点粘合到填料膜上。这种层压制品是经过拉伸的,使得填料膜本身的水蒸气透过值(WVTR)为至少300g/m2·24小时。拉伸后的层压制品的WVTR为至少200g/m2·小时。
在一种应用中,弹性连续膜层在经过一个达到约150%无偏长度的拉伸长度的拉伸循环后,其立即回复长度至少为其伸长的约50%。在另一个应用中,本发明的弹性连续膜在经过一个达到约200%无偏长度的拉伸长度的拉伸循环后,其立即回复长度至少为其伸长的约50%。在一个具体实施方案中,填料膜层也是弹性的,且具有一个永久变形,所以微孔仍保持开放状态。在另一个具体实施方案中,弹性连续膜的永久变形小于填料膜的永久变形。
所得到取向多层膜层压制品较好是柔性的、可透气的和斥液的,且具有阻挡不希望的微生物的作用。填料膜层中和连续膜中所包含的材料的选择以及各层之间所采用的粘合方法的类型均会影响层压制品的拉伸性能、外观和透气性。
在第一个应用中,弹性连续膜为微孔填料膜提供了支承和增强结构。在第二个应用中,甚至在层压制品包含具有大微孔的填料膜的情况下,该连续膜仍然能保持对液体的总的阻挡作用和对不希望的蒸气的阻挡作用。在第三个应用中,该多层膜层压制品包括一层弹性连续膜,该膜被点粘合到非弹性填料膜上,使得该层压制品可在取向方向上进行拉伸。在第四个应用中,该多层膜层压制品粘合到另一支承层如非织造纤维网上。
这类多层膜层压制品作为整个用品或部件有各种用途,其中包括,但不限于在包装、包括工业工作服等防护服用品,以及个人护理吸收用品,包括尿布、运动短裤、卫生巾、失禁设备、绷带方面的应用。这类同样的薄膜也可用在医用服装中例如手术帘布和手术衣,以及各种衣服物品中,即可作为整个物品,也可只作为物品的一个部件。
附图简述
图1是按照本发明连续粘合到连续膜上的填料膜的示意图。
图2是按照本发明点粘合到连续膜上的填料膜的示意图。
图3是按照本发明制备多层膜层压制品的方法的示意图。
图4是使用本发明的多层膜层压制品的尿布的示意图。
优选具体实施方案的详述
本发明涉及包含连续弹性膜和填料膜的多层膜层压制品。
这里使用的“连续膜”这一术语描述拉伸后膜中不含孔的单片膜,以使得该膜具有阻挡作用,因而具有高水压头值。
这里所使用的术语“连续粘合”描述两个膜表面之间的粘合,其中该粘合基本上不会破裂。相反,这里所使用的术语“点粘合”是指两个膜表面之间的粘合,其中该粘合是不连续的,而且在该表面的一些具体点上。
现在参考图1,本发明的未拉伸多层膜层压制品10用图解说明包含填料膜层12,填料膜层含有聚合物材料和填料15。填料膜层12连续地粘合到含有弹性体材料的连续膜层16上。拉伸后产生一种取向的多层膜层压制品20。层压制品20含有在拉伸过程中在取向的填料膜层22中由填料15产生的微孔或细孔23和取向的连续膜层26。
填料膜层12、22中的聚合物材料可以是弹性材料或非弹性材料。“弹性”这一术语在这里用来表示在施加一个偏置力时会被拉伸到,或者说,可伸长(或延伸)到一个拉伸的偏置长度的任何材料,所述偏置长度至少为其松弛无偏长度的约150%,当拉伸、伸长力解除时,该材料会回复其伸长的至少50%。一个假设的例子是1英寸(2.54cm)样品的材料可伸长到至少1.50(3.81cm)英寸,当伸长到1.50(3.81cm)英寸然后使其松弛时,该样品将会回复到不大于1.25(3.18cm)英寸的长度。许多材料可以拉伸大大高于其松弛长度的50%,例如,100%或更高,在解除拉伸力后,这些材料中很多材料都能基本上回复到其原始松弛长度,例如,回复到其原始松弛长度的105%以内。
这里所用的术语“非弹性”是指不能落在上述“弹性”定义范围内的任何一种材料。
可用于填料膜10的聚合物材料的例子包括非弹性热塑性聚合物、弹性体、塑性体以及它们的组合。
可用于本发明的非弹性热塑性材料是可挤塑的热塑性聚合物,例如聚酰胺、尼龙、聚酯、聚烯烃或包括均聚物、共聚物在内的聚烯烃的共混物,以及这些材料的共混物。
可用于实施本发明的弹性体可以是由共聚物制成的那些弹性体,共聚物的例子是:聚氨酯、共聚醚酯、聚酰胺聚醚共聚物、乙烯乙酸乙烯酯(EVA)共聚物、通式为A-B-A′或A-B的嵌段共聚物,例如共聚(苯乙烯/乙烯-丁烯)、苯乙烯-聚(乙烯-丙烯)-苯乙烯、苯乙烯-聚(乙烯-丁烯)-苯乙烯、聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯、聚(苯乙烯/乙烯-丁烯/苯乙烯)。
有用的弹性体树脂包括通式为A-B-A′或A-B的嵌段共聚物,式中A和A′各是热塑性聚合物含有苯乙烯部分的端部嵌段,例如聚(乙烯基芳烃),B是弹性体聚合物中部嵌段,例如共轭二烯或低级链烯烃聚合物。A-B-A′型的嵌段共聚物对A和A′嵌段而言,可以有不同或相同的热塑性嵌段聚合物,本发明用的嵌段共聚物包括线型、支链和辐射型嵌段共聚物。在这方面,辐射型嵌段共聚物可表示为(A-B)m-X,其中X是多官能原子或分子,且其中各个(A-B)m-以A为端部嵌段的方式从X向外辐射。在辐射形嵌段共聚物中,X可以是一个有机或无机多官能原子或分子,m是与X中原先存在的官能基数目相同的整数。m的值一般至少是3,常常是4或5,但不限于此。因此,在本发明中,“嵌段共聚物”一词,特别是“A-B-A′”型和“A-B”型嵌段共聚物,用来包括含有这种橡胶类嵌段和热塑性嵌段的所有嵌段共聚物。这类弹性体共聚物的商品实例是,例如称为KRATON的那些材料,这些材料可从得克萨斯州休斯敦市的壳牌化学公司得到。KRATON嵌段共聚物有几种不同的配方,其中数种可参见美国专利4,663,220、4,323,534、4,834,738、5,093,422和5,304,599,这些专利并入本文作为参考。
由弹性体A-B-A-B四嵌段共聚物构成的聚合物也可用于实施本发明。这类聚合物详述于泰勒(Taylor)等人的美国专利5,332,613中。在这类聚合物中,A是热塑性聚合物嵌段,B是氢化异戊二烯。这种四嵌段共聚物的一个例子是苯乙烯一聚(乙烯-丙烯)-苯乙烯-聚(乙烯-丙烯)或SEPSEP弹性体嵌段共聚物,可从得克萨斯州休斯敦市的壳牌化学公司得到。
其它可以使用的弹性体材料的例子包括聚氨酯弹性材料,例如B.F.Goodrich公司的ESTANE(商标)或Morton Thiokol公司的MORTHANE,聚酯弹性体材料,例如杜邦公司的HYTREL,和以前可从荷兰Arnhem市的AKZO塑料公司得到,现在从荷兰Sittard市的DSM公司得至的ARNITEL。
另一种适用的材料是通式如下的聚酯嵌段酰胺共聚物:式中n是正整数,PA代表聚酰胺聚合物链段,PE代表聚醚聚合物链段。具体地说,聚醚嵌段酰胺共聚物按照ASTM D-789测得的熔点为约150℃~约170℃;按照ASTM D-1238,条件Q(235C/lkg载荷)测得的熔体指数为约6g/10分钟~25g/10分钟;按照ASTMD-790测得的挠曲弹性模量为约20MPa~约200MPa;按照ASTMD-638测得的断裂拉伸强度为约29MPa~约33MPa;以及按照ASTMD-638测得的断裂极限伸长为约500%~约700%。聚醚嵌段酰胺共聚物的一个具体例子按照ASTM D-789测得的熔点为约152℃;按照ASTM D-1238,条件Q(235 C/1kg载荷)测得的熔体指数为约7g/10分钟;按照ASTM D-790测得的挠曲弹性模量为约29.50MPa;按照ASTM D-639测得的断裂拉伸强度为约29MPa;以及按照ASTMD-638测得的断裂伸长为约650%。这类材料有各种级别,可从新泽西州Glen Rock市的ELF阿托化学公司得到,其商品名为PEBAX。使用这类聚合物的例子可参见Killian等人转让给本发明同一受让人的美国专利4,724,184、4,820,572和4,923,742,这些专利并入本文作为参考。弹性体聚合物也包括乙烯和至少一种乙烯基单体的共聚物,乙烯基单体的例子例如有乙酸乙烯酯、不饱和脂族单羧酸,和这类单羧酸的酯类。这些弹性体共聚物和从这些弹性体共聚物形成弹性非织造纤维网的方法公开于例如美国专利4,803,117中。
热塑性共聚酯弹性体包括如下通式的共聚醚酯:式中“G”选自由下列组成的一组:聚(氧乙烯)-α,ω-二醇、聚(氧丙烯)-α,ω-二醇、聚(氧四亚甲基)-α,ω-二醇,“a”和“b”是包括2、4和6的正整数,“m”和“n”是包括1-20的正整数。这类材料当按照ASTM D-638测定时,其断裂伸长通常为约600%~750%,当按照ASTM D-2117测定时,其熔点为约350°F~约400°F(176~205℃)。
这类共聚酯材料的商品例子是例如被称为ARNITEL的那些材料,以前可从荷兰Arnhem市的AKZO塑料公司得到,现在从荷兰Sittard市的DSM公司得到,或者被称为HYTREL的那些材料,可从特拉华州威明顿市的杜邦公司得到。
可用于实施本发明的塑性体既具有非弹性的热塑性塑料的物理性能又具有弹性体的物理性能。有用的塑性体的例子包括金属茂催化的基于乙烯的材料。
这里使用的术语“金属茂催化的基于乙烯的材料”包括采用金属茂或受限几何催化剂,即一类有机金属配合物作为催化剂,由至少乙烯进行聚合而生产的那些聚合物材料。例如,一般的金属茂催化剂是二茂铁,即由金属夹在2个环戊二烯基(Cp)配体之间而形成的一种配合物。金属茂工艺催化剂包括二氯化二(正丁基环戊二烯基)钛、二氯化二(正丁基环戊二烯基)锆、氯化二(环戊二烯基)钪、二氯化二(茚基)锆、二氯化二(甲基环戊二烯基)钛、二氯化二(甲基环戊二烯基)锆、二茂钴、三氯化环戊二烯基钛、二茂铁、二氯化二茂铪、二氯化异丙基(环戊二烯基,-1-芴基)钴、二氯化二茂钼、二茂镍、二氯化二茂铌、二茂铷、二氯化二茂钛、氯化氢化二茂锆、二氯化二茂锆等。这类化合物更详尽的清单包括在转让给道化学公司的Rosen等人的美国专利5,374,696中。这类化合物也详述于同样是转让给道化学公司的Stevens等人的美国专利5,064,802中。
金属茂工艺,以及尤其催化剂和催化剂载体体系是许多专利的主题。Kaminsky等人的美国专利4,542,199叙述了一种程序,其中将甲基铝氧烷(MAO)加入到甲苯中,再加入通式为Cp2MeRHal的金属茂催化剂,式中Me是过渡金属,Hal是卤素,R是环戊二烯基(即Cp)或C1~C6烷基或卤素,然后加入乙烯以生成聚乙烯。转让给道化学公司的LaPointe等人的美国专利5,189,192叙述了通过金属中心氧化作用来制备加成聚合催化剂的方法。埃克森化学专利公司的美国专利5,352,749叙述了在流化床中使单体聚合的方法。美国专利5,349,100叙述了手性金属茂化合物及通过用对映选择性氢化物转移剂产生手性中心的方法来制备手性金属茂化合物的方法。
助催化剂是下列一些材料:例如最普通的MAO、其它烷基铝化合物和含硼化合物,如三(五氟苯基)硼、四(五氟苯基)硼锂,和四(五氟苯基)硼二甲基苯胺。现正继续研究其它助催化剂体系或尽量减少,甚至消除烷基铝化合物的可能性,因为处理困难,并产生产品污染。关键在于金属茂催化剂必须活化或离子化成为阳离子形式,才能与要聚合的单体反应。
本发明中使用的金属茂催化的基于乙烯的聚合物能赋予薄膜与拉伸和回复性能。优选地,金属茂催化的基于乙烯的聚合物选自乙烯与1-丁烯的共聚物、乙烯与1-己烯的共聚物、乙烯与1-辛烯的共聚物及这些的组合。具体地说,优选的材料包括商品牌号为EngageTM的由金属茂衍生的乙烯与1-辛烯的弹性共聚物,可从特拉华州威明顿市的杜邦/道化学弹性体公司得到。特别优选的材料也包括商品牌号为ExactTM的由金属茂衍生的共聚物和三元共聚物,可从得免萨斯州休斯敦市的埃克森化学公司得到。
按照本发明,连续层16、26是一种可伸长的材料。这里所用的术语“可伸长的材料”是用来描述连续层中的材料包围着以至少1.5,或50%的拉伸比进行拉伸之后倾向于回缩的那些材料。可以认为这是要达到至少300g/m2·24小时的WVTR所需的最小拉伸比。可伸长材料的例子包括弹性体、某些聚烯烃和塑性体。可伸长聚烯烃包括聚乙烯(尤其线型低密度聚乙烯)、聚丙烯,以及乙烯与丙烯的共聚物和乙烯或丙烯与其它α-烯烃的共聚物。
在另一个应用中,填料膜12是弹性的,此时填料膜12中的聚合物材料最好具有永久变形。这里所使用的“永久变形”这一术语是聚合物材料的一个物理特性,即,当具有一定原始长度的材料被拉伸,然后解除拉伸力,样品不恢复到其原始长度,但回复到比原始长度更长的长度。永久变形这一特性能允许松弛膜27保留拉伸所产生的微孔或细孔23。
填充膜层10除了包含聚合物材料之外,还包含在膜取向过程中能产生微孔的填料。这里所用的“填料”是指包括可以被加入到聚合物中并能均匀地分散在整个膜中的颗粒和其它形式的材料。膜中填料含量为聚合物树脂总体积的至少10%,优选约25~50%。按照本发明,填料颗粒的尺寸对于产品的功能并不是关键的。有机填料和无机填料只要不影响膜的成形工艺,都包括在本发明的范围之内。
填料的例子包括碳酸钙(CaCO3)、各种粘土、二氧化硅(SiO2)、氧化铝、硫酸钡、碳酸钠、滑石、硫酸镁、二氧化钛、沸石、硫酸铝、纤维素类粉末、硅藻土、硫酸镁、碳酸镁、碳酸钡、高岭土、碳、氧化钙、氧化镁、氢氧化铝、纸浆粉、木粉、纤维素衍生物、聚合物粒子、几丁质和几丁质衍生物。填料颗粒可任选地用脂肪酸进行涂布,例如用硬脂酸和二十二烷酸进行涂布,这些酸可能有利于颗粒(整体)的自由流动,而且易于分散到聚合物基体中。
图1中表示的填料膜12、22连续地被粘合到连续膜16、26上。这种类型的粘合可通过,例如,在层12、22之间涂布一个连续的粘合剂层来达到。其它类型的连续粘合包括,例如,热粘合和共挤出层12、22。此外,可以通过从其中加入了增粘剂的聚合物材料形成各膜层12、16来实现连续粘合。
作为替代的方案,如图2所示意的,本发明的层压制品中的膜层32、36可以通过点粘合相互粘在一起。图2说明层压制品30中所含的填料膜32通过粘合点38附贴在连续膜36上。然后将该层压制品30进行拉伸,形成含有伸展的填料膜层42的层压制品40,所述填料膜层42含有在拉伸过程中由于填料颗粒35而形成的微孔43。一旦让层压制品40松弛,所形成的层压制品50就含有具有择优收缩,即有皱纹朝上的收缩树脂材料57的微孔填料膜层52。所形成的收缩的层压制品就可容易地被拉伸到其原来的拉伸长度。这种择优收缩为层压制品的微孔填料膜52一侧提供了更象布的手感。相反,如图1所示,树脂材料27在填料膜层22中仍然是伸展的,所述填料膜层22连续地粘合到连续层26上。粘合点38例如可用粘合剂、热点粘合或超声粘合等方法产生。
填料膜与连续膜之间的粘合类型以填料膜的材料种类都会影响多层膜层压产品的特性。在一个填料膜32为弹性材料的应用场合中,构成填料膜32的聚合物树脂的永久变形特性最好大于连续膜层36的永久变形,以便获得“起皱”效果。在另一个应用中,填料膜32是非弹性的,且优选类似布的手感,此时将填料膜32点粘合到连续膜36的点粘合作用就会达到在层压制品50上的收缩树脂57中的择优收缩。在又一个应用中,不希望有类似布的手感,此时较好的是,填料膜32包含弹性体材料,其永久变形特性相当于连续膜层36的永久变形。
此外,粘合类型对于多层膜层压产品的可拉伸性也有影响。按这里所用的,一个从初始长度A开始取向至某一拉伸长度B之后,其松弛长度为C的产品,如果该产品可以反复地重新拉伸到长度B,那么该产品就是“可拉伸的”。参看图2,如果填料膜52是点粘合到弹性连续膜56上的非弹性材料,则所形成的层压制品20是可拉伸的。相反,参看图1,如果22是连续粘合到弹性连续膜26上的非弹性材料,则所形成的层压制品20就很可能不象上面讨论的层压制品50那样可拉伸。
当然。应该理解的是,本发明包括一种多层膜层压制品(未表示出),其中多个填料膜层相互粘合在一起,并附贴在一层或多层连续膜上。此外,多层层压制品可包括相互交替附贴在一起的填料膜层和连续膜层。
一般来说,现在已经能够生产水蒸气透过率(WVTR)为至少约200g/m2·24小时的层压制品了,测定方法按照ASTM E-96-80WVTR试验,用Celgard2500作为对照样品。一般来说,影响透气性数值的因素包括填料含量、膜的拉伸条件(例如,是在环境温度下还是在高温下进行)、取向比和膜厚。较好是,可作为有限使用或用可弃物品中的部件使用的本发明的多层膜层压制品的WVTR值在约1,000~约5,000g/m2·24小时之间,取决于该物品的应用场合。
膜或层压制品的水压头值是材料液体阻挡性能的一种度量。水压头试验确定在预定量的液体通过之前织物所能支承的液体高度(厘米)。织物的水压头读数较高,说明该织物对液体水渗透的阻力比水压头较低的织物大。水压头试验按照联邦试验标准191A,方法5514进行。
多层膜层压制品的渗透性受该层压制品中连续膜层的渗透性的限制。按这里所使用的,膜或层压制品的渗透性是指膜或层压制品的渗透系数。该渗透系数具有下面方程式I中所述的量纲:
(I) P=〔(渗透量)×(膜/层制品厚度)〕/
〔(面积)×(时间)×(跨过膜/层制品的压力降)〕想要阻挡的不希望的分子的类型在某种程度上将界定层压制品中连续膜的组成。膜层的渗透性通常受包括其密度、可拉伸材料的结晶度、分子量和交联度以及该层中的取向量和添加剂的类型等因素的影响。因此,选择适当的可拉伸材料就能获得例如对水蒸气分子,而不是例如对氨蒸气分子通过所形成的层压制品的选择性的渗透性。
通过下列步骤可以获得所需的性能:第1.制备上述聚合物树脂材料、在树脂中加入填料、将该加有填料的树脂挤出制成填料膜;第2.制备弹性体树脂、将该弹性体树脂挤出制成连续膜;第3.将填料膜粘合到连续膜上。另一种替代方法是可采用图3所说明的方法,即共挤出法来制备该未拉伸的填料膜/连续膜。然后将该填料膜/连续膜层压制品在至少1个方向上,通常在机器方向上进行拉伸或取向。如下面更详细说明的,所形成的膜的层压制品是可透气的、具有阻挡性能,而且在取向方向上的强度增加。
一般而言,形成填料膜/连续膜层压制品100的方法如附图中的图3所示。参考该图,层压制品100从一台诸如浇注或吹塑装置的膜共挤出设备140中形成。典型地,设备140将包括2台挤出机141、141a。包括聚合物材料和填料的填料树脂在混炼机143中制备,然后引入到挤出机141中。弹性体树脂在另一台混炼机143a中制备,然后引入到挤出机141a中。层压制品100共挤出到一对夹辊或冷却辊142上,其中的一个辊可以有图案,以便使新形成的层压制品100具有压花。
将层压制品100从膜挤出设备140引导到诸如机器方向取向机之类的膜拉伸装置144中,这种装置可从卖主例如罗得岛,Providence的Marshall and Williams公司买到。这种装置144有许多牵伸辊146,以比相对于配置在它前面的那对辊子更快的前进速度转动。这些牵伸辊146施加一定量的应力,从而将层压制品100沿膜的纵向拉伸到某一拉伸长度,这个方向就是层压制品100通过该工艺的运行方向,如图3所示。牵伸辊146可以加热便于更好的加工。较好的是,装置144也包括一些从牵伸辊146来的上游辊和下游辊(未示出),可以用来在定向之前对层压制品进行预热和/或在拉伸之后将它进行退火(或冷却)。
达到拉伸长度时,在层压制品100的填料膜中形成许多微孔。层压制品中无填料的膜没有孔。较好的是,拉伸长度为拉伸前该膜无偏长度的约160~约500%,更好为约200~约400%。如果希望的话,可将层压制品100引出装置144,以便除去应力,使拉伸的层压制品100松弛。
将填料膜/连续膜层压制品100粘合到1个或几个基质支承层130上,如图3所示,可能是理想的。多层膜层压制品100的这种进一步的层叠可能提高膜层压制品的强度和耐用性。如果希望的话,膜层压制品100可附贴到1个或多个支承层130上,以形成增强的层压制品132。再参考图3,形成设备148,如一对纺粘贮料器的传统非织造纤维网被用来形成支承层120。基本上连续的长纤维150沉积在成形网152上作为未粘合纤网154,然后该未粘合的纤网154通过一对粘合辊156送去将纤维粘合在一起,从而提高所得到的纤网支承层130的撕裂强度。通常将1个或2个辊加热以有助于粘合。典型地,粘合辊156中之一也有图案,以便使纤网130具有有预定粘合表面面积的不连续的粘合图案。另一个辊通常是平滑的砧辊,但这个辊也可以有图案,如果需要这样的话。一旦膜层压制品100被充分拉伸,且支承层130业已形成,就可将这两层放在一起,用一对层压辊或其它设备158将它们相互粘合在一起。象用粘合辊156一样,可以将层压辊158进行加热。同样,这两个辊中的至少一个辊可以加有图案,以便使所形成的层压制品132具有有预定粘合表面面积的不连续粘合图案。一般而言,对于在层压制品132一例上的某一给定表面面积来说,最大粘合点表面面积将不超过总表面面积的约50%。有许多不连续粘合图案可以使用。请参见,例如,Brock等人的美国专利4,041,203,该专利全文并入本文作为参考。层压制品132从层压辊158出来后可卷绕成卷160,用于下一步的加工。或者,该层压制品132也可以继续在线进行进一步加工或转换。
尽管支承层120与图3中所示的膜层压制品是通过热点粘合方法粘合在一起的,但也可以采用其它粘合方法。适用的替代方法包括,例如,粘合剂粘合及使用增粘剂。在粘合剂粘合中,将粘合剂,如热熔粘合剂涂布在膜和非织造纤维材料之间,使该膜与非织造材料粘合在一起。粘合剂可通过,例如,熔体喷射、印刷或熔喷等方法进行涂布。可以得到各种类型的粘合剂,包括由无定型聚α-烯烃、基于乙烯乙酸乙烯酯热熔体制得的那些粘合剂,和可从得克萨斯州休斯顿市的壳牌化学公司得到的牌号为Kraton7的粘合剂,以及从得克萨斯州Odessa市的Rexene公司得到的牌号为RextacTM的粘合剂。
当膜层压制品与支承层用增粘剂粘合时,增粘剂可进入膜本身中。增粘剂的作用主要是增加膜层与纤维层之间的粘着力。随后可通过加热方法将多层膜与纤维层压制品点粘合在一起,但通常只需极少量的热量,因为增粘剂倾向于增加膜的压敏性,从而可形成有点粘合剂粘合的粘合作用。有用的增粘剂的例子包括可从俄亥俄州Akron市的固特异轮胎和橡胶公司得到的WingtackTM 95和可从得克萨斯州休斯顿市的埃克森化学公司得到的EscorezTM 5300。
如果希望具有弹性的层压制品,则该层压制品的弹性方向可通过膜在与支承层的粘合过程中的状态,即看它是松弛的还是拉伸的状态,以及支承层材料的物理性能来调整。例如,如果在膜粘合到非织造材料上时该膜仍处于拉伸状态,而且支承层在横向(“CD”)可延伸,则可生产出CD方向和机器方向(“MD”)均可拉伸的层压制品。如果在拉伸状态将膜粘合到非CD方面可延伸的支承层上,则只能生产出MD方向可拉伸的层压制品。
图3所示的支承层130和130a是非织造纤维网。这种非织造纤维网的制造方法是公知的。这种非织造纤维网可使膜层压制品100具有额外的性能,例如更柔软,类似布的手感。当膜层压制品100在作为个人护理吸收用品的外覆盖层的这类应用中用作液体阻挡层时,和用于医院、外科手术以及清洁房间用的阻挡材料如手术帘布、手术衣及其它形式的服装时,这种性能是特别有利的。
含有本发明膜层的层压制品中的支承层可以是颈缩或非颈缩的聚丙烯纺粘材料、卷曲聚丙烯纺粘材料、粘合梳理纤网、熔喷或纺粘织物。一种特别好的支承层是非织造纤维网。这种纤维网用许多方法成形,包括,但不限于纺粘、熔喷和粘合梳理纤维网工艺。熔喷纤维的成形方法是:使熔融热塑性材料通过许多细的,通常是圆形的毛细管挤出成熔融的线或丝,进入通常 加热的高速气流如空气中,将该熔融热塑性材料的丝拉细,以减少其直径。然后,由通常加热的高速气流将熔喷纤维带走,并沉积在收集表面上,形成无规散的熔喷纤维网。熔喷工艺是众所周知的,可参见各种专利文献及出版物,包括NRL报告4364:B.A.Wendt、E.L.Boone和D.D.Fluharty的“超细有机纤维的制造方法”;NRL报告5265:K.D.Lawrence、R.T.Lukas和J.A.Young的“用于超细热塑性纤维成形的改进设备”;1972年7月11日公布的Prentice的美国专利3,676,424;以及1974年11月19日公布的Buntin等人的美国专利3,849,241。上述文献全部并入本文作为参考。
纺粘纤维的成形方法如下:使熔融热塑性材料以丝的形式从许多细的、通常是圆形的喷丝板中具有挤出丝直径的毛细管挤出,然后迅速拉细,通过,例如,非教学或教学的液体拉伸机或其它众所周知纺粘机。纺粘非织造纤网的生产可参见例如下列专利:Appel等人的美国专利4,340,563、Matsuki等人的美国专利3,802,817、Dorschner等人的美国专利3,692,618、Kinney的美国专利3,338,992和3,341,394、Levy的美国专利3,276,944、Peterson的美国专利3,502,538、Hartman的美国专利3,502,763、Dobo等人的美国专利3,542,615,和Harmon的加拿大专利803,714。上述所有专利文献全部并入本文,作为参考。
也可使用多个支承层130。这类材料的例子包括,例如,纺粘熔喷层压制品和纺粘/熔喷/纺粘层压制品,如在Brock等人的美国专利4,041,203中所述的,该专利全文并入本文,作为参考。
粘合梳理纤维网由短纤维制成,短纤维通常以成包购得。将纤维包置于清棉机中,将纤维分开。然后将纤维送至梳毛机或梳理装置中进一步打开,并使该短纤维沿机器方向排列,以形成沿机器方向取向的非织造纤网。这种纤网一旦形成,就用一种或几种粘合方法进行粘合。一种粘合方法是粉末粘合,在该方法中,将粉状粘合剂分散在整个纤网上,然后进行活化通常用热空气加热纤网和粘合剂。另一种粘合方法是花样粘合,在这种方法中,用加热的压延辊或超声粘合设备将纤维粘合在一起,通常以局部粘合图案的方式粘合,但也可以横贯整个纤维网表面将其粘合,如果希望这样做的话。当使用双组分短纤维时,对许多应用而言,使用穿透空气粘合设备是特别有利的。
图3所示的方法也可用来制造其中支承层130、130a附贴在膜层压制品100的对面上的层压制品。对前述方法的唯一修改是将第二非织造纤维网支承层130a从供料辊162送入到与另一非织造纤维网支承层130一侧相反的膜层压制品100的一例上的层压辊158上。可以在线直接形成一个或两个这样支承层,就象支承层130那样。或者,也可以以预成形辊162的形式供给一个或2个支承层,就象支承层130a那样。无论是哪种情况,第二支承层130a都是送入到层压辊158上,并按与第一支承层130相同的方式层压到膜层压制品上。
正如前面已经说明的,可透气的阻挡膜层压制品100和可透气的层压制品132可用于多种用途,其中包括,但不限于,个人护理吸收用品,例如,尿布、运动短裤、失禁设备和妇女卫生用品,例如卫生巾。一个示例性的用品200,在这种情况下是尿布,示于附图中的图4。参考图4,大多数这样的个人护理吸收用品200包括一个液体可渗透的上部片材或衬料202,一个背部片材或外罩204,和配置在上部片材202和背部片材204之间并被其包裹的吸收剂芯层206。诸如尿布之类的用品200还可以包括某种类型的紧固设施208,例如粘合紧固带或机械扣和环型固定器,以便使该用品维持在穿戴者身上。紧固设施可以包含拉伸材料以形成“伸长耳”,提高舒适性。
膜层压制品100本身或其它形式,如多层膜/支承层层压制品132,可用来制作用品的各种部分,包括,但不限于,拉伸区210、上部和背部片材204。如果膜或层压制品打算用作衬料202,则它很可能必须是多孔的或制成液体可渗透的。当用膜/非织造层压制品作为外罩204时,则将非织造材料一例置于远离使用者的位置是有利的。此外,在这种实施方案中,可以用层压制品中的非织造材料部分作为扣的环形部分和环组合件。
下列实例充分说明了本发明的优点和其它特点。
实例1~7(弹性体膜和层压制品)
下面的弹性体膜和层压制品样品是制造的或从供应商得到的。各种膜和层压制品的WVTR是用下述方法测定的。给出的WVTR值是各实例3个样品的平均值。
实例 | 膜或层压制品的认别 | 定量g/m2 | 膜或层压制品的描述 | WVTRg/m2·24小时 |
1 | Deerfield膜 | 40.7 | 商品聚氨酯膜(1密耳),用于下面的层压品A和B以及点粘合层压品中。 | 1270 |
2 | 未拉伸填料膜 | 63.7 | 60%CaCO3(平均粒径1微米),40%EngageCL 8002聚烯烃弹性体,得自Wilmington,D.E.的杜邦/道弹性体公司 | 97 |
3 | 拉伸填料膜(测试前松驰) | 40.8 | 60%CaCO3(平均粒径1微米),40%EngageCL 8002聚烯烃弹性体,得自Wilmington,D.E.的杜邦/道弹性体公司 | 130 |
4 | 层压品A(未拉伸) | 139.7 | 未拉伸填料膜,用粘合剂粘合到未拉伸聚氨酯膜(Estane 58661,得自BF Goodrich,定量=40.7g/m2)上。 | 44 |
5 | 层压品B(拉伸后松驰,然后再测试) | 146.3 | 填料膜,用粘合剂粘合到聚氨酯膜(Estane58661,得自BFGoodrich,定量=40.7g/m2)上,接着将该层压制品进行拉伸。 | 89 |
6 | Celgard2500 | 13.1 | 商品透气膜,微孔聚丙烯,得自Charlotte,N.C的CelaneseSeparation产品公司 | 5000 |
7 | 点粘合层压品(拉伸后松驰,然后再测试) | 未得到数据 | 填料膜,以断续点方式用粘合剂粘合到聚氨酯膜(Estane58661,得自BFGoodrich,定量=40.7g/m2)上,接着将该层压制品进行拉伸。 | 110 |
样品的拉伸
拉伸的样品(如实例3和5)是通过在膜的机器方向上进行拉伸而制成的。各样品切成约8英寸(20.32cm)宽,17英寸(43.18cm)长。两端用透明胶带连在木棍(约0.75英寸×0.50英寸×24英寸(1.91cm×1.27cm×60.96cm))上。各样品围绕木棍缠几圈以便加固,使得缠有伸展膜样品的棍之间的距离约为11英寸(27.94cm)。将木棍拉离直到样品被拉伸约400%(即拉长至约其原长的500%)为止,使样品在拉伸状态下保持2分钟。然后让样品收缩,再测定其WVTR值。
定量的测量
从各实例取3个样品来测定其定量。用3英寸(7.62cm)直径的冲模从各实例材料中切取各样品。称其重量。用面积去除重量就计算出各样品的定量(即单位面积的重量)。各实例取3个样品的平均定量报告于上表中。
WVTR(水蒸气透过率)的测量
直径为3英寸(7.62cm)的经定量试验后的样品也用来进行WVTR试验。同样,各实例取3个样品进行试验,结果以平均值记录。WVTR是按照ASTM方法E-96-80测量的。将各样品置于加有100cm3自来水的WVTR试验杯上。让放有样品的WVTR试验杯在室温下平衡,然后称重。然后将该有样品的WVTR试验杯放入设定在38℃的Lindberg/Blue,型号MO 1440强制空气烘箱中,并记录时间。经过规定的时间后,再次将有样品的WVTR试验杯称重,以测定在该时间内从杯中通过样品透气的水量。其结果表示为克水/m2·24小时。
层压制品的制备
对于实例4和5,将3M工业胶带和专门产品分部(St.PaulMinn.)制造的超级77粘合剂均匀地分别喷涂在填料膜和聚氨酯膜上。使两个膜涂有粘合剂的面相互接合在一起。让粘合剂干燥至少1小时,然后才可以对该层压制品进行处理或试验。
对于实例7,将具有0.25英寸(0.64cm)孔径、间隔为1英寸(2.54cm)的方形图案的栓钉板放在填料膜的上面和聚氨酯膜的上面,通过栓钉板上的孔将超级77粘合剂分别涂布在这两个膜(填料膜和聚氨酯膜)上。将这两个膜从栓钉板上剥下来,并以粘合剂面对粘合剂面的方式将其相互接合在一起。让粘合剂干燥至少1小时,然后才可以对该层压制品进行处理或试验。
WVTR试验结果(实例1~7)的讨论
虽然对弹性填料膜和层压制品进行拉伸能导致WVTR某种程度的提高,但是与商品Deerfield和Celgard对照样品相比,其总的WVTR不能令人满意。可以认为在拉伸之后弹性膜和层压制品的吸缩使得一部分在拉伸过程中所形成的孔闭合。孔的闭合限制了弹性膜和层压制品性能的提高。
水压头试验(实例1~7)
对实例1~7的膜和层压制品进行了水压头试验。用来试验的液体是70%异丙醇和30%水的混合物,其商品名为Homebest,是密苏里州Hazelwood市的Glendale食品公司销售的。所用的水压头试验设备是Textest,型号FX 3000,可从Spartanburg,S.C的Schmid公司购得。
试验程序如下。在试验装置中灌入上述醇溶液。将各样品放入测试仪中。测试仪按制造商说明进行校正。然后开始试验,使液压增至20毫巴(20.4×107kg/m2)。在该压力下观察样品的液体渗透情况至少10分钟。
结果如下。就Celgard膜(实例6)而言,在小于20毫巴(20.4×107kg/m2)压力时渗透液体,并在1分钟内在外表面形成大量糊状物。
对于未拉伸的填料膜(实例2),至少在6分钟内未观察到泄漏。当样品开始暴露于20毫巴(20.4×107kg/m2)液压时,就开始伸展,并形成高约2英寸(5.08cm),宽约4.5英寸(11.43cm)的穹面。在8分钟时,形成小液滴。在13分钟时小液滴覆盖外露膜表面的约15%,其频率为约10滴/cm2。
经拉伸的填料膜(实例3)开始时能耐受20毫巴(20.4×107kg/m2)液压。4分钟后,膜的外露表面上形成许多小液滴,其频率为约50滴/cm2。在液压的作用下,该膜也形成了2英寸(5.08cm)高的穹面。在6分钟时,这些小液滴聚结。在8分钟后,小液滴聚结成流,从膜的穹面上流下。
就拉伸的层压制品(实例5)而言,对液体的压力有一个总的阻力。在20毫巴(20.4×107kg/m2)液压时,经10分钟后未观察到层压制品上的液体渗透现象。
层压制品中的聚氨酯膜本身也进行过测试。在20毫巴(20.4×107kg/m2)液压时经10分钟后未观察到液体渗透现象,说明聚氨酯对层压制品所显示出的耐渗透性起了主要作用。
实例8~11
按上述方法制备实例1、3、5和6的膜和层压制品的试样,并在拉伸(与收缩相反)条件重新测试WVTR。对下面所有实例(除实例11外)来说,膜和层压制品跟上述一样,开始时发生伸展,在伸展条件下保持2分钟,然后让其收缩。与上述程序不同,然后将实例8~10的膜和层压制品重新拉伸到其原长的约270%,并在该再拉伸下测定其WVTR。得到下列结果。
实例 | 膜或层压制品的认别 | 相当于前述实例 | 定量g/m2 | 再拉伸条件下的WVTR(g/m2·24小时) |
8 | Deerfield膜 | 1 | 24.7 | 1530 |
9 | 拉伸填料膜 | 3 | 28.9 | 1260 |
10 | 层压品B(拉伸的) | 5 | 77.0 | 224 |
11 | Celgard 2500 | 6 | 14.6 | 5000(未拉伸) |
如上所示,填料膜在再拉伸条件下(实例9)的WVTR值可以和Deerfield膜对照样品相比,且比未经再拉伸的同样的膜(实例3)好得多。层压品B由于存在粘合剂和聚氨酯层,所以其WVTR较低。这些实例支持了这样的假设,即经拉伸的填料膜的WVTR取决于收缩量(这种收缩作用倾向于使孔闭合)。
拉伸条件下样品定量通过在各拉伸样品冲压一个直径为2.25英寸(5.72cm)的圆面来测定。在样品从WVTR测试装置上取下并让其收缩后,切下圆形区域并称重。用这种方法就测得了各拉伸样品的重量。
因此,本发明的膜具有高的水蒸气透过率和弹性,使得它具有多种功能,包括水蒸气渗透性、化学品蒸气和/或液体不透性,以及舒适性和可拉伸性。此外,这类膜可以附贴在支承层上形成层压制品。
当然,应该理解的是,对于上述的具体实施方案可以做各种各样的改变和修改。因此,这就意味着上面的描述是说明,而不是限制本发明,而且,界定本发明的是下列的权利要求。
Claims (28)
1.一种可透气、取向多层膜层压制品,其中包含:
一个取向的填料膜层,包括一种聚合物树脂和一种填料,填料含
量至少为所述聚合物树脂体积的10%,所述填料膜的水蒸气透过值为至少300g/m2·24hrs.;
至少一个粘合到所述填料膜层上的连续膜层,其中所述连续膜层是一种可拉伸树脂。
而且其中所述层压制品是在所述层压制品形成后取向的,使得在所述层压制品中所述连续膜层仍然是无孔的,且所述层压制品显示出再拉伸后的水蒸气透过率至少为200g/m2·24hrs。
2.权利要求1的层压制品,其中所述填料含量为所述聚合物树脂体积的25~50%。
3.权利要求1的层压制品,其中所述聚合物树脂选自包含弹性体、热塑性聚合物、热塑性弹性体,以及它们的组合在内的聚合物树脂。
4.权利要求1的层压制品,其中所述聚合物树脂选自包含聚氨酯弹性体、硅氧烷弹性体、丁烯-异戊二烯弹性体、异戊二烯橡胶、聚丙烯酸酯弹性体、氯丁橡胶、丁腈橡胶、聚丁二烯弹性体、乙丙橡胶、氟碳弹性体、磷腈弹性体、氯化聚乙烯弹性体、氟硅氧烷弹性体、聚硫弹性体、氯磺化聚乙烯弹性体、表氯醇弹性体、丁苯橡胶、聚烯烃类、聚苯乙烯类、聚酯-聚氨酯、聚醚-聚氨酯、己酯-聚氨酯、共聚醚酯等热塑性弹性体在内的聚合物树脂。
5.权利要求1的层压制品,其中所述可拉伸树脂选自包含聚氨酯弹性体、硅氧烷弹性体、丁烯-异戊二烯弹性体、异戊二烯橡胶、聚丙烯酸酯弹性体、氯丁橡胶、丁腈橡胶、聚丁二烯弹性体、乙丙橡胶、氟碳弹性体、磷腈弹性体、氯化聚乙烯弹性体、氟硅氧烷弹性体、聚硫弹性体、氯磺化聚乙烯弹性体、表氯醇弹性体、丁苯橡胶,以及它们的组合在内的聚合物树脂。
6.权利要求1的层压制品,其中所述填料膜层是弹性的,且具有第一永久变形拉伸特性。
7.权利要求6的层压制品,其中所述连续膜层具有第二永久变形拉伸特性,该永久变形小于所述第一永久变形。
8.权利要求1的层压制品,其中进一步包含至少一个支承层。
9.权利要求8的层压制品,其中所述支承层粘合到所述连续膜层上。
10.权利要求8的层压制品,其中第一支承层粘合到所述填料膜层上,第二支承层粘合到所述连续膜层上。
11.权利要求8的层压制品,其中所述支承层是一种非织造纤维网。
12.权利要求1~11中任何一项所述的层压制品用于医用服装的用途,所述医用服装包含一种可透气、取向多层膜层压制品和至少一个支承层,所述层压制品包含:
一个微孔填料膜层,包括一种聚合物树脂和一种填料,填料含量至少为所述聚合物树脂体积的10%,所述填料膜的水蒸气透过值为至少300g/m2·24hrs.;
至少一个粘合到所述填料膜层上的连续膜层,其中所述连续膜层是一种弹性体树脂,所述连续膜层是水蒸气可透过的,但对引起气味的微生物是不可透过的;
其中所述层压制品是在所述层压制品形成后取向的,使得在所述层压制品中所述连续膜层仍然是无孔的,且所述层压制品显示出再拉伸后的水蒸气透过率至少为200g/m2·24hrs。
13.权利要求12的用途,其中第一支承层粘合到所述填料膜层上,第二支承层粘合到所述连续膜层上。
14.权利要求1~11中任何一项所述的层压制品用于个人护理吸收用品的用途,其中所述用品包含一个液体可透过的上部片材和一个背部片材,其间配置一个吸收剂芯层,所述背部片材和所述上部片材中至少有一个包含权利要求1的层压制品。
15.权利要求14的用途,其中所述用品进一步包含一个从外周配置到所述上部片材和所述背部片材上的拉伸区域,其中所述拉伸区域、所述背部片材和所述上部片材中至少有一个包含所述层压制品。
16.权利要求14的用途,其中所述用品是尿布。
17.权利要求14的用途,其中所述用品是运动短裤。
18.权利要求14的用途,其中所述用品是卫生巾。
19.权利要求14的用途,其中所述用品是失禁设备。
20.权利要求14的用途,其中所述用品是绷带。
21.形成一种填料膜和连续膜层压制品的方法,包括:
提供一个包含聚合物树脂和填料的填料膜层,填料含量至少为所述聚合物树脂体积的10%;
将至少一个连续膜层粘合到所述填料膜层上形成一种层压制品,所述连续膜层包括第一弹性体树脂,所述连续膜层是水蒸气可透过的,但对引起气味的微生物是不可透过的;
将所述层压制品拉伸以形成一种拉伸的层压制品,其中所述填料膜的水蒸气透过值为至少450g/m2·24hsr.;
让所述拉伸后的层压制品松弛,以形成一种微孔膜和连续膜层压制品。
22.权利要求21的方法,其中所述的粘合是粘合剂粘合。
23.权利要求21的方法,其中所述的粘合是热点粘合。
24.权利要求21的方法,进一步包括将所述拉伸的层压制品在其松驰之前粘合到非织造纤维网上的步骤。
25.权利要求21的方法,进一步包括在让所述拉伸后的层压制品松弛之后将所述层压制品粘合到非织造纤维网上的步骤。
26.权利要求21的方法,其中所述连续膜和所述填料膜是通过点粘合方法粘合在一起的。
27.权利要求21的方法,其中所述连续膜和所述填料膜是连续粘合在一起的。
28.权利要求1的层压制品,其中该层压制品中的连续膜层是水蒸气可透过的,但对会产生气味的微生物是不可透过的。
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US08/774,477 US5914184A (en) | 1996-12-30 | 1996-12-30 | Breathable laminate including filled film and continuous film |
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US5914184A (en) | 1999-06-22 |
AU726667B2 (en) | 2000-11-16 |
KR100493840B1 (ko) | 2005-06-10 |
EP0948429A1 (en) | 1999-10-13 |
KR20000069762A (ko) | 2000-11-25 |
EP0948429B1 (en) | 2004-06-16 |
US5993589A (en) | 1999-11-30 |
CA2273910A1 (en) | 1998-07-09 |
DE69729576D1 (de) | 2004-07-29 |
CN1241964A (zh) | 2000-01-19 |
DE69729576T2 (de) | 2005-07-07 |
BR9714241A (pt) | 2000-04-18 |
AU5617898A (en) | 1998-07-31 |
WO1998029239A1 (en) | 1998-07-09 |
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