CN1270552A - 弹性膜层压件 - Google Patents

弹性膜层压件 Download PDF

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CN1270552A
CN1270552A CN98809153A CN98809153A CN1270552A CN 1270552 A CN1270552 A CN 1270552A CN 98809153 A CN98809153 A CN 98809153A CN 98809153 A CN98809153 A CN 98809153A CN 1270552 A CN1270552 A CN 1270552A
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casting die
fabric
polymer
film
rete casting
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CN1123441C (zh
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F·P·阿布托
W·B·哈夫纳
J·F·乔丹
A·L·麦科尔马克
D·G·乌尼藤布勒克
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Abstract

一种弹性的不透液层压件,它具有可拉伸的阻挡层膜,其包括密度小于约0.89g/cm3的低密度聚乙烯的纤维的基重为8g/m2～100g/m2的弹性非织造织物;以及可拉伸的布状外层例如纺粘纤维的非织造织物。此阻挡层层压件可以通过热点粘合层压,而形成具有改进了膨松性和有优良手感的花纹,同时使剥离强度大于1000g。

Description

弹性膜层压件
发明领域
本发明涉及膜层压件。更具体地说，本发明涉及膜与非织造织物的弹性层压件。
发明背景
膜层压件已成为重要的商品，求得了广泛的应用，这些应用包括用作个人贴身制品如尿布、训练短裤、失禁衣着、妇女卫生制品等的外罩。此外，膜层压件还已发现用于室外织物、防水布、防护服、控制感染的产品、衣着等。这种膜能为制品提供所需的阻挡层性质，而其他层压到其上面的材料则能提供另外的特性如强度、耐磨性和/或良好的手感。
包括有这种膜层压件的许多制品最好至少是部分弹性的。例如，尿布的是弹性的外罩与非弹性的制品相比就能改进身体的适应性。但要在实现所需弹性的同时来保持其他所需特性如透气性、良好的外观和低成本，便成为问题。低成本的膜层压件，例如用于一次制品中的层压件常遭遇剥离强度差。膜层压件的分层现象是不利的，因为这会降低制品的表观质量，同时会增加在膜中形成扯破或撕裂的风险。
为此，需要有这样的膜层压件，其能在显示出弹性的同时又能保持所需的特性，如透气性、良好的手感和优越的剥离强度。此外，还需要有这样的层压件，它具有界限分明的粘合花纹、膨松感和全面改进的美感。也还需有这样的阻挡层压件，它具有布状的外表面、耐用、同时可采用多种的膜和层压件结构。进而还需有这样的膜层压件，它可以用可靠的方法制成，而这种方法可以在广泛的处理条件和参数下使用。
发明概述
借助本发明的弹性层压件，可以满足上述的种种需要和解决内行的人士遇到的一些问题，这种弹性层压件包括可延伸的底膜、弹性的中间非织造织物和粘合于其上的可延伸外部纤维材料。此弹性中间织物的第一侧粘合到底膜上，而以其第二侧粘合到外部纤维材料上。在另一方面，此弹性中间织物包括无定形聚合物，举例来说，此无定形聚合物可以包括低密度的乙烯弹性料组份，而此组份则包括乙烯和α-烯烃的共聚物。在又一方面，此低密度的乙烯弹性料的密度最好为约0.86g/cm3～约30.89g/cm3。此外，上述无定形聚合物还能包括具有第二种聚烯烃聚合物的混合物，例如具有较高密度的第二种乙烯聚合物。这种低密度聚乙烯弹性料最好包括至少约50％重量百分比的纤维。上述弹性中间织物则最好包括非织造织物，如熔喷纤维的织物。
上述可延伸的底膜可以包括弹性膜且最好包括透气膜。在本发明的一个方面，这种膜可以包括弹性的透气阻挡层，例如包含有弹性聚乙烯聚合物和填料的拉伸的填充膜。底膜、弹性中间织物和外纤维料三者集合的基重最好小于约100g/m2。外纤维料层可以包括热塑性非织造织物。这种非织造的外层最好包括布状的织物，具有良好的手感和悬垂性。在本发明的一个方面，此非织造的外层包括拉细(颈缩)的或反向拉细的非织造织物。本发明的层压件的剥离强度最好要大于200g/cm2而尤为最好是超过500g/cm2。此外，透气的阻挡层压件的WVTR应大于300g/m2/天、800g/m2/天甚至是1500g/m2/天。外纤维料可以包括非织造织物，而在另一方面可以通过将各层层压到一起而叠层到粘合层上。层压各层的适用方法包括但不限于热点粘合、超声粘合等。
定义
这里所用的词“非织造”织物是指其各个纤维或丝取交互铺叠但不同于网络式或针织式织物中可识别方式结构的织物。非织造织物或织幅已可由多种加工方法形成，例如熔喷法、纺粘法、氢缠结法、气流成网法和粘合粗梳成网法等。
这里所用的词“微纤维织物”是指包括有平均纤维直径至少在一个维数上小于约10μ的纤维的织幅。
这里所用的词“纺粘纤维”指实质上是分子取向的聚合物材料的小直径纤维。纺粘纤维可以由喷丝板上许多细小的通常为圆形的毛细孔将熔融热塑材料挤压成丝，然后使该挤压丝快速减径而成，例如可采用下述美国专利号中所述的技术No.4340563(Appel等人)、No.3692618(Dorschner等人)、No.3802817(Matsuki等人)、No.3338992与No.3341394(Kinney)、No.3502763(Hartman)、No.3542615(Dobo等)以及No.5382400(Pike等人)。纺粘纤维当其沉积于凝聚面上时通常是不发粘的且为连续的，纺粘纤维的直径通常约10μ或更大。而且可以用，但不限于下述种种方法获得微纤维的纺粘织物，这些方法例如描述于：共同转让的美国专利申请No.08/756426，1996年11月26日提交(Marman等人)，美国专利申请No.08/565261，1995年11月30日提交(Pike等人)，其中的内容已综合于此供参考。
这里所用的词“熔喷纤维”是指一般通过将熔融热塑性材料通过许多细小的通常为圆形的模板毛细孔挤压成的熔融丝或纤维，引入会聚的高速的且常为热的气体(例如空气)流，将这种熔融的热塑性材料的丝拉细减径而成的聚合材料纤维。然后可用此高速气流将熔喷纤维载运并沉积到凝聚面上而形成无规分散的熔喷纤维。这方面的工艺例如已叙述于授予Butin等人的美国专利No.3849241和授予Timmons等人的美国专利No.5271883中。熔喷纤维可以是连续的或不连续的，且当其沉积于凝聚面上时一般是发粘的。熔喷纤维可以包括微纤维织物。
这里所用的“SME层压件”是指纺粘/熔喷/纺粘(SMS)的层压件。多层非织造层压件的例子公开于下述美国专利号中：No.4041203(Brock等人)、No.5178931(Perkins等人)以及No.5188885(Timmens等人)。这种层压件可以按下述方式制成：于运动的成形带上相续地沉积先是纺粘织物层、继之为熔喷织物层而最后是另一纺粘层，然后用例如下述的热点粘合法粘合此层压件。或者可把这些织物层单个地集合成卷而由单独的粘合步骤结合。
这里所用的词“聚合物”一般包括但不限于均聚物；共聚物，如嵌段、接枝、无规和交错的共聚物，三聚物等；以及它们的混合物和变型。此外，除非另有明确的限制，“聚合物”一词包括了有关分子的所有可能空间构型。这些构型包括但不限于等规的、间规的和无规的对称构型。
这里所用的词“无定形聚合物”当在此用来描述或作为中间层或作为单独施加的粘合层时，是指这样的热塑性聚合物，例如密度约0.85～约0.89g/cm3和例如小于30的低结晶度的某些聚烯烃。
这里所用的词“机器方向”或MD是指织物的长向处于其被生产的方向。“横截机器方向”、或CD一词则指织物的宽向，即一般垂直于MD的方向。
这里所用的词“超声粘合”是指例如使织物通过如美国专利No.4374888(Barnslaeger)或No.5591278(Goodman等人)所述的，在超声扬声器和砧辊之间的工艺。
这里所用的词“点粘合”是指在多个分散的点上粘合一层或多层织物。例如，热点粘合通常涉及使待粘合的一层或多层通过加热辊之间，加热辊例如一个是刻花辊而另一个是平滑的轧辊。刻花辊以某种方式刻有花纹。以使整个织物不会在其全部表面上粘合，而轧辊或砧辊通常是平滑的。结果，出于功能和美观的原因，已开发了用于压花辊上的花纹。花纹的例子之一为点状的，同时是所谓Hansen Pennings或“H & P”花纹，在新的时候具有约30％的粘合面积，同时有着约200粘合点/英寸2，如授予Hansen和Pennings的美国专利No.3855046中所说明的。H & P花纹具有方形点或销的粘合区，各销点的边长为0.038英寸(0.965mm)，销间距为0.070英寸(1.778mm)、粘合深度为0.023英寸(0.584mm)。此最终形成的花纹在新的时有约29.5％的粘合面积。另一种典型的点粘合花纹图案是展开的Hansen-Pennings或“EHP”粘合花纹，它在新的时产生15％的粘合面积，方形销点边长0.037英寸(0.94mm)、销间距0.097英寸(2.464mm)、深0.039英寸(0.991mm)。另一种点粘合花纹称为“714”有着方形销点粘合区，各销点边长0.023英寸、点间距0.062英寸(1.575mm)、粘合深度0.033英寸(0.838mm)。形成的花纹在新的时具有约15％的粘合面积。另一种普通的花纹是C星形花纹，其在新的时的粘合面积约16.9％。这种C星形花纹具有为流星截断的横条或“灯芯绒”设计。其它普通的花纹包括菱形花纹，它有着重复和略微错开的菱形和约16％的粘合面积；及金属丝网花纹，外观如其名称所示，例如类似窗纱，有约15％粘合面积。再一种花纹是“S形”花纹，其在新的时有约17％的粘合面积。一般，这种百分粘合面积从这种织物层压件面积的约10％变化到约30％。
这里所用的词“阻挡层”指膜、层压件或其他织物，基本上不透液，且液位差至少50mbar(水)。这里所用液位差是指织物阻液性质的一种测度。但应知本发明的阻挡层织物的液位差可以大于80、150或甚至300mbar(水)。
这里所用的词“可透气的”涉及到最低具有约300g/m2/24小时的WVTR(水汽透过率)的可透水蒸汽的材料。织物的WVTR在一个方面能表明所穿用织物的舒适性。WVTR(水汽透过率)按以后所述测量，并以g/m2/天报告其结果。但通常应用的可透气阻挡层最好具有较高的WVTR，而本发明的可透气层压件的WVTR可以超过约800、1500甚至约3000g/m2/天。
这里所用的词“可拉伸的”是指至少可沿一个方向伸长或拉伸。
这里所用的“弹性”是指一种材料在偏压力的作用下可拉伸即可延伸到至少是此材料松驰无偏压力长度的150％的偏压长度，而在松释这种伸长力后将回缩其伸长部分的至少50％。设想某种材料的，1英寸长试样，它在偏压力作用下可拉长到至少1.50英寸，而在松释该偏压力后将回缩到不超过1.25英寸的长度。
这里所用的词“非弹性”或“无弹性”是指任何不属于上述“弹性”定义范围的任何材料。
这里所用的词“单组份纤维”是指只用一种聚合物由一台或多台挤压机形成的纤维。这并不意味着要排除由一种聚合物出于着色、抗静电、润滑、疏水等目的而添有少量添加剂形成的纤维。
这里所用的词“多组份纤维”是指已由不同挤压机挤压出的至少两种聚合物形成的纤维但纺到一起而形成一根形式的纤维。多组份纤维有时也称作共轭纤维或双组份纤维。多组份纤维的聚合物于纤维的横剖面上基本上恒定地位于不同的区域而连续地沿纤维的长度延伸。这种纤维的构型例如可以是：皮/芯型结构，其中一种聚合物为另一种聚合物围绕；并列型结构；馅饼型结构或是“天星状基体”型结构。多组份纤维已描述于下述美国专利中，No.5108820(Kaneko等人)、No.4795668(Krueger等人)、No.5236552(Strack等人)。共轭纤维则描述于美国专利No.5382400(Pike等人)中，可以通过使用两(或多)种纤维的不同结晶率于纤维中形成卷曲。对于双组份纤维，两种聚合物之比可以是75/25、50/50、25/75或任何其他所需的比率。这种纤维所具有的形状，例如还可以是以下描述非常规形状纤维的美国专利中所说明的形状：No.5277976(Hogle等人)、No.5466410(Hills)以及No.5069970与No.5057368(Largman等人)。
这里所用的词“混和”是指混合两种或多种聚合物，而词“掺合物”则指混合物的一个子类，其中各组份是不溶混的但是相容的。
这里所用的词“双成份纤维”或“多成份纤维”是指至少两种聚合物从同一挤压机作为一种混合物挤出而形成的纤维。“混合”已定义如上。双成份纤维在纤维的横剖面上并不会有各种聚合物组份较恒定地位于不同的区域中，而且各种聚合物沿着纤维的整个长度常常是不连续的；相反，它们常常形成无规则地开始和无规则地终止和原纤维或原微丝。双组份和双成份纤维也见述于教科书《Polymer Blendsand Composities(聚合物的混合物和组成)》中，由John A.Mansonand Leslie H.Sperling，1976版权，由Plenum Press出版，PlenumPublishing Corparation of New York的分社，IBSNO-306-30831-2，PP273-277。
这里所用的词“粘合窗”是指用来将非织造织物粘合到一起的机构例如一对加热的粘合辊的温度范围，在此温度范围内这种粘合是成功的。
这里所用的词“纱布”是指用作背衬料的轻量织物。纱布常用作涂层的或层压的产品的底部织物。
这里所用的词“衣着”指任何类型可穿用的服装，其包括工作服和罩衣、内衣、短裤、衬衣、外套、手套、袜子，等等。
这里所用的词“感染控制产品”是指医疗专用品，如外科长服与窗帘、面罩、类似膨松裙的头罩、外科帽与外科罩、类似于鞋盖的护袜、靴罩和拖鞋、绷带、纱带、灭菌外罩、毛巾试验室外衣之类的衣着、工作服、围裙与夹克衫、病人床上用品、担架与摇篮布单，等等。
这里所用的词“个人贴身制品”是指尿布、训练短裤、吸湿性内裤、成人失禁衣着和妇女卫生用品。
这里所用的词“防护罩”是指运输工具如轿车、卡车、船、飞机、摩托车、自行车、高尔夫球器械装运小车等的罩布；常置于户外的设备如铁格子窗、庭院和公园设备(发动机、旋转碎土机等)与草坪设备以及地板的盖布、桌板和野餐区的铺布。
附图的简要描述
图1是本发明的层压件的横剖图；
图2是本发明的层压件的横剖图；
图3制造本发明的压层件的生产线及示意图；
图4示明适用于本发明的粘合花纹；以及
图5示明适用于本发明的粘合花纹。
发明详述
参考图1，本发明涉及多层层压件10，它包括膜12、外纤维层20和中间弹性非织造织物。此中间非织造织物14有第一侧16和第二侧18。外纤维层20接附到此中间非织造织物14的第二侧18上而膜12接附到此中间非织造织物14的此第一侧16上。
上述中间弹性非织造织物包括一层无定形聚合物纤维。这种聚合物成分最好包括弹性料，且还可包括增粘剂或其他助粘剂，以改进此中间非织造织物与相对的膜和外非织造层之间的粘合性。适用的聚合物例子包括但不限于弹性聚烯烃、乙烯醋酸乙烯酯(EVA)、EPDM橡胶、乙烯乙酸乙酯(EEA)、乙烯丙烯酸(EAA)、乙烯甲基丙烯酸酯(EMA)、聚氨酸(PU)，聚酰胺聚醚嵌段共聚物，通式为A-B-A’或A-B状的共聚物(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)、苯乙烯等的嵌段共聚物。
在最佳实施例中，上述无定形聚合物包括一种或多种弹性聚烯烃，如低密谋聚乙烯弹性料、弹性聚丙烯、挠性聚烯烃和增粘的聚合物，如苯乙烯嵌段共聚物、聚氨酯或嵌段聚酰胺聚醚。在本发明的一个方面，上述中间弹性非织造织物至少是部分地包括密度小于0.89g/cm3的低密度乙烯弹性料组份的低密度弹性聚烯烃聚合物组份。这种乙烯弹性料最好包括基本上是线性的乙烯，其密度小于0.89g/cm3，更好是约0.86～约0.88g/cm3而最好是约0.87g/cm3。这样的乙烯弹性料应包括至少约50％重量百分比的聚合物部分的纤维，而更好是约70％～约100％重量百分比。这种乙烯弹性料最好包括这样的聚合物，其中的乙烯单体与α-烯烃聚合而使得最终的聚合物料中有很窄的分子量分布( Mw/ Mn)，均匀的分支并且是受控的长链分支。合适的α-烯烃包括但不限于1-辛烷、1-丁烷、1-已烯和4-甲基戊烯。典型的这类聚合物包括本技术中周知的那些，如“金属茂”、“受约束几何结构”或“单一位置”催化的聚合物，例如描述于下述美国专利No.5472775(Obijeski等人)、No.5451450(Erderly等人)、No.5539124(Etherton等人)以及No.5554775(Krishnamurti等人)中，它们的整体内容已综合于此供参考。
金属茂方法一般采用由助催化剂激活的即离子化的金属茂催剂。金属茂催化剂的例子包括二(正丁基环戊二基)二氯化钛、二(正丁基烷戊二基)二氯化锆、二(环戊二基)氯化钪、二(叉基)二氯化锆、二(甲基环戊二基)二氯化钛、二(甲基环戊二基)二氯化锆、二茂钴、环戊二基三氯化钛、二茂铁、二茂铪二氯化物、异丙基(环戊二基，-1-芴基)二氯化锆、二茂钼二氯化物、二茂镍、二茂铌二氯化物、二茂铷、二茂钛二氯化物、二茂锆二氯化物的氢化物、二茂锆二氯化物，等等。这类化合物的更详尽的清单包括在授予Rosen等人的并转让给Dow Chemical Company的美国专利No.5374696中。这类化合物也在授予Stevens等人的同样转让给Dow ChemicalCompany的美国专利No.5064802中讨论到。但是，在本技术中已知有众多的其他金属茂催化剂，单一位置催化剂、受约束几何结构的催化剂和/或类似的催化剂体系，例如参考《The Encyclopedia ofchemical Technology(化学技术百科全书)》，Kirk-Othermer，第4版，Vol，17，“烯烃聚合物”，PP765 767(John Wiley & Sons1996)；其中的内容已综合于此供参考。
至于弹性共聚物，授予Kaminsky等人的美国专利No.5204429描述了一种工艺，可用立体刚性手性金属茂过渡金属化合物和铝噁烷的催化剂，从环烯烃和线性烯烃来生产弹性共聚物。都授予Lai等人且转让给Dow Chemical的题为“弹性的基本线性的烯烃聚合物”的美国专利No.5278272与No.5272236描述了具有特殊弹性性质的聚合物，其总体内容已综合于此供参考。适用的低密度乙烯弹性料可以购自Dow Chemical Company of Midland，Michigan，商品名AFFINITyTM，包括AFFINITYTMEG8200(5MI)、XU58200.02(30MI)、XU58300.00(10MI)；还可以购自EXXON Chemical Co.Of Houston，TX，商品名EXACTTM4049(4.5MI，0.873g/cm3)、401l(2.2MI，0.888g/cm2)、4041(3MI，0.878g/cm3)、4006(10MI，0.88g/cm3)。
此外，中间弹性纤维层可以包括无定形聚合物与一种或多种其他聚合物的聚合物混合物，这里的其他聚合物则包括最高可达约75％重量百分比的纤维，而最好是最高可达约50％重量百分比的纤维。相信这种纤维可以包括低密谋聚乙烯弹性料和其它的热塑性聚合物，而最好是较高密度和/或结晶度较高的聚烯烃。可以适用于本发明的聚烯烃包括但不是限于LLDPE(密度为约0.90g/cm3～0.92g/cm3)，LDPE(0.915～0.925g/cm3)乙烯-丙烯共聚物、乙烯乙酸乙烯酯、乙烯丙烯酸乙酯、乙烯丙烯酸、乙烯甲基丙烯酸酯，等等。
其他的市售弹性聚合物的例子包括但不限于Himont CATALLOYKS350、KS357和KS359。Himont Catalloy聚合物是聚烯烃的多级反应产物，其中无定形乙烯丙烯无规共聚物是以分子形式分散于主要是半结晶的高丙烯单体/低乙烯单体的连续基质中，例如描述于授予Ogale的美国专利No.5300365中的。此外，使用的弹性树脂包括通式为A-B-A，或A-B的嵌段共聚物，其中A和A’各是热塑性聚合物的终端嵌段，它包含苯乙烯的一部份，例如聚(乙烯基芳环)，而其中B是弹性聚合物的中间嵌段，例如共轭二烯或低链烯的聚合物。这种A-B-A’型的嵌段共聚物对于A嵌段和A’嵌段可以具有不同或相同的热塑性嵌段聚合物，而这里的嵌段共聚物则包括线性、分支和径向的嵌段共聚物。在这方面，径向嵌段共聚物可以表示为(A-B)m-X，其中X是多官能原子或分子，而其中各(A-B)m从X幅射出使A是终端嵌段。在此径向嵌段聚合物中，X可以是有机或无机的多官能原子或分子，而m是整数，其值与X中原先存在的官能组数相同。此数通常至少是3，常常是4或5，但并不局限于此。这样，在本发明中，“嵌段共聚物”一词，特别是“A-B-A”和“A-B”嵌段共聚物，用来包括例如上面讨论到的具有那种橡胶式嵌段和热塑性嵌段的所有嵌段共聚物，它们能够挤压(例如通过熔喷)，同时嵌段数不限。这种弹性非织造织物例如可以由弹性(聚苯乙烯/聚(乙烯-丁烯)/聚苯乙烯)嵌段共聚物形成。这类弹性共聚物市售品的例子例如有称作KRATON的材料，可购自shell Chemical Company ofHouston，Texas。KRATON嵌段共聚物市售有几种不同的配方形式，其中有许多已指出于美国专利No.4663220和No.5304599中，它们的整体内容已综合于此供参考。
包括弹性的A-B-A-B四嵌段共聚物的聚合物也可以用于实施本发明。这类聚合物已公开于授予Taylor等人的美国专利No.5332613中。在这类聚合物中，A是热塑性聚合物嵌段，而B是异戊间二烯单体单元经氢化成基本上是聚(乙烯丙烯)单体单元。这种四嵌段共聚物的例子是苯乙烯-聚(乙烯-丙烯)-苯乙烯-聚(乙烯-丙烯)，或是SEPSEP弹性嵌段共聚物，后者可在商品牌号KRATON下购自shell Chemical Company of Houston，Texas。
其他据信可用于本发明的典型的弹性材料包括聚氨酯弹性材料，例如商品名ESTANE，可购自B.F.Goodrich & Co.的，或商品名MORTHANETM可购自Morton Thiokol Corp.的聚酯弹性材料，例如商品名HYTREL可购自E.I.DuPont De Nemours & company的，以及称作为ARNITEL以前可购自Akzo plastics of Arnhem，Holland而现在所购自DSM of Sittard，Ho1land的。
为了改进这种中间非织造织物与其相邻层的热匹配性，再好给此弹性聚合物料增添增粘剂或助粘剂。适用的增粘剂例子包括但不限于授予Kieffer等人的美国专利No.4789699中所述的。市售的增粘剂例子是：REGALREZ1126，可购自Hercules Inc.Of Wilmington，De；ESCOREZ5300，可购自EXXON Chemical Co.；WINGTACK 95，可购自Goodyear Chemical Co.of Akron，Ohio。所添加的增粘剂的量将相对于中间弹性纤维层中所用具体的弹性聚合物和构成相邻层的聚合物而变化。尽管加到弹性中间层的增粘剂的量可以不同，但通常最好添加按聚合物料重量计的约5～约20％。
在最佳实施例中，此中间弹性非织造织物包括纤维的基质，例如熔喷纤维的织物。另一方面，这种纤维质弹性层可以包括一层纺粘纤维和/或有类似基重的一层短切纤维，此非织造织物的基重最好是约10～约100g/m2，而尤为最好是约25g/m2～约60g/m2。这一基重的选择将相对于整个层压件的基重以及此膜和/或外部非织造层的回复性质而变化。当此外部非织造层和膜是可拉伸的但是非弹性材料时，常常需要较高基重的中间弹性纤维层来给整个层压件提供弹性。但当膜和/或外非织造层也是弹性的，此中间弹性织物的基重可以小于整个层压件的基重。
上述可拉伸的膜可以是单层或多层膜。此外，无孔和微孔膜据信也适用于本发明。这种膜最好包括阻挡层和能具有良好的悬垂性；这种膜的基重最好约为15～100g/m2而尤为最好是约20～60g/m2。用于制造本发明的这种膜的热塑性聚合物包括但不限于这样的聚烯烃类，后者包括均聚物、共聚物、三聚物以及它们的混合物。此外，挠性的聚烯烃膜据信也适用于本发明。其他适用于在本发明中成膜的聚合物包括(单独或与其他聚合物结合)乙烯醋酸乙烯酯(EVA)、乙烯乙酸乙酯(EEA)、乙烯丙烯酸(EAA)、乙烯甲基丙烯酸酯(EMA)、乙烯正丁基丙烯酸酯(EnBA)、聚氨酯(DU)、聚(醚-酯)和聚(酰胺-醚)嵌段共聚物。但是弹性聚烯烃聚合物最好，例如乙烯与丙烯的聚合物以及它们的共聚物、三聚物及其混合物，例如包括，但不限于弹性聚烯烃和乙烯-丙烯共聚物混合物。
在本发明的一个方面，上述膜可以包括透气阻挡层，这种透气阻挡层例如包括WVTR至少为300g/m2/天最好超过800g/m2/天或1500g/m2/天的微孔膜。透气的微孔膜可以用本技术中周知的任何方法形成。例如，这种透气阻挡膜可以包括由热塑性聚合物和填料组成的拉伸填料膜。上述这些(和其他)组份可以混合到一起、加热，然后挤压成单层或多层膜。这种充填的膜可以由本技术中周知的任何一种成膜工艺，例如铸膜或吹膜设备制造。热塑性聚合物和填料可以至少沿一个方向拉伸，由此能减少膜厚并形成某种尺寸和频率的微孔网络，以实现所需水平的透气率。适用于本发明的可透气阻挡膜的例子描述于：WO95/16562(1995年6月22日McCormack)；WO96/19346(1996年6月27日提交，McCormack等人)；下述的美国专利申请序号：No.08/722726(1996年10月1提交；McCormack等人)；No.08/883164(1997年6月26日提交；McCormack等人)；No.08/882712(1997年6月25日提交，HcCormack等人)；No.08/843147(1997年4月25日提交；Gwaltney等人)；No.09/122326(1998年6月24日提交；Shawver等人)；以及快递No.RB879664401US(1997年9月15日提交；Shawver等人)，上述各参考文献的整体内容已综合于此供参考。这类膜在拉伸前的基重最好小于约100g/cm2而尤为最好是小于约60g/cm2。经拉伸后，这种多层膜的基重最好小于60g/cm2。而尤为最好是约15～35g/m2适用的膜例如还可以包括由其挤压工艺形成的多层膜，例如公开于美国专利No.4522203、No.4494629以及No.4732324中的成形多层膜的方法，它们的内容已综合于此供参考。
外层包括能层压到所述弹性中间织物上的可延伸纤维料。此外层例如可包括：能拉伸的非织造材料、带网眼的纤维、窗纱、松散织造的织物、弹性复合料和/或其他类似材料。这种织物最好包括一层或多层热塑性纤维，它们是固有地可延伸的或经处理成可拉伸的和/或是弹性的，同时具有布状的手感和悬垂性。适用的可拉伸和/或弹性材料的例子描述于下述美国专利中No.4965122(Morman等人)；No5114781(Morman等人)、No.5536545(Morman等人)；No.4720415(Vander Wielen等人)；No.4789699(Kieffer等人)；No.5332613(Taylor等人)；No.5288791(Collier等人)；No.4663220(Wisneski等人)；No.5540976(Shawver等人)；以及欧洲专利申请No.0712892A1(Djiaw等人)、美国申请序列号No.08/603961(Shawver等人)和No.08/674365(Levy等人)，它们的整个内容都已综合于此供参考，这种热塑料聚合物的组成可以根据需要选择以实现所需例如弹性、手感、抗拉强度、低成本等性质的材料。另外，可对外非织造层施加例如压花、氢化缠结、机械方式软化、印花、抗静电处理或其他方式处理，以获得所需的美观和/或功能特性。
还能够在本发明的弹性层压件内压成各种有吸引力的花纹，例如适合于婴儿尿布外罩的花纹。示例性的粘合和/或压合花纹可以参照图4和5看到，其他粘合花纹也可结合本发明使用，例如描述于1996年12月17日提交的美国专利申请序列号08/754419的。在此方面业已发现，本发明的层压件已表现出改进了花纹轮廓的清晰度和更具立体感的花纹粘合。此外，在实现了优质的花纹同时，也提供了有优越悬垂性和良好的剥离强度的层压件。本发明的层压件有着超过500g甚至1000g的剥离强度。而且可在实现具有这种剥离强度的弹性层压件时，使它具有约1～7cm的悬垂度。这种外层的一种实施形式可以包括基重为8～35g/m2的聚丙烯纺粘缩径纤维的织物，上面印有花纹和/或在其中压有花纹。
此外，这种包括纤维和/或膜的聚合物组成还可以有选择地包括一种或多种稳定剂、添加剂或其他材料来实现所需的属性。上述组成最好还包括抗氧化剂，例如受阻酚稳定剂。市售的抗氧化剂包括但不限于IRGANOX E 17(α-生育酚)和IRGANOX1076(十八烷基3，5二叔丁基-4羟基氢化内桂酸盐)，可以购自Ciba Specialty Chemicals ofTerrytown，N.Y。此外，本发明中也可采用与成膜工艺、拉伸和任何后续层压步骤相匹配的其他稳定剂和添加剂。例如为了使薄膜具有所需还可添加另外的添加剂，如熔体稳定剂、处理稳定剂、热稳定剂、光稳定剂、热老化稳定剂以及本技术中周知的其他添加剂。一般地说，磷酸盐稳定剂(即IRGAFOS 168，可购自Ciba SpecialtyChemicals of Terrytown，N.Y；和DOVERPHOS，可购自DoverChemical Corp of Dover，Ohio)是良好的熔体稳定剂，而受阻胺稳定剂(CHIMASSORB944和119，可购自Ciba Specialty Chemicalsof Terrytown，N.Y)是良好的热与光稳定剂。包括上述稳定剂的一种或多种的混合料的包装形式已有市售，例如可自Ciba SpecialtyChemicals购到的B900。
在本发明的另一方面，参看图2，可透气的阻挡层压件21可以包括阻挡层膜22，膜22的两侧粘附有相对的弹性熔喷纤维层24a和24b。外部非织造层26a和26b再粘合到弹性熔喷纤维层24a和24b，例如可以采用点粘合的形式。这相对的层22a和22b以及相对的层26a和26b可以取相同或不同的材料。
参看图3，其中概示了用来制造本发明的阻挡件层压件的生产线。图3中，薄膜105如上所述可以由铸膜或吹膜单元之类的挤压膜设备100形成。通常，设备100将包括一台或多台聚合物挤塑机102。未拉伸的膜105通过一对钳口或冷却辊104，而辊之一可以刻花以给新形成的膜105以凹凸的花纹。未拉伸膜的基重最好约50g/m2～约100g/m2。但内行的人士应知，此未拉伸膜的基重将基于其所需拉伸的膜的基重、拉伸比和其他因素。如上所述，可以在膜的挤压中增添填料，以在拉伸时获得可透气的膜。
未拉伸的膜105从挤压膜设备100引到膜拉伸单元106例如机器方向取向机，后者可以购自销售部门，如Marshall and Williamscompany of Providence，Rhode Island。此设备106有许多预热和拉伸辊，它们沿膜105经生产线的方向即膜105运行方向的机器方向拉伸和减薄未拉伸的膜105。此膜可以用一步或多步离散的拉伸作业拉伸。图3中，加热辊108a和108b可以起到预热辊的作用。低速辊110也是加热的，且按慢于快速辊12的圆周速度运行。这些相邻辊的不同速度起到了拉伸膜105的作用。经拉伸后，可让膜115稍稍回撤和/或由一个或多个加热辊例如加热的退火辊114再加热或退火。在膜从膜拉伸单元106出来后，拉伸了膜115的基重最好最大为50g/m2而尤为最好约为15～约35g/m2。
拉伸的膜115接附到上述弹性无定形聚合物纤维织物以及一个或多个外非织造层22上，以形成膜/非织造织物层压件125。再来参见图3，传统的非织造织物形成设备111例如熔喷机以及第二种常规的非织造织物成形设备110如纺粘机，可以用来形成弹性熔喷层121和覆盖的外非织造层122。长的基本上连续的纺粘纤维112作为一种未粘合的织物116沉积到成形网114上，然后可以送过一对紧致和/或粘合辊118，以给织物增加充分的整体性用于进一步处理。纺粘纤维可以通空气粘合或点粘合，例如用图4所示的S形花纹。一旦膜115减薄到所需程度而弹性无定形聚合物纤维织物121和外层122已形成后，就可把这些层放到一起而用一对粘合辊或层压辊116层压。粘合辊116最好加热，而其中至少一个辊可以带花纹，以给成品层压件125按预定的粘合表面区形成所需粘合花纹。层压件126的粘合点最大表面积一般不超过总的表面积的约50％，最好为约5％～约30％。有许多的粘合花纹可供采用，例如图5所示的婴儿对像图案。层压件125一从粘合或层压辊116出来，就可卷绕到卷取辊120上。
本发明的阻挡层层压件可以用来制造和/或包括防护罩、感染控制产品、个人贴身制品、衣着和其他希望有阻挡液体性质和贴身性的制品。例如，这种阻挡层层压件可以用作尿布或成人失禁衣着或外科睡衣的外罩。
试验
液位差：织物的阻液性质的测度是用液位差试验，此液位差试验确定织物在液体从中通过前将支承的水高或水压量(mbar)。具有较高液位差读数的织物表明它比具有较低液位差的织物能更好地阻挡液体的渗透。液位差试验依据联邦试验标准191A，方法5514。这里列出的液位差数据是用类似于上述联邦试验标准取得的，只是作了下述的修正。用购自Marlo Enterprise，Inc.Of Concord，N.C.的流体静压液位差试验机测定了液位差。试样置于标准的水压下(不同于采用实际的水柱)，以恒定的速率加压，直至织物的表面在三个不同的区域出现漏泄。(与夹具相邻边缘处的漏泄忽略不计)。可以支承住未支承的织物例如薄膜以防试样过早破裂。
熔体指数：熔体指数是在给定的条件组下对聚合物粘度的测度。MI表示作物料从已知尺寸的毛细管在特定载荷或剪切速率下于测量的时间内流出的重量，根据ASTM试验1238-906是以g/10分钟于190℃和2160g的载荷下测量。
WVTR：试样材料的水汽透过率(WVTR)是根据ASTM标准E96-80计算出。从各试验材料上按3英寸直径切下环形试样，对比试样是一片CELGARDTM2500膜，购自Hoechst Celansese Corporation ofSommerville，New Jersey。CELGARDTM2500膜是微孔聚丙烯膜。对各种材料制备了三个试样。试验皿是N060-1蒸汽计盘，购自ThwingAlbert Instrument Company of Philadelphia，Pennsyluania。将100cc水注入各蒸汽计量，而将试验材料和对比材料的各个试样跨置于各个盘的敞开顶部。紧固上螺旋式凸缘以沿盘的边缘形成密封，让相关的试料或对比材料暴露于环境温度下，同时是在6.5cm直径圆周上具有约33.17cm2的暴露区域。这些盘置于强制通风炉，100°F(37℃)下约1小时至平衡。此炉是恒温炉，有外部空气循环通过它，以防止水蒸汽聚集其内。适用的强制通风炉例如是Blue M Power-0-Matic 60炉，可购自Blue M.Electric Company of Blue Island，Illinois。结果这种平衡后，从炉中取出盘，称重并立即置回炉中。经24小时，再次从炉中取出这些盘并称重。用下述式(I)计算此初步试验的水汽透过率：
(I)试验WVTR＝(24小时的重量损失，g)×315.5g/m2/24小时炉中的相对温度未作特殊控制。
在100°F(37℃)和环境相对温度的预定条件下，CELGARDTM2500对比试验的WVTR已确定为5000g/m2/24小时。因此，可将此对比试样用于各个试验中，并用下述方程(II)将上述初步试验值校准到设定条件
(II)WVTR＝(试验的WVTR/对比的WVTR)×5000g/m2/24小时
剥离试验：在剥离或分层试验中，试验了能把层压件各层拉开的拉力大小。用特定宽度的织物、特定的夹具的爪宽和恒定的拉伸率测定了剥离强度的值。对于具有膜侧面的试样，要用屏蔽带或其他某种合适材料覆盖该试样的膜侧面，以防膜在试验中剥离。屏蔽带只在层压件的一侧，因而不会影响试样的剥离强度。此试验采用两个夹具，各夹具有两个爪，各爪有一面与试样接触，在同一平面，通常是垂直地将试样保持住，且在开始时分开2英寸。试样的尺寸是宽4英寸，并有足够的长度允许进行分层。爪面尺寸为1英寸高和至少4英寸宽，恒定的拉伸率为300mm/mim。试样用手以充足的使其夹定就位的量分离，然后使夹具以特定的拉伸速率分离，把层压件拉开。此试样在两层之间拉开分离180°，以克(g)为单位作为平均峰值载荷报告此剥离强度。这一载荷力的测量是在层压件已拉开16mm时开始，继续到已总体剥离了170mm。Sinteck2试验机，1001 Sheldon Dr.，Cary，NC27513，Instron Model TM，可购自Instron Corporation，2500；Washington St.Conton，MA02021，或Thwing-Albert ModelINTELLECT II，可购自Thwing-Albert Instrument Co.，10960Dutton Rd.，Phila.，PA19154，都可用于这项试验。所报导的结果是作为三个试样的平均值，并可以由试样依横截方向(CD)或机器方向(MD)进行。
悬垂性：悬垂硬挺度试验利用织物在自重下悬臂弯曲的原理确定了织物的弯曲长度、此弯曲长度是织物重量与织物硬挺度之间相互作用的测度。将1英寸(2.54cm)×8英寸(20.3cm)的织物带按4.75英寸/分(12cm/分钟)的速度沿平行于其长向的方向滑行，使其前沿从水平面的边缘突出。当试样的前梢在其自重下下沉到将此织物前梢与试验台的边缘连接的线同水平面构成41.5°角时，测量其悬垂的长度。悬垂硬挺度即作为作弯曲长度的0.5倍计算。对各织物应总共取5个试样。试验方法依据ASTM标准试验D-1388，只是此织物的长度不同(较长)。所用的试验设备是悬臂式弯曲试验机，型号79-10，可购自Testing Machines Inc.400 Bayview Ave.，Amityville，NY11701。如在大多数试验中，试验前应将试样调节到ASTM条件：65±2百分相对湿度和72±2°F(22±1℃)；或是TAPPI条件：50±2百分相对湿度和72±1.8°F。
例1
用传统的铸模方法挤压出膜，所用化合物(按重量百分比)具有下述组成：47％Supercoat碳酸钙(平均粒度1μ，可购自EnglishChina Clay of America，Sylacauga，AL)；53％AFFINITY-PL-1280树脂(一种乙烯-1-辛烯共聚物，密度0.90g/cm3，MI5，可购自Dow Plastics，Freeport，TX)，混合有2000ppm的B900稳定剂混合物(可购自Ciba-Geigy Corp.Terrytown，NY)拉伸的膜近似1.5mil厚。然后用机器方向定向器(MDO)，这种设备例如可以购自Marshall and Williams Company，将其拉伸成可透气的。预热拉伸辊为160°F，退火辊在室温和在180°F，膜的进入速度为50(英尺/分)(fpm)，出口速度为200fpm，由此产生出4×10拉伸比(原始膜长的300％的伸长率)。此定向的膜然后在线上热层压成事先已在施加了熔喷层的缩颈式纺粘织物。粘合温度控制器对砧辊(光滑钢辊)设定到180°F，对于C星形花纹辊设定到250°F。所用的纺粘织物为17g/m2金属丝网花纹粘合的聚丙烯均聚物，缩径45％和铺陈以17g/m2熔喷纤维织物则包括低密度的聚乙烯弹性料，后者在牌号ENGAGE(52800.02树脂(30MI，0.870g/cm3密度))下可购自Dow。在粘合机辊隙中，此膜与砧辊接触，熔喷织物在膜与纺粘织物之间，而纺粘织物与轧花辊接触。最终的层压件具有有吸引力的轮廓分明的花纹。剥离强度为384.5gMD和308.2CD，而WVTR为790g/m2/24小时。此层压件还显示出所需的弹性行为：当于第一个延伸循环中沿CD延伸到150％，使其拉伸到130％的力为657g/3英寸宽，而于第二个循环中在130％延伸率下的回缩力是130g/3英寸宽。
例2
制备了三层弹性阻挡液体的层压件，它包括弹性膜层、纤维质弹性熔喷粘合层和CD可延伸非织造外层。此弹性膜12是1.0mil的无空隙膜型号MAX264.0，购自Consolidated Thermoplastics Companyof Chippewa Falls，Wisconsin。此弹性中间层为聚乙烯弹性料制成的30g/m2的熔喷织物，AFFINITY 58200.02。这种弹性树脂的熔体指数(MI)为30，密度为0.87g/cm3。上述非织造的CD可延伸支承层包括36％缩径拉伸的并列聚丙烯/聚乙烯双组份纺粘织物，基重33.9g/m2这里的聚丙烯为ESCORENETMPD3445，购自Exxon ChemicalCompany of Houston Texas，牌号为Dow6831。这三层用EHP粘合花纹于135°F(57°F)温度下，辊隙压力约30psi(206.9kPa)，在速度小于3m/分钟下热点粘合。76.2MDX152.4mmCD宽的层压件拉伸到304.8mm长。在释去偏压力后，此层压件返回到109.5mm的最终长度。此层压件的CD/MD剥离强度约2000g而悬垂度约2～4cm。
上面虽已相对具体实施形式描述了本发明，但内行人士应知，在不背离本发明的精神与范围的前提下是可以对本发明作出种种变更、改进和其它变动的。应该认为所有这类变更、改进和其它变动而为后附权利要求书所涵盖。

Claims (20)

1.一种膜层压体，它包括：可拉伸的聚合物阻挡层膜；可拉伸的热塑性聚合物非织造织物外层；以及包括无定形聚合物纤维的弹性中间非织造织物，其中，上述非织造织物粘合到所述阻挡层膜和所述可拉伸的非织造织物外层两者之上；且其中所述层压件是弹性的。
2.如权利要求1所述的膜层压件，其中，所述弹性纤维织物包括的弹性熔喷纤维织物的基重约8g/m2～100g/m2，且其中所述膜层压件具有的剥离强度大于200g。
3.如权利要求2所述的膜层压件，其中，所述可拉伸非织造织物外层包括缩径的非织造织物。
4.如权利要求2所述的膜层压件，其中，所述可拉伸非织造织物外层包括可反向缩径的非织造织物。
5.如权利要求2所述的膜层压件，其中，包括所述可拉伸聚合物阻挡层膜的聚合物是弹性聚合物且所述膜也是弹性的。
6.如权利要求2所述的膜层压件，其中，所述可拉伸非织造物外层包括弹性非织造织物。
7.如权利要求4所述的膜层压件，其中，所述弹性溶喷纤维织物的基重小于约34g/m2。
8.如权利要求1所述的膜层压件，其中，所述弹性中间非织造织物包括的聚乙烯弹性料具有约0.86g/cm3～约0.89g/cm3的密度。
9.如权利要求2所述的膜层压件，其中，所述弹性中间非织造织物包括密度约0.86g/cm3～0.89g/cm3的聚乙烯弹性体和密度大于0.90g/cm3的第二种聚乙烯两者的混合物。
10.如权利要求8所述的膜层压件，其中，所述可拉绅非织造外层包括缩径的非织造织物，而所述可拉伸的聚合物阻挡层膜包括具有WVTR大于300g/m2/小时的弹性充填膜。
11.如权利要求1所述的膜层压件，其中，所述阻挡层膜的WVTR大于800g/m2/24小时。
12.如权利要求11所述的膜层压件，其中，所述弹性中间非织造织物包括聚烯烃纤维的织物。
13.如权利要求12所述的膜层压件，其中，所述弹性中间非织造织物包括熔喷纤维织物。
14.如权利要求13所述的膜层压件，其中，所述中间非织造织物具有小于约34g/m2的基重。
15.如权利要求13所述的膜层压件，其中，所述阻挡层膜包括微孔膜。
16.如权利要求15所述的膜层压件，其中，所述阻挡层膜包括聚烯烃聚合物，而所述可拉伸非织造织物外层包括聚烯烃聚合物，且其中所述膜层压件具有大于500g的剥离强度。
17.如权利要求16所述的膜层压件，其中，所述阻挡层膜包括聚乙烯聚合物和填料，且其中在所述填料邻近有空隙。
18.如权利要求16所述的膜层压件，其中，所述阻挡层膜包括聚丙烯聚合物和填料且其中在所述填料邻近有空隙。
19.如权利要求16所述的膜层压件，其中，所述弹性中间非织造织物包括的聚乙烯弹性料具有约0.86g/cm3～约0.89g/m2的密度。
20.如权利要求16所述的膜层压件，其中，所述弹性中间非织造织物包括密度约0.86g/cm3～约0.89g/cm3的聚乙烯弹性料和密度大于0.90g/cm3的第二种聚乙烯两者的混合物。
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EP1015241A1 (en) 2000-07-05
KR100508608B1 (ko) 2005-08-17
CA2301002A1 (en) 1999-03-25
US6096668A (en) 2000-08-01
BR9812205A (pt) 2000-07-18
AU735677B2 (en) 2001-07-12
DE69811250T2 (de) 2003-11-27
EP1015241B1 (en) 2003-02-05
AU9390398A (en) 1999-04-05
KR20010023954A (ko) 2001-03-26
DE69811250D1 (de) 2003-03-13
WO1999014039A1 (en) 1999-03-25
CN1123441C (zh) 2003-10-08

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