CN1210147C - 柔韧性膜 - Google Patents
柔韧性膜 Download PDFInfo
- Publication number
- CN1210147C CN1210147C CNB998123544A CN99812354A CN1210147C CN 1210147 C CN1210147 C CN 1210147C CN B998123544 A CNB998123544 A CN B998123544A CN 99812354 A CN99812354 A CN 99812354A CN 1210147 C CN1210147 C CN 1210147C
- Authority
- CN
- China
- Prior art keywords
- film
- glycol
- polyurethane
- layer
- polymer composite
- 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 - Lifetime
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- 239000004814 polyurethane Substances 0.000 claims description 67
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 63
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- SSYDTHANSGMJTP-ZXZARUISSA-N (3s,4r)-oxolane-3,4-diol Chemical compound O[C@H]1COC[C@H]1O SSYDTHANSGMJTP-ZXZARUISSA-N 0.000 claims 1
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Abstract
描述了包括具有至少约10个微层的微层聚合物复合材料(30，30A)的膜(28A-F，124)。该微层(32，34，112，114，116)各自独立地是至多大约100微米厚并在至少一种流体阻隔材料和至少一种弹性材料之间交替存在。该膜(28)能够被制成增压气囊或缓冲装置以用于许多应用，其中包括鞋类和压气动蓄力器。
Description
本发明的领域
本发明涉及适合于同时需要阻隔性能和柔韧性的应用的膜。本发明的膜特别可用于增压气囊(包括缓冲装置)的构造。本发明的膜是弹性的和对氮气和用于填充气囊和缓冲装置的其它气体有非常低的气体透过速率。本发明进一步涉及包括本发明的一个或多个气囊或缓冲装置的鞋类。
本发明的背景
热塑性和热固性聚合物材料因为它们的流体(气体或液体)阻隔性能已经广泛用于膜中。此类流体阻隔膜例如用于塑料包裹材料和用于其它包装材料。具有良好的流体阻隔性能的聚合物材料的另一常见用途是用于可充气的气囊的形成。
可充气的气囊已经用于许多产品如车辆轮胎，球，重型机械上使用的蓄力器，和用于鞋类，尤其鞋子，作为缓冲装置。通常希望使用热塑性的聚合物材料，因为热塑性材料可以回收和再成形为新的制品，因此减少了在制造操作中的废料和有利于在制品的使用期之后回用。尽管热塑性阻隔膜因为它们的薄而可以挠曲到一定程度，但是对于许多应用来说，热塑性阻挡膜一般不具有足够的弹性。弹性材料或弹性体能够在解除变形力之后基本上恢复它们的最初形状和尺寸，即使当该部分具有较大的变形时。弹性在许多应用，包括用于鞋类和液压蓄力器的可充气式气囊中是重要的。
鞋类，和尤其鞋子，通常包括两个主要部分，鞋上层部分和鞋底。鞋上层部分的一般用途是舒适和舒服地包围脚。理想地，该鞋上层部分应该从有吸引力的高度耐用的舒适材料或材料混合物制造。从耐用材料制成的鞋底被设计来在使用过程中提供摩擦力和保护脚。鞋底还典型地在体育运动中提供增强的缓冲和振动吸收作用以保护穿用者的脚、踝和腿免受所产生的巨大冲击力。在跑步运动过程中产生的冲击力能够相当于穿用者的体重的两倍或三倍，而其它运动项目如打篮球可产生穿用者体重的六至十倍的力。许多鞋子，尤其运动鞋，现在包括一些类型的回弹性减震材料或组分以便在剧烈运动过程中对脚和身体提供缓冲作用。这些回弹性减震材料或组分通常在制鞋业中被称作中底(midsole)。这类回弹性减震材料或组分也能够用于鞋子的鞋内底部分，它一般被定义为鞋上层部分的直接处在脚的脚底表面之下的那一部分。
充气的气囊可用于鞋子的鞋底内部的中底或***件。充气式气囊通常充气到较大压力，为的是缓冲在剧烈运动过程中在脚上产生的力。此类气囊典型地分入两个大类中，“永久”充气的那些如在Rudy的US专利No.4,183,156和4,219,945中公开的那些，和使用泵和阀门***的那些，如在Huang的US专利No.4,722,131中公开的那些。
具有“永久”充气气囊的在US专利No.4,183,156中公开的那一类型的运动鞋已经由俄勒冈州Beaverton市的Nike，Inc.以商标“Air-Sole”和其它商标销售。这些鞋子的永久充气气囊是通过使用由工业上称作“超级气体”的具有低溶度系数的大分子气体膨胀的弹性热塑性材料制造的。气体如SF6，CF4，C2F6，C3F8等以这种方式用作超级气体。然而，超级气体是昂贵的，因此希望用价格比较低廉的气体象空气或氮气来永久充气。例如，1982年7月20日公布的授权于Rudy的标题为“扩散泵送设备的自充气装置”的US专利No.4,340,626(被引入本文供参考)公开了被制成气囊并用气体或气体混合物填充到规定压力的膜的选择性透过片。理想的是所用气体具有较低的通过选择性透过气囊到达外部环境中的扩散速率，而在大气中含有的气体如氮气、氧气和氩气具有较高的穿过气囊的扩散速率。通过将来自大气的氮气、氧气和氩气的分压增加到最初填充气囊的气体的分压上，使气囊内的总压力增加。气体的相对单向增加以增强气囊的总压的这一概念已知为“扩散泵送”。
在推出Air-SoleTM运动鞋之前和之后不久在鞋类制造工业中使用的许多早期中底气囊由单层气体阻隔型膜组成，该膜是从聚偏二氯乙烯型材料如Saran(它是Dow Chemical Co.的注册商标)制备且本质上属于硬质塑料，具有较差的曲挠疲劳，热封性和弹性。两种气体阻隔材料的复合膜也已经使用。Momose的US专利No.5,122,322(被引入本文供参考)描述了第一热塑性树脂的膜，它具有与该膜的平面平行的第二热塑性树脂的多个连续胶带。第一热塑性树脂选自聚烯烃，聚苯乙烯，聚丙烯腈，聚酯，聚碳酸酯，或聚氯乙烯树脂和改性树酯。第二树脂可以是聚酰胺，皂化乙烯-乙酸乙烯酯共聚物，乙烯-乙烯醇共聚物，聚偏二氯乙烯，或聚丙烯腈共聚物。该膜是通过如下制备的：从第一挤出机中挤出第一树脂和从第二挤出机中挤出第二树脂，将两挤出物料流同时引入到静态混合器中，在该混合器中形成了层(胶带)。该膜可有一个或多个外膜层压合到它上面。尽管这些膜被公开在20℃下具有0.12-900cc/m2.天.大气压的透氧速率，使它们一般适合用于形成包装和装运材料的缓冲材料，但该膜不具有足够的回弹性或柔韧性以用于鞋类的缓冲气囊。
已经公开了两种不同类型的阻隔材料的其它层压材料，其中层压材料具有不同材料的许多较薄层。Schrenk等人，US专利No.3,565,985，4,937,134，5,202,074，5,094,788，和5,094,793，5,380,479，5,540,878，5,626,950；Chisolm等人，US专利No.3,557,265；Ramanathan等人，和US专利No.5,269,995，所有这些文献被引入本文供参考(包括其中引用的参考文献)，公开了通过使用至少两种不同热塑性塑料的料流制备多层膜(至少约10层)的方法。熔化热塑性树脂的料流被合并成层状料流，然后被引导通过层叠装置以获得多层膜。在这些专利中描述的多层叠加方法用于获得虹彩膜。为了产生虹彩效应，起虹彩作用的层必须具有0.05微米到5微米的厚度。不同的热塑性材料在选择好后应具有折射率的最大差异，以在多层膜中获得最大虹彩效果。气体阻隔材料无法生产能够吸收反复冲击但没有变形或疲劳破坏(而这些是可充气的气囊或缓冲装置的膜所必需的)的膜。
为复合材料或层压材料的已知气囊膜也能够在鞋类气囊中产生各种问题，如层离，剥离，在熔合界面的气体扩散或毛细管作用，低的伸长率导致充气产品起皱，成品气囊的雾状外观，降低的抗穿刺性和撕裂强度，在吹塑和/或热封和RF熔合时耐变形性下降，高成本加工，和泡沫密封和胶合都比较困难，等等。在制备层压材料时一些以前已知的多层气囊使用粘结层或粘合剂，以获得足够高的中间层粘合强度以避免上述问题。然而，此类粘结层或粘合剂的使用一般会妨碍在产品重新形成为可利用产品过程中形成的任何废料的再次研磨和回用，使制造花费更大和带来更多浪费。粘合剂的使用还增加了制造层压材料的成本和复杂性。现有技术的这些及其它所公知的缺点更详细地描述在US专利No.4,340,626，4,936,029和5,042,176中，它们中的每一件被引入本文供参考。
除了两个气体阻隔层的结合以外，该复合材料可从具有非常不同的性能的材料的各层形成。不同材料的复合材料特别可用于鞋类气囊，因为对用于鞋类气囊的膜有许多要求，其中一些是相互冲突的。例如，该膜必须同时对填充气体和周围气体显示出早已提及的优异气体阻隔性能，而同时该膜必须是弹性的和耐疲劳破坏。用于构造鞋类气囊的材料必须进一步耐受所含液体和鞋类所处环境的降解作用。这一类型薄膜或膜的各项不同的和有时对立的性能要求的问题一般通过形成至少两层明显不同的材料的层压材料来解决，其中一层提供弹性体的耐久柔韧性和另一层提供流体阻隔性能。
一种措施是将至少两种明显不同的材料进行反应或共混在一起，以使不同材料中的每一种都对接枝共聚物或共混物层的性能发挥各自的作用。Moureaux，US专利No.5,036,110(被引入本文供参考)是接枝共聚物组合物的实例。Moureaux公开了用于包括热塑性聚氨酯和乙烯-乙烯醇共聚物的接枝共聚物膜的压气动蓄力器的回弹性膜。该乙烯-乙烯醇共聚物占接枝共聚物的5-20％。该乙烯-乙烯醇共聚物被分散在聚氨酯聚合物中和在两聚合物之间有一些接枝。该接枝共聚物在聚氨酯基质中形成乙烯-乙烯醇共聚物的小岛。该膜是在液压气动的膜中两层热塑性聚氨酯之间的中心层。尽管与未改性聚氨酯相比降低了氮气透过率，但包括气体阻隔树脂的颗粒的基质膜不会提供与具有流体阻隔材料的连续层的复合膜同样低的气体透过速率。
在另一种可供选择的措施中，描述了通过提供一种膜来省略掉粘合剂粘结层的层压材料，该膜包括热塑性弹性体如热塑性聚氨酯的第一层和包括阻隔材料如乙烯和乙烯醇的共聚物的第二层，其中氢键存在于该膜的在第一和第二层之间的部分上。具有柔韧性材料层和流体阻隔材料层的此类层压材料描述在例如US专利No.5,713,141(1998年2月3日公布，被引入本文供参考)和共同未决的US申请序列号08/299,287(1994年8月31日提交，标题“有改进的柔韧性阻隔膜的缓冲装置”)；序列号08/684,351(1996年7月19日提交，标题“层压的回弹性柔韧性阻隔膜”；序列号08/475,276(1995年6月7日提交，标题“包括使用脂族热塑性聚氨酯的阻隔层的阻隔膜”)；序列号08/475,275(1995年6月7日，标题“包括使用聚酯多元醇的阻隔层的阻隔膜”)；和序列号08/571,160(1995年12月12日提交，标题“包括聚酯多元醇的聚氨酯型材料的膜”)中，这些文献的每一件被引入本文供参考。尽管在这些参考文献中公开的膜可提供据信在现有技术中有重要改进的柔韧性“永久”膨胀、充气的鞋子缓冲组分，但根据本发明的教导仍然需要进一步的改进。
本发明的目的是提供膜和膜材，它们表现出增强的柔韧性和对流体如填充气体的不希望有的透过性的阻力。本发明的另一目的是提供用于可由气体如氮气膨胀的可充气气囊的弹性膜，其中该膜提供大约10立方厘米/平方米/大气压/天(cc/m2.atm.天)或更低的气体透过速率。
本发明的概述
我们现在已经发现，具有改进的弹性和低的气体透过速率的可充气气囊能够从微层(microlayer)聚合物复合材料制成。本发明的微层聚合物复合材料可用于形成在许多应用(尤其在鞋类)中使用的增压气囊和其它缓冲装置或用于蓄力器的耐用弹性膜。“耐用”是指该膜具有优异的抵抗疲劳破坏的能力，它意味着该膜能够经历反复挠曲和/或变形和恢复但沿层界面没有层离和没有在膜的整个厚度上产生裂纹，优选在宽的温度范围内。对于本发明的目的，术语“膜”用于优选表示将一种流体(不论气体还是液体)与另一种流体分离的自立式(free-standing)膜。被层合到或涂敷到不用于分离流体的另一种制品上的膜优选从本发明膜的定义中排除。
该微层聚合物复合材料包括提供回弹性和柔韧性的第一聚合物材料(也称作结构或弹性材料)的微层，和提供低气体透过速率的第二聚合物材料(也称作流体阻隔材料)的微层。对于同样总体量的流体阻隔材料，非弹性流体阻隔材料的微层提供更具弹性、更具回弹性的膜，与现有技术的具有厚得多的阻隔材料层的层压材料相比。
尤其，本发明提供用于诸如鞋类或液压蓄力器之类应用的可充气气囊，该气囊具有包括至少一层本发明的微层聚合物复合材料的膜。本发明的微层聚合物复合材料具有由结构材料提供的橡胶状或弹性机械性能，使它在使用过程中反复和可靠地吸收高的力量但没有降解或疲劳破坏。在诸如鞋类和液压蓄力器之类的应用中该膜在周期载荷中具有优异稳定性是特别重要的。该微层聚合物复合材料具有由气体阻隔材料提供的低气体透过速率，使它保持膨胀和因此基本上在鞋类或液压蓄力器的预期寿命中提供缓冲作用，而无需周期性地再充气和再次增压气囊。
膜的氮气透过速率应该低于大约10立方厘米/米2/大气压/天(cc/m2.atm.day)。测量不同膜材料的相对透过性、渗透性和扩散性的可接受方法列于指定为ASTM D-1434-82-V的程序中。根据ASTMD-1434-82-V，由下面等式测量透过性、渗透性和扩散性：
透过性
(气体量)/[(面积)×(时间)×(压差)]
＝透过性(GTR)/(压差)
＝cc/(sq.m)(24hr)(Pa)
渗透性
[(气体量)×(膜厚度)]/[(面积)×(时间)×(压差)]
＝渗透性[(GTR)×(膜厚度)]/(压差)
＝[(cc)(mil)]/[(m2)(24hr)(Pa)]
扩散性(一大气压下)
(气体量)/[(面积)×(时间)]
＝气体透过速率(GTR)
＝cc/(m2)(24hr)
附图的简述
图1是运动鞋的侧视图，其中中底的一部分被切开来说明剖视图；
图2是图1的运动鞋的底视图，一部分被切开以暴露另一剖视图；
图3是沿着图1的线3-3取下的剖视图；
图4是管形两层缓冲装置的一个实例的截段侧视图；
图5是沿着图4的线4-4取下的剖视图；
图6是管形三层缓冲装置的第二个实例的截段侧视图；
图7是沿着图6的线6-6截取的截面视图；
图8是形成为鞋子缓冲装置的本发明膜实例的透视图；
图9是在图8中说明的膜的侧视图；
图10是形成为鞋子缓冲装置的本发明膜实例的透视图；
图11是制成被引入到鞋子中的缓冲装置的本发明膜实例的侧视图；
图12是在图11中说明的膜的透视图；
图13是在图11和12中说明的膜的顶视图；
图14是制成被引入到鞋子中的缓冲装置的本发明膜实例的侧视图；
图15是在图14中说明的膜的透视图；
图16是在图14和15中说明的膜的顶视图；
图17是制成鞋子缓冲装置的根据本发明教导的膜实例的透视图；
图18是在图17中说明的膜的侧视图；
图19是从根据本发明教导的层压膜形成的产品的剖视图；
图20是使用根据本发明教导的层压膜所制造的第二种产品的剖视图；
图21是片材共挤出组合件的侧面视图；
图22是图21的片材共挤出组合件的歧管部分的剖视图；
图23是管材共挤出组合件的侧视图；
图24是单层管状膜的剖视图；
图25是从根据本发明教导的单层膜形成的产品的剖视图；和
图26是根据本发明的微层聚合物复合材料的截面的照片。
详细说明
本发明的气囊是从包括本发明的微层聚合物复合材料层的弹性膜制备的。本发明的微层聚合物型复合材料具有至少一个流体阻隔材料和至少一种结构、弹性材料的交替薄层。也考虑的是包括不同流体阻隔材料的层和/或不同弹性材料的层的微层聚合物复合材料，所有不同层按规则重复顺序排列。除弹性层和流体阻隔层之外且与它们一起按规则、重复顺序交替存在的其它层任选包括在内。微层聚合物复合材料应该具有至少约10层。优选地，该微层聚合物复合材料具有至少约20层，更优选至少约30层，和更优选至少约50层。该微层聚合物复合材料能够具有几千层，所属领域的技术人员将会认识到，层的数目将取决于一些因素，如所选择的具体材料，各层的厚度，微层聚合物复合材料的厚度，制备多层的加工条件和复合材料的最后应用。该微层弹性体膜优选具有约10层到约1000层，更优选约30层到约1000层和甚至更优选它具有约50层到约500层。
流体阻隔材料的各单层的平均厚度可以低至几个纳米到高达几个密耳(大约100微米)厚。优选地，单层具有平均厚度最多约0.1密耳(大约2.5微米)。大约0.0004密耳(大约0.01微米)到大约0.1密耳(大约2.5微米)的平均厚度是特别优选的。例如，各阻隔材料层能够是平均约0.05密耳(大约1.2微米)。流体阻隔层材料的较薄层改进了气囊膜的延性。
适合于形成结构层的弹性材料包括但不限于聚氨酯弹性体，包括基于芳族和脂族异氰酸酯的弹性体；柔韧性聚烯烃，包括柔韧性聚乙烯和聚丙烯均聚物和共聚物；苯乙烯系热塑性弹性体；聚酰胺弹性体；聚酰胺-醚弹性体；酯-醚或酯-酯弹性体；柔韧性离聚物；热塑性硫化橡胶；柔韧性聚(氯乙烯)均聚物和共聚物；柔韧性丙烯酸类聚合物；和这些物质的共混物和合金，如聚(氯乙烯)合金如聚(氯乙烯)-聚氨酯合金。这些不同的弹性材料可作为共混物被结合在微层聚合物复合材料的结构层中，或作为微层聚合物型复合材料的隔离层被包括在内。
特别合适的是热塑性聚酯-聚氨酯，聚醚-聚氨酯，和聚碳酸酯-聚氨酯，包括但不限于使用聚四氢呋喃，聚酯，聚己内酯聚酯，和环氧乙烷、环氧丙烷的聚醚，和包括环氧乙烷和环氧丙烷的共聚物作为二醇反应物所聚合的聚氨酯。这些聚合物二醇型聚氨酯是由聚合物二醇(聚酯二醇，聚醚二醇，聚己内酯二醇，聚四氢呋喃二醇，或聚碳酸酯二醇)，一种或多种多异氰酸酯，和任选的一种或多种扩链化合物反应制备。这里所使用的扩链化合物是具有两个或两个以上可与异氰酸酯基团反应的官能团的化合物。优选该聚合物二醇型聚氨酯是基本上线性的(即，基本上所有反应物是二官能化)。
用于形成本发明的优选热塑性聚氨酯的聚酯二醇一般是通过多元酸化合物和多元醇化合物的缩聚反应制备的。优选，多元酸化合物和多元醇化合物是二官能的，即二酸化合物和二醇用于制备基本上线性的聚酯二醇，但少量单官能，三官能，和更高官能的物质(也许至多5mol％)能够包括在内。合适的二羧酸不受限制地包括戊二酸，琥珀酸，丙二酸，草酸，邻苯二甲酸，六氢邻苯二甲酸，己二酸，马来酸和这些的混合物。合适的多元醇不受限制地包括，其中扩链剂选自乙二醇，二甘醇，三甘醇，四甘醇，丙二醇，二丙二醇，三丙二醇，四丙二醇，环己烷二甲醇，2-乙基-1，6-己二醇，Esterdiol 204(由EastmanChemical Co.销售)，1，4-丁二醇，1，5-戊二醇，1，3-丙二醇，丁二醇，新戊二醇，和它们的混合物。少量的三醇或更高官能度的多元醇，如三羟甲基丙烷或季戊四醇有时也包括在内。在一个优选实施方案中，该羧酸包括己二酸和该二醇包括1，4-丁二醇。酯化聚合反应用的典型催化剂是质子酸，路易斯酸，钛的醇盐，和二烷基锡氧化物。
用于制备优选热塑性聚氨酯的聚合物聚醚或聚己内酯二醇反应物是通过二醇引发剂(例如乙二醇或丙二醇)与内酯或烯化氧扩链剂反应所制备的。优选的扩链剂是ε-己内酯，环氧乙烷，和环氧丙烷。能够通过活性氢开环的内酯是现有技术中熟知的。合适内酯的例子不受限制地包括ε-己内酯，γ-己内酯，β-丁内酯，β-丙内酯，γ-丁内酯，α-甲基-γ-丁内酯，β-甲基-γ-丁内酯，γ-戊内酯，δ-戊内酯，γ-癸内酯，δ-癸内酯，γ-壬内酯，γ-辛内酯，和它们的混合物。在一个优选实施方案中，该内酯是ε-己内酯。可用于实施本发明的内酯也能够由下式表示：
其中n是1到7的正整数和R是一个或多个H原子，或具有1-7个碳原子的取代或未取代烷基。有用的催化剂包括以上对于聚酯合成所提及的那些。另外，该反应能够通过形成在将要与内酯环反应的分子上的羟基的钠盐来引发。
在本发明的另一实施方案中，二醇引发剂与含有环氧乙烷的化合物反应，生产用于聚氨酯聚合的聚醚二醇。含环氧乙烷的化合物优选是烯化氧或环醚，尤其优选从环氧乙烷，环氧丙烷，氧化丁烯，四氢呋喃，和它们的混合物中选择的化合物。烯化氧聚合物片段不受限制地包括环氧乙烷，环氧丙烷，1，2-环己烯氧化物，1-丁烯氧化物，2-丁烯氧化物，1-己烯氧化物，叔丁基乙烯氧化物，苯基缩水甘油醚，1-癸烯氧化物，异丁烯氧化物，环戊烯氧化物，1-戊烯氧化物，和这些单体的混合物的聚合产物。该烯化氧聚合典型是碱催化的。该聚合反应例如可通过加入羟基官能化引发剂和催化量的苛性碱如氢氧化钾、甲醇钠或叔丁醇钾，和以一种保持单体满足反应需要的足够速率添加该烯化氧来进行。两种或更多种不同的烯化氧单体可通过一起添加进行无规共聚合和通过顺序添加进行嵌段聚合。环氧乙烷或环氧丙烷的均聚物或共聚物是优选的。
四氢呋喃在已知条件下聚合形成重复单元
-[CH2CH2CH2CH2O]-。
通过使用诸如SbF6 -，AsF6 -，PF6 -，SbCl6 -，BF4 -，CF3SO3 -，FSO3 -，和ClO4 -之类的抗衡离子，由阳离子开环反应来聚合四氢呋喃。通过形成叔氧鎓离子来引发。该聚四氢呋喃链段能够制备成“活性聚合物”并通过与二醇如以上提及的任何二醇的羟基反应来封端。
脂肪族聚碳酸酯二醇是通过在催化剂如碱金属、锡催化剂或钛化合物存在下由二醇与碳酸二烷基酯(如碳酸二乙酯)，碳酸二苯酯，或二氧杂环酮类(dioxolanones)(如具有5员-和六员环的环状碳酸酯)反应来制备。有用的二醇不受限制地包括任何早已提及的那些。芳族聚碳酸酯通常是从双酚例如双酚A与光气或碳酸二苯酯反应来制备。
用于聚氨酯合成的聚合物二醇如以上所述的聚合物型聚酯二醇优选具有数均分子量(例如通过ASTM D-4274方法测定)为大约300到大约4,000；更优选大约400到大约3,000；和进一步优选大约500到大约2,000。聚合物型二醇通常形成弹性聚氨酯的“软链段”。
弹性聚氨酯的合成可通过一种或多种以上聚合物二醇，一种或多种具有至少两个异氰酸酯基团的化合物，和任选的一种或多种扩链剂反应来进行。弹性聚氨酯优选是线性的和因此多异氰酸酯组分优选是基本上二官能化的。用于制备本发明的热塑性聚氨酯的有用二异氰酸酯化合物不受限制地包括异佛尔酮二异氰酸酯(IPDI)，亚甲基双-4-环己基异氰酸酯(H12MDI)，环己基二异氰酸酯(CHDI)，m-四甲基二甲苯二异氰酸酯(m-TMXDI)，p-四甲基二甲苯二异氰酸酯(p-TMXDI)，亚乙基二异氰酸酯，1，2-二异氰酸根丙烷，1，3-二异氰酸根丙烷，1，6-二异氰酸根己烷(六亚甲基二异氰酸酯或HDI)，1，4-亚丁基二异氰酸酯，赖氨酸二异氰酸酯，1，4-亚甲基双(环己基异氰酸酯)，甲苯二异氰酸酯的各种异构体，间二甲苯二异氰酸酯和对二甲苯二异氰酸酯，4-氯-1，3-亚苯基二异氰酸酯，1，5-四氢-萘二异氰酸酯，4，4’-二苄基二异氰酸酯，和1，2，4-苯三异氰酸酯，亚二甲苯基二异氰酸酯(XDI)，和它们的混合物。特别有用的是二苯甲烷二异氰酸酯(MDI)。
有用的含活性氢的扩链剂通常含有至少两个活性氢基团，例如，二醇，二硫醇，二胺，或具有羟基、硫醇和氨基的混合基团的化合物，如链烷醇胺，氨基烷基硫醇，和羟烷基硫醇。扩链剂的分子量优选是大约60-大约400。醇类和胺类是优选的。可用作聚氨酯扩链剂的有用二醇的典型实例不受限制地包括1，6-己二醇，环己烷二甲醇(由Eastman Chemical Co.以CHDM销售)，2-乙基-l，6-己二醇，Esterdiol204(由Eastman Chemical Co.销售)，1，4-丁二醇，乙二醇和乙二醇的低级低聚物(包括二甘醇、三甘醇和四甘醇)；丙二醇和丙二醇的低级低聚物(包括二丙二醇、三丙二醇和四丙二醇)；1，3-丙二醇，1，4-丁二醇，新戊二醇，二羟烷基化芳族化合物如氢醌和间苯二酚的双(2-羟乙基)醚；对二甲苯-α，α’-二醇；对二甲苯-α，α’-二醇的双(2-羟乙基)醚；间二甲苯-α，α’-二醇和双(2-羟乙基)醚和它们的混合物。合适的二胺扩链剂不受限制地包括对苯二胺，间苯二胺，联苯胺，4，4’-亚甲基二苯胺，4，4’-亚甲基双(2-氯苯胺)，乙二胺，和这些的混合物。其它典型的扩链剂是氨基醇如乙醇胺，丙醇胺，丁醇胺，和这些的混合物。优选的扩链剂包括乙二醇，二甘醇，三甘醇，四甘醇，丙二醇，二丙二醇，三丙二醇，四丙二醇，1，3-丙二醇，1，4-丁二醇，1，6-己二醇，和这些的混合物。
除以上描述的双官能扩链剂外，少量的三官能扩链剂如三羟甲基丙烷，1，2，6-己烷三醇和甘油，和/或单官能活性氢化合物如丁醇或二甲胺，也可存在。三官能扩链剂和/或单官能化合物的用量优选基于反应产物和所用含活性氢基团的总重量为5.0当量百分率或更低。
多异氰酸酯，聚合物二醇和增链剂的反应典型通过加热这些组分来进行，例如在双螺杆挤出机中进行熔体反应。该反应的典型催化剂包括有机锡催化剂如辛酸亚锡。通常，聚合物二醇如聚酯二醇与扩链剂的比例可在较宽范围内变化，这大大取决于最终聚氨酯弹性体的所需硬度。例如，聚酯二醇与扩链剂的当量比可在1∶0到1∶12和更优选1∶1到1∶8的范围内。优选，所使用的二异氰酸酯在比例上进行调整，以使异氰酸酯当量与含活性氢的物质的当量之比是在0.95∶1到1.10∶1，和优选0.98∶1到1.04∶1范围内。聚合物二醇片段典型占聚氨酯聚合物的大约35％到大约65％(按重量计)，和优选占聚氨酯聚合物的大约35％到大约50％(重量)。
希望在某些应用条件下包括聚氨酯的共混物以形成微层聚合物复合材料的结构层，例如当水解的敏感性特别需要关注时。例如，包括从羧酸和二醇的反应混合物形成的聚醚二醇或聚酯二醇(其中反应产物的重复单元具有8个以上碳原子)的软链段的聚氨酯能够与包括具有8个或8个以下碳原子的重复单元的聚酯二醇或支化二醇产物的聚氨酯共混。优选，除了包括具有8个或8个以下碳原子或有氧原子连接于叔碳的的聚酯二醇重复单元的那些聚氨酯以外的聚氨酯将以至多约30wt.％(即70.0wt.％聚己二酸乙二醇酯型聚氨酯，30.0％间苯二甲酸酯聚酯二醇型聚氨酯)的量存在于共混物中。其中反应产物具有8个以上碳原子的聚酯二醇的特定实例包括聚(间苯二甲酸乙二醇酯)，聚(间苯二甲酸1，4-丁二醇酯)和聚(间苯二甲酸1，6-己二醇酯)。
作为各种热塑性聚氨酯的共混物的替代物，可使用具有各种软链段的单种聚氨酯。再一次，不想受限制，软链段除包括具有总共8个或8个以下碳原子的软链段外，还包括具有总共8个以上碳原子的聚醚二醇，聚酯二醇或它们的混合物。可以认为，包括羧酸和具有8个以上总碳原子数的二醇的反应产物的软链段组成部分的总量能够是包括在聚氨酯中的软链段总重量的至多约30wt.％。因此，至少70wt.％的软链段重复单元是羧酸和二醇的反应产物，其中反应产物的总碳原子数是8个或低于8个。
也应指出的是，有许多方式将其中至多30wt.％聚酯具有含8个以上碳原子的重复单元的聚氨酯加入到本发明的聚氨酯中。30wt％或更少的从含有带8个以上碳原子的重复单元的聚酯二醇形成的聚氨酯能够作为成品聚合物与70wt％或更高的从具有含8个或8个以下碳原子的重复单元的聚酯二醇形成的聚氨酯进行共混，或单种聚氨酯能够从聚酯二醇的混合物制备，其中70wt.％或更多含有带8个或8个以下碳原子的重复单元和余量含有具有8个以上碳原子的重复单元，如前面所述。聚氨酯能够从二羧酸和二醇的反应制备的单种二醇制备，以使聚酯二醇中70wt.％的重复单元含有8个或8个以下碳原子。这些技术的结合也是可能的。能够使用的含有6个以上碳原子的酸是间苯二甲酸和邻苯二甲酸。
可用于形成外层32的许多热塑性聚氨酯当中，聚氨酯如所有酯型或醚型的聚氨酯已被证明是特别有用的。
合适材料的特定例子包括由Elf Atochem以商品名PEBAX销售的聚酰胺-醚弹性体，由DuPont以商品名HYTREL销售的酯-醚弹性体，由DSM Engineering以商品名ARNITEL销售的酯-酯和酯-醚弹性体，由Advanced Elastomeric Systems以商品名SANTOPRENE销售的热塑性硫化产物，由Emser以商品名GRILAMID销售的弹性聚酰胺，和由DowChemical Company，Midland，MI以商品名PELLETHANE销售的弹性聚氨酯，由BASF Corporation，Mt.Olive，NJ销售的ELASTOLLAN聚氨酯，由Bayer销售的TEXIN和DESMOPAN聚氨酯，由Morton销售的MORTHANE聚氨酯，和由B.F.Goodrich Co销售的ESTANE聚氨酯。
除结构层的弹性材料之外，本发明的微层聚合物型复合材料包括流体阻隔材料的层。合适的流体阻隔材料不受限制地包括乙烯-乙烯醇共聚物，聚(氯乙烯)，聚亚乙烯基聚合物和共聚物，尤其如聚偏二氯乙烯，聚酰胺，包括无定形的聚酰胺在内；丙烯腈聚合物，包括丙烯腈-丙烯酸甲酯共聚物在内；聚氨酯工程塑料，聚甲基戊烯树脂；乙烯-一氧化碳共聚物，液晶聚合物，聚对苯二甲酸乙二醇酯，聚醚酰亚胺，聚丙烯酸酰亚胺，和已知具有较低气体透过速率的聚合物材料。这些材料的共混物和合金，如聚酰亚胺和结晶聚合物如液晶聚合物，聚酰胺和聚对苯二甲酸乙二醇酯，和聚酰胺与苯乙烯系塑料的结合物也是合适的。乙烯-乙烯醇共聚物是优选的，尤其其中乙烯共聚物比率为大约25mol％-大约50mol％和更特别为大约25mol％-大约40mol％的那些共聚物。乙烯-乙烯醇共聚物是通过完全水解乙烯-乙酸乙烯酯共聚物所制备的。这些不同的流体阻隔材料可作为共混物被结合在微层聚合物复合材料的结构层中，或作为微层聚合物复合材料的隔离层被包括在内。
合适特定例子的实例包括：丙烯腈共聚物，如购自BP Chemicals，Inc.的BAREX；聚氨酯工程塑料如购自Dow Chemical Corp.，Midland，MI的ISOPLAST；由EVAL Company of America(EVALCA)，Lisle，Illinois以商品名EVAL销售的乙烯-乙烯醇共聚物；Nippon GosheiCo.，Ltd.(U.S.A.)of New York，NY的SOARNOL，Solvay的CLARENE和DuPont的SELAR OH；以商品名SARAN购自Dow Chemical和以商品名IXAN购自Solvay的聚偏二氯乙烯；液晶聚合物如HoechstCelanese的VECTRA和Amoco Chemicals的XYDAR；MDX6尼龙，可从Mitsubishi Gas Chemical Co.，Ltd，Solvay，和Toyobo获得和无定形尼龙如Mitsubishi的NOVAMID X21，DuPont的SELAR PA和General Electric Company的GELON A-100；可从Rohm & Haas获得的KAMAX聚丙烯酸-酰亚胺共聚物；由General Electric以商品名ULTEM销售的聚醚酰亚胺；可从Air Products获得的VINEX聚(乙烯醇)；和可从Phillips 66 Company以商品名CRYSTALOR和从MitsuiPetrochemical Industries以商品名TPXv获得的聚甲基戊烯树脂。非常优选的市场上可买到的乙烯和乙烯醇共聚物，如可从EVAL获得的那些典型地具有大约25mol％到大约48mol％的平均乙烯含量。
本发明的微层聚合物复合材料的一个其它特征是在弹性材料和流体阻隔材料的各层之间存在的增强粘结。这种所谓的增强粘结通常例如通过对于这两层使用具有带有能够参与氢键的氢原子(如羟基中的氢原子或连接于聚氨酯基团中的氮原子的氢原子)的可用官能团和各种受体基团(如羟基中的氧原子，聚氨酯基团和酯基团中的羰基氧，和PVDC中的氯原子)的材料来达到。该微层聚合物复合材料的特征在于氢键据信存在于构成交替层的弹性材料和流体阻隔材料之间。例如，当弹性材料包括聚酯二醇型聚氨酯和流体阻隔材料包括从乙烯和乙烯醇的共聚物，聚偏二氯乙烯，丙烯腈和丙烯酸甲酯的共聚物，聚对苯二甲酸乙二醇酯，脂肪族和芳族聚酰胺，结晶聚合物和聚氨酯工程热塑性塑料中选择的聚合物时，上述氢键据信存在。除该氢键之外，理论上推断在弹性第一材料和流体阻隔第二材料的各层之间一般还存在一定量的共价键，如果例如在相邻层中有聚氨酯或如果这些层中的一层包括聚氨酯和相邻层包括阻隔材料如乙烯和乙烯醇的共聚物的话。再一些其它因素如取向力和诱导力，另外已知为范德华力，它们从任何两个分子之间存在的伦敦力产生以及在极性分子之间存在的偶极-偶极力据信有利于提高热塑性聚氨酯和主层的毗邻层之间的粘合强度。
除该弹性聚合物和阻隔聚合物之外，该微层聚合物复合材料的各层可包括各种普通添加剂，其中不受限制地包括水解稳定剂，增塑剂，抗氧化剂，紫外线稳定剂，热稳定剂，光稳定剂，有机防粘连化合物，着色剂(包括颜料，染料等)，杀真菌剂，抗微生物剂(包括杀菌剂等)，脱模剂，加工助剂，和这些的混合物。水解稳定剂的例子包括已知为STABAXOL P和STABAXOL P-100的两种可市购的碳化二亚胺型水解稳定剂，它们从新泽西州Trenton市的Rhein Chemie获得。其它碳化二亚胺-或聚碳化二亚胺型水解稳定剂或基于环氧化大豆油的稳定剂也可以使用。水解稳定剂总用量通常是小于组合物总量的5.0wt％。
还能够包括增塑剂以便增加最终产物的柔韧性和耐久性，以及促进材料从树脂形式加工成膜或片材。例如，和没有限制意义，增塑剂如基于邻苯二甲酸丁基苄酯(它作为例如Santicizer 160从Monsanto购买)的那些已证明特别有用。无论使用增塑剂还是增塑剂混合物，增塑剂(如果有的话)的总量通常是小于总组合物的20.0wt.％。
结构聚合物和流体阻隔聚合物的交替层具有基本上与复合材料的主表面平行排列的主表面。需要有足够的流体阻隔聚合物的层数，以使微层复合材料具有所需流体透过速率。
多层聚合物复合材料可由至少两种不同的方法形成。在第一方法中，本发明的多层聚合物复合材料能够使用两层、三层或五层供料头来制备，该供料头将层状料流引导至静态混合器或层叠器中。该静态混合器具有多个混合元件，优选至少大约5个元件，以便以几何方式增加层数。
在第二方法中，本发明的多层聚合物复合材料能够通过提供包括聚合物材料的离散层的第一料流来制备。这一方法的优选实施方案被详细描述在Schrenk等人的US专利No.5,094,793(1992年3月10日公布)中，它的全部内容被引入本文供参考。简短地说，包括离散层的第一料流能够再次通过将来自挤出机的分别含有弹性材料和流体阻隔材料的熔化挤出物引导至双层，三层，或五层供料头中来形成。第一料流然后被分成多个分支料流，该分支料流然后被重新引导或复位和各自对称地膨胀和收缩，最后以重叠关系再组合以形成具有更多离散层数的第二料流。另外，根据Ramanathan等人美国专利No.5,269,995(1993年12月14日公布)的方法可引入保护性界面层，该文献的全部内容被引入本文供参考。保护层保扩结构层和流体阻隔层以防止在层形成和叠加过程中产生不稳定性和破裂。该保护层是由熔化热塑性材料的料流提供，该材料被提供到复合材料料流的外表面上以在共挤压装置的壁上形成保护性界面层。保扩层可能为微层聚合物复合材料附加特殊光学或物理性能上的益处，如特殊的着色，包括通过在保护性界面层中包含金属或其它片状颜料所获得的金属化着色。
虽然没有必要让所有的层是完整的层，即在该层的平面上延伸至整片的所有边缘，但还是希望大多数层是基本上完整的层，即延伸到膜的边缘。
本发明的弹性膜包括微层聚合物复合材料，或作为唯一的层或作为层压构造中的一层。该膜可具有任何适宜的长度和宽度以形成所需要的鞋类气囊或液压蓄力器。膜的微层聚合物复合材料的平均厚度可在宽范围内变化，例如它可以是大约3密耳(大约75微米)到大约200密耳(大约0.5厘米)。优选，微层聚合物复合材料的平均厚度是至少约50微米，优选大约75微米到大约0.5厘米，更优选大约125微米到大约0.5厘米，和特别优选大约125微米到大约0.15厘米。当该微层聚合物复合材料用于制备鞋类的气囊时，优选的是该微层材料具有平均厚度为大约3密耳(大约75微米)到大约40密耳(大约0.1厘米)，而用于压气动蓄力器的膜通常更厚。在一个优选实施方案中，该微层聚合物复合材料具有平均厚度为至少大约125微米。
本发明的膜能够是包括微层聚合物材料作为一个或多个层合层的层压材料。优选，交替层选自以上被列举适合作为微层材料的结构材料的那些聚合物，和更优选交替层是聚氨酯材料。任何数目的微层，优选一层至约5层，更优选一层至三层用作层压材料的交替层。层压材料的其它层优选是弹性的并包括选自早已被提及适用于微层聚合物复合材料的结构层的那些聚合物的热塑性弹性体。本发明的一种优选膜是包括弹性聚氨酯的至少一层A和微层聚合物复合材料的至少一层B的层压材料。在其它优选实施方案中，该膜是具有多层A-B-A或多层A-B-A-B-A的层压材料。
当该微层聚合物膜用于制备层压材料时，该层压材料可具有平均厚度为大约3密耳(大约75微米)到大约200密耳(大约0.5厘米)，和优选它具有平均厚度为大约3密耳(大约75微米)到大约50密耳(大约0.13厘米)。层压材料的微层聚合物膜层优选是大约0.25密耳(大约6.35微米)到大约102密耳(2600微米)。
该气囊可通过RF(射频)熔合该微层材料或含微层的层压材料的两片来生产，特别当一层是极性材料如聚氨酯时。非极性材料如聚烯烃能够通过使用超声或热封技术来熔合。其它熟知的熔合技术也可使用。
当用作鞋类如鞋子中的缓冲装置时，气囊可充气(优选用氮气)到至少大约3psi和至多大约50psi的内压力。优选气囊被充气至内压力为大约5psi到大约35psi，更优选大约5psi到大约30psi，进一步优选大约10psi到大约30psi，和更优选大约15psi到大约25psi。本技术领域的熟练技术人员将会认识到，在鞋类应用以外的其它应用中所需要的和优选的压力范围可有较大变化并能够在具体应用领域中由技术人员来决定。蓄力器压力，例如，也许能够至多达1000psi。
优选，这里所描述的膜可用于形成鞋类的缓冲组件。在此类应用中，该膜优选能够较长时间地含有被包封住的气体。在非常优选的实施方案中，例如，该膜经过大约两年的时间应该不会丧失初始充气气压的约20％以上。换句话说，最初充气至20.0-22.0psi的稳态压力的产品应该在至少约两年的时间保持压力在大约16.0到18.0psi范围内。
该材料对于膨胀气体(它优选是氮气)的膨胀气体透过速率应该低于10立方厘米/米2/大气压/天(cc/m2.atm.天)，优选低于约3cc/m2.atm.天，和特别优选低于约2cc/m2.atm.天。
该微层聚合物复合材料为层离和开裂提供更多的阻碍。将阻隔层分成多个层将会增大各层对开裂的抵抗作用。尽管不想受理论的束缚，但据信若给定相同的外形尺寸和裂纹的恒定密度，具有较薄层的层压材料有可能在各层中含有较少的裂纹。因此，总体上与传统的层压材料含有同样量的阻隔材料、但阻隔材料分配在许多层之间而不是分配在传统层压材料的一层或几层中的该微层聚合物复合材料将在未开裂层中含有比传统层压材料更多的阻隔材料，如果在该材料承受负荷时从各裂纹形成裂缝的话。另外，如果在微层复合材料中的阻隔材料产生裂缝，沿着界面的耗散过程有助于将裂缝限制到一层。如果在一些阻隔层中产生裂缝，流体透过速率不应受到较大影响，因为相邻的阻隔层将强迫扩散物质走迂回通路来渗透该膜。
现有技术中已知的这些技术是挤出，吹塑，注塑，真空模塑，转移模塑，加压模塑，热封，浇铸，熔体流延和射频熔合等。
参见图1-3，显示了运动鞋，它包括鞋底结构和缓冲装置，后者作为从根据本发明教导的膜所形成的产品的一个例子。该鞋子10包括鞋子上层部分12，鞋底14与它相连。该鞋子上层部分12能够从各种常规材料形成，其中包括但不限于，皮革，乙烯基树脂，和尼龙及其它通常机织纤维材料。典型地，该鞋子上层部分12包括位于脚趾16周围的增强材料，鞋带束紧孔眼18，鞋子的顶部20和后跟区域22。与大多数运动鞋一样，该鞋底14一般在鞋子10的整个长度上从脚趾区域20延伸通过拱形区域24和回到脚后跟部分22。
鞋底结构14被显示包括一个或多个根据本发明的缓冲装置或气囊28，它们一般被设置在鞋底结构的中底之中。例如，本发明的膜28能够形成为具有各种几何形状的产品如多个管状部件，这些部件在中底26的脚后跟区域22内以相互间隔开、平行的关系设置，如图1-3中所说明的那样。管形部件被密封含有注射进去的被束缚气体。膜28的阻隔性能可通过图24中所示的微层聚合物复合材料30A的单层提供或通过如图4-5中所示的沿着热塑性弹性体外层32的内表面布置的微层聚合物复合材料层30提供。如图8-18中所说明，本发明的膜28，不论单层还是多层，能够形成具有许多构型或形状的产品。在这一点上应该认识到的是，制成在鞋类中使用的缓冲装置的膜28可以完全或部分包封在鞋类的中底或基底中。气囊因此作为鞋底的一部分被引入并可构成鞋子在鞋底上的外表面的至少一部分。
再次参见图1-3，根据本发明教导的膜28是作为缓冲装置的形式(如用作鞋类的组成部分的那些)来说明。根据图24中所说明的实例的膜28包括弹性材料的微层聚合物复合材料和包括一种或多种流体阻隔聚合物的第二材料的单层30A，优选该弹性材料包括一种或多种聚酯二醇型聚氨酯。
现在参见图6和7，其中说明了长管形多层组件形式的可供选择的膜实例A。改性膜A与图4和5中说明的膜28基本上相同，只是沿着层30的内表面连续提供第三层34，以使层30被夹在外层32和最内层34之间。最内层34也优选从热塑性聚氨酯材料制造。除了增强对层30的保护防止其降解的已知益处之外，层34也倾向于协助提供高质量的熔合，从而有利于产品如在鞋类中使用的缓冲装置形成三维形状。
膜如在图1-7和图24中示出的那些膜优选从挤出管状物制造。各种长度的管状物被连续挤出和典型地缠绕大约50英尺长，当被制造用于鞋类的可充气气囊时。管状物的截面被RF熔合或热封至所需长度。通过RF熔合或热封所生产的各个密封的可充气气囊然后通过在相邻气囊之间的熔合区域裁切开来分离。气囊然后能够充气至3psi(环境)到100psi的所需初始充气压力，优选在3到50psi范围内，其中被束缚的气体优选是氮气。也应指出的是，气囊能够从现有技术中已知的所谓扁平挤出管(flat extruded tubing)制造，其中内部几何形状被熔合到管中。
从这里所述膜形成的其它实例示于图8-10中。挤出的单层膜或共挤出的两层或三层膜的片材或膜材被制成所需厚度。例如，共挤出片材或膜材的厚度范围优选分别是在0.5密耳到10密耳(对于层30)之间和在4.5密耳到大约100密耳(对于层32和34)之间。对于单层缓冲装置实例，平均厚度通常是在5密耳到大约60密耳之间和更优选在大约15密耳和大约40密耳之间。
参见图12-16，示出了通过吹塑方法制成可充气气囊的膜。为了形成气囊，微层聚合物复合材料的单层型坯被挤出或两层或三层膜的型坯(一层是微层聚合物复合材料)被共挤出，如图21-23中所示。其后，该型坯使用普通的吹塑技术来吹塑和成形。所获得的气囊(它们的例子示于图12和15)然用所需被束缚气体膨胀至优选的初期充气压力，然后充气口(例如充气口38)通过射频熔合来密封。
从本发明的膜形成的再一实例示于图17和18中。通过形成具有所需厚度范围的挤出单层或共挤出多层管状物来制备气囊。管状物瘪成平折构型，通过使用普通的热封或RF熔合技术将相对的壁在所选择的点和在每一端熔合在一起。该缓冲装置然后用被束缚气体如氮气通过所形成的充气口38被膨胀至所需充气压力，后者是在5psi(环境)至100psi之间，和优选5-50psi。
除了如上所述使用本发明的膜作为缓冲装置或气囊之外，本发明膜的另一高度理想的应用是用于蓄力器，如图19，20和25中所述。
参见图25，示出了从以上所述单层膜形成的蓄力器实例。同样地，参见图19和20，示出了从本发明的多层膜形成的两种做为选择的蓄力器实例。蓄力器和特别是液压蓄力器可用于车辆悬架***，车辆制动***，工业液压蓄力器或用于在两种电势不同的流体介质之间有差压的其它应用。该膜124将液压蓄力器分成两个室或腔，其中一个含有气体如氮气和其中另一个含有液体。膜124包括环状颈圈126和柔韧性主体部分128。环状颈圈126经过调整后在圆周上与球型储能器的内表面相吻合，以使主体部分128将蓄力器分成两个单独的腔。柔韧性主体部分128一般在球型储能器内沿着直径方向运动，而且在任何给定时间，它的位置取决于在一侧上气体的压力以及在相对侧上液体的压力。
进一步举例，图20说明了呈现为包括本发明的微层聚合物复合材料的第一层114的液压蓄力器形式的一种产品。另外，该产品包括从一种或多种热塑性弹性体形成的层112和116。正如所示，第一层114仅仅沿着整个蓄力器主体部分的片段延伸。希望使用这样的实施方案，在这里被称作“非连续构造”，在这种情形下沿着产品的某些片段的层离潜力是最大的。一个这样的位置是在层压材料实例中沿着用于液压蓄力器的气囊或隔膜的环状颈圈126。因此，尽管本发明的层压膜一般来说更抗层离和在防止气体利用毛细管作用沿着层间的界面逃逸(如沿环状颈圈发生的那些)方面有更好的性能，但是应该认识到这里所述的膜110能够包括不含层114的片段。
这里所公开的膜能够通过各种加工技术来形成，其中包括但不限于挤出，型材挤出，注塑，和吹塑并通过管形和片形挤出膜材料的热封或RF熔合方法被密封形成可充气膨胀的气囊。优选，这些材料在大约300°F到大约465°F之间的温度和至少大约200psi的压力下相结合获得分别在层30、32和34的彼此接触部分之间最佳的润湿作用进而有最高粘合力而且增强了在所用材料容易形成氢键的各层之间的氢键结合。多层式层压膜是通过将微层聚合物复合材料形成层30与包括弹性材料的层32一起共挤出所形成的膜来制造。在形成多层式层压膜材料后，该膜材料通过RF熔合方法被热封或熔合形成回弹性可充气膨胀的气囊。
类似地，膜110(它随后被形成图19、20和25中所说明的产品)可进行共挤出得到在各层114与112和116之间显示上面所需要的氢键结合的产品。为了通过多层方法如吹塑方法形成诸如液压蓄力器气囊或隔膜的产品，许多在市场上可买到的吹塑机当中的任何一种如利用共挤出式机头型号No.BKB95-3B1(未示出)的Bekum BM502或利用型号No.VW60/35共挤出式机头(未示出)的Krup KEB-5型机器都能够使用。
该膜，不管呈现片形，基本上密闭的容器，缓冲装置，蓄力器或其它结构，优选具有大概至少约2500psi的拉伸强度，在约350-3000psi之间的100％拉伸模量，和/或至少大约250％到大约700％的伸长率。
强迫在挤出机中所形成的熔化聚合物通过衣架模头来形成片材。在吹塑中使用的瘪管和型坯可通过强迫由挤出机产生的熔化塑料通过环形模口来制备。
该微层聚合物复合材料能够用作多层式层压材料的一层。已知为片材共挤出技术的多层方法也是一种形成根据本发明教导的膜材的有用技术。片材共挤出一般涉及两种或更多种聚合物材料被同时挤出通过单个模头，在模头中这些材料被结合在一起以使它们形成了构成单一挤出产品的清晰、充分粘结的各层。
生产共挤塑片材所需要的设备是由一台用于每一种类型的树脂的挤出机组成，这些挤出机连接于如图21和23中所示的共挤塑供料头，它们能够从许多供应商(包括德克萨斯州Orange的Cloeren Company和威斯康辛州Eau Claire的Production Components，Inc.等)获得。
共挤塑供料头150由三区段组成。第一区段152是连接到各挤出机并将树脂的各圆形料流通过端口输入程序控制区段154的进料口区段。该程序控制区段154然后将树脂的各料流再成形为矩形，它的尺寸与各自所需层厚成正比。过渡区段156将独立的各矩形层相结合到一个方形端口中。TPU层的每一个的熔体温度应该一般是在约300°F到约465°F之间。为了优化各层之间的粘合作用，各熔体料流的实际温度应该使得各熔体料流的粘度非常匹配。结合的层式熔体料流然后在片材模头158中形成单个矩形挤出熔体，该模头优选具有如图22中所示的“衣架”设计，它目前用于塑料成形工业。之后，挤出物能够利用辊160冷却，通过铸塑或压延过程形成硬质片材。
与片材挤出类似，生产共挤出管所需要的设备由一台用于每一种类型的树脂的挤出机组成，每一挤出机连接于共同的多歧管式管形模头。来自各挤出机的熔体进入模头歧管如在图23中所说明的那一种(它可从许多供应商(包括乔治亚州亚特兰大市的CanterberryEngineering，Inc.和佛罗里达州Clearwater市的Genca Corporation)商购)中，和对于不同的熔体在独立的环流通道172A和172B中流动。流动通道然后成形为圆环形，它的尺寸与各层的所需厚度成正比。各熔体然后相结合，刚好在模头入口174之前形成一股共同的熔体料流。熔体然后流过由圆柱形芯轴180的外表面178和圆筒形模头壳体184的内表面182之间的圆环形成的通道176。管形挤出物离开模头壳体和然后通过许多普通管或管路校准方法被冷却成管的形状。尽管在图23中示出了两个组分的管，但所属领域的技术人员应该理解，通过单独的流动通道能够添加附加的层。
与所使用的塑料成形过程无关，希望获得所用各材料的一致性熔体，以便沿着层压产品的预定长度或片段在层间实现粘结。再一次，所用的多层方法应该在大约300°F到大约465°F的维持温度下进行。而且，在各层相结合以获得上述氢键结合时保持至少200psi的足够压力是重要的。
正如前面所指出的，除了对于本发明的层压膜实例所能够实现的优异结合以外，另一目的，尤其对于用作鞋类的缓冲装置的膜材，是提供一种膜材，它能够长时间保持住被束缚在其中的气体。一般而言，根据ASTM D-1434-82规定的程序对氮气测得可提供15.0或更低的气体透过速率的膜材是能够长时间使用的可接受的备选者。因此，尽管本发明的膜能够主要取决于最终产品的预定用途而具有不同厚度，但本发明的膜优选具有15.0或更低的气体透过速率，与膜的厚度无关。同样地，尽管氮气是许多实施方案的优选被束缚气体并用作基准物根据ASTM D-1434-82分析气体透过速率，该膜材可含有各种不同的气体和/或液体。
在优选的实施方案中，本发明的膜对于氮气具有10.0的气体透过速率和更优选具有7.5或更低的气体透过速率。更优选，本发明的膜对氮气具有5.0或更低的气体透过速率，进一步优选具有2.5或更低的气体透过速率。在大多数非常优选的实施方案中，本发明的膜对氮气具有2.0或更低的气体透过速率。
除了通过从这里所述的聚酯二醇型聚氨酯形成的各种产品所提供的改进耐气体透过性能外，从聚酯二醇型聚氨酯制得的产品也在耐久性上比不包括聚酯多元醇的热塑性聚氨酯有显著的改进。
在用氮气将缓冲装置充气膨胀至20.0psig之后，各样品间歇性地通过具有4.0英寸直径台板的往复活动式活塞进行压缩。各活塞的冲程经过校准后运动一定的高度，以使得在最大冲程下将各样品压缩至初始充气膨胀高度的平均25.0％。往复活塞然后进行周期循环或冲程运动，直至检测到部分破坏为止。这里所使用的术语“部分破坏”被定义为氮气的充分泄漏和缓冲装置的放气引起在相同位置沿着这些缓冲装置的每一个上放置的杠杆与停止该往复活塞冲程的微型开关接触。对于各样品记录周期循环或冲程的总数，高的冲程次数是更耐久材料的指标。优选，永久充气的缓冲装置应该能够承受对于用作鞋类组件的应用所考虑的至少约200,000个周期。除高度的耐久性之外，时常希望形成性质比较透明的产品，即满足针对所检测黄度指数和透过材料的光透射率来说的某些标准的产品。例如，产品的透明度常常是缓冲装置如用作其中缓冲装置可以看见的鞋类的组件的那些装置的考虑因素。从Pellethane 2355-85 ATP或Pellethane 2355-87AE形成的缓冲装置已被证明可用于鞋子组件，因为这些材料针对所检测的黄度指数和透过材料的光透射率来说已达到可接受的程度。
尽管对于鞋类和蓄力器的缓冲装置的非常有用的应用已经描述了本发明的气囊，应该认识到本发明的膜材具有宽范围的应用，其中包括但不限于可充气膨胀物体如足球、篮球，英式足球、内胎的气囊；柔韧性漂浮装备如管或椽子；作为医疗设备的组件如导管气球；作为家具如椅子和座位的一部分，作为自行车或鞍的一部分，作为防护设备(包括护胫和安全帽)的一部分；作为家具的支持元件和更尤其腰椎支持件；作为弥补术或整形外科装置的一部分；作为车辆轮胎的一部分，尤其轮胎的外层；和作为某些娱乐设备的一部分如同轴滑冰鞋或溜冰鞋的轮子的组件。
程序
微层层压材料通过下面的方法来制备。两台挤出机，一台用于聚氨酯弹性体和一个用于乙烯-乙烯醇共聚物，连接于供料头。来自挤出机的熔融聚合物被加入到供料头中，生产三层聚氨酯/EVOH/聚氨酯料流或五层聚氨酯/EVOH/聚氨酯/EVOH/聚氨酯料流。供料头的料流被连续加入到静态混合器中，生产具有聚氨酯和EVOH的微层的料流。该微层料流被加入到挤片模头中和然后到达三辊堆积机上。层压材料被冷却和纵切并在线卷绕。
实施例1
在上述程序中，Pellethane 2355 85ATP(具有肖氏A硬度为85、购自Dow Chemical Co.，Midland，MI的聚酯-聚氨酯共聚物)用作聚氨酯和LCF 101A(具有32％的购自Eval，Chicago，IL的乙烯-乙烯醇共聚物)用作EVOH，被加入到五料流式供料头中。来自供料头的料流被引入到具有七个元件的静态混合器中。所获得的微层聚合物复合材料具有15％(按重量计)的LCF101A和具有厚度为20密耳。图26是所生产的微层聚合物复合材料的截面的照片，使用光学显微镜按反射模式拍取。EVOH层使用碘溶液染色。该照片显示材料的至少28层。
测量微层聚合物复合材料的物理性能。
拉伸强度 6494psi
破坏伸长率 490％
拉伸模量 44,200psi
50％模量 1860psi
100％模量 2016psi
200％模量 2586psi
300％模量 3741psi
实施例2
根据实施例1生产微层聚合物复合材料，但是具有7.5％(按重量计)的LCF101A。测量微层聚合物复合材料的物理性能。
拉伸强度 7569psi
破坏伸长率 545％
拉伸模量 28,175psi
50％模量 1562psi
100％模量 1777psi
200％模量 2419psi
300％模量 3636psi
气体透过速率(对于氮气) 0
Claims (41)
1.一种弹性阻隔膜，它包括平均厚度至少50微米的微层聚合物复合材料，其中所述微层聚合物复合材料包括至少10个微层，每一微层各自至多100微米厚，所述微层在至少一种流体阻隔材料和至少一种弹性材料之间按规则重复顺序交替存在。
2.根据权利要求1的膜，其中所述膜包封膨胀气体以构成增压气囊。
3.根据权利要求2的膜，其中所述膜具有对于膨胀气体而言的氮气透过速率为10cc/m2·atm.天或更低。
4.根据权利要求1的膜，其中所述弹性材料包括从聚氨酯弹性体，柔韧性聚烯烃，苯乙烯系热塑性弹性体，聚酰胺弹性体，聚酰胺-醚弹性体，酯-醚弹性体，酯-酯弹性体，柔韧性离聚物，热塑性硫化橡胶，柔韧性聚氯乙烯均聚物和共聚物，柔韧性丙烯酸类聚合物，和它们的混合物中选择的一种。
5.根据权利要求1的膜，其中所述弹性材料包括聚氨酯弹性体。
6.根据权利要求1的膜，其中所述弹性材料包括从热塑性聚酯二醇型聚氨酯类，热塑性聚醚二醇型聚氨酯类，热塑性聚己内酯二醇型聚氨酯类，热塑性聚四氢呋喃二醇型聚氨酯类，热塑性聚碳酸酯二醇型聚氨酯类，和它们的混合物中选择的一种。
7.根据权利要求6的膜，其中弹性材料包括热塑性聚酯二醇型聚氨酯。
8.根据权利要求7的膜，其中所述聚氨酯的聚酯二醇是至少一种二羧酸和至少一种二醇的反应产物。
9.根据权利要求8的膜，其中二羧酸选自己二酸，戊二酸，琥珀酸，丙二酸，草酸，和它们的混合物。
10.根据权利要求8的膜，其中二醇选自乙二醇，二甘醇，三甘醇，四甘醇，丙二醇，二丙二醇，三丙二醇，四丙二醇，1，3-丙二醇，1，4-丁二醇，新戊二醇，1，5-戊二醇，1，6-己二醇，和它们的混合物。
11.根据权利要求8的膜，其中二羧酸包括己二酸和该二醇包括1，4-丁二醇。
12.根据权利要求7的膜，其中使用选自二醇和二胺的至少一种扩链剂化合物来聚合该聚氨酯。
13.根据权利要求12的膜，其中扩链剂选自乙二醇，二甘醇，三甘醇，四甘醇，丙二醇，二丙二醇，三丙二醇，四丙二醇，1，3-丙二醇，1，4-丁二醇，1，6-己二醇，和它们的混合物。
14.根据权利要求12的膜，其中聚酯二醇的当量与扩链剂的当量之比是1∶1到1∶8。
15.根据权利要求1的膜，其中流体阻隔材料包括从乙烯-乙烯醇共聚物，聚偏二氯乙烯，丙烯腈共聚物，聚对苯二甲酸乙二醇酯，聚酰胺，结晶聚合物，聚氨酯工程热塑性塑料，和它们的混合物中选择的一种。
16.根据权利要求1的膜，其中流体阻隔材料包括乙烯-乙烯醇共聚物。
17.根据权利要求16的膜，其中乙烯-乙烯醇共聚物具有乙烯共聚物比率为25mol％到50mol％。
18.根据权利要求16的膜，其中乙烯-乙烯醇共聚物具有乙烯共聚物比率为25mol％到40mol％。
19.根据权利要求1的膜，其中所述微层聚合物复合材料包括至少50个微层。
20.根据权利要求1的膜，其中所述微层聚合物复合材料包括30个微层到1000个微层。
21.根据权利要求1的膜，其中所述微层聚合物复合材料包括50个微层到500个微层。
22.根据权利要求1的膜，其中各流体阻隔材料微层的平均厚度独立地是至多2.5微米厚。
23.根据权利要求1的膜，其中各流体阻隔材料微层的平均厚度独立地是0.01微米至2.5微米厚。
24.根据权利要求1的膜，其中微层聚合物复合材料的平均厚度是125微米到0.5厘米。
25.根据权利要求1的膜，其中微层聚合物复合材料的平均厚度是125微米到0.1厘米。
26.根据权利要求1的膜，其中所述膜是一种层压材料，包括包含弹性聚氨酯的至少一层A和包含所述微层聚合物复合材料的至少一层B。
27.根据权利要求26的膜，其中所述层压材料包括层A-B-A。
28.根据权利要求26的膜，其中所述层压材料包括层A-B-A-B-A。
29.根据权利要求1的膜，其中在该微层聚合物复合材料上形成外保护性界面层。
30.根据权利要求26的膜，其中所述层压材料的平均厚度是至多0.5厘米。
31.根据权利要求26的膜，其中所述层B的平均厚度是6.35微米至2600微米。
32.根据权利要求2的膜，其中该膜具有氮气透过速率为低于10cc/m2·atm.天。
33.根据权利要求2的膜，其中该膜具有氮气透过速率为低于3cc/m2·atm.天。
34.根据权利要求2的膜，其中该膜具有氮气透过速率为低于2cc/m2·atm.天。
35.包括权利要求1的膜的缓冲装置。
36.根据权利要求2的膜，其中膨胀气体处在至少3psi的压力下。
37.根据权利要求2的膜，其中膨胀气体处在3至50psi的压力下。
38.根据权利要求2的膜，其中所述膨胀气体是氮气。
39.鞋子，包括至少一个根据权利要求36的增压气囊。
40.根据权利要求39的鞋子，其中所述气囊是作为所述鞋子的鞋底的一部分被引入。
41.根据权利要求39的鞋子，其中所述气囊构成所述鞋子的外表面的至少一部分。
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| CN1324222A CN1324222A (zh) | 2001-11-28 |
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| CNB998123544A Expired - Lifetime CN1210147C (zh) | 1998-09-11 | 1999-09-10 | 柔韧性膜 |
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| US (2) | US6582786B1 (zh) |
| EP (1) | EP1109468B1 (zh) |
| JP (1) | JP4597373B2 (zh) |
| KR (1) | KR100573611B1 (zh) |
| CN (1) | CN1210147C (zh) |
| AT (1) | ATE343939T1 (zh) |
| AU (1) | AU752631B2 (zh) |
| BR (1) | BR9914489A (zh) |
| CA (1) | CA2343816C (zh) |
| DE (1) | DE69933878T2 (zh) |
| HK (1) | HK1040595B (zh) |
| HU (1) | HUP0103729A2 (zh) |
| ID (1) | ID28637A (zh) |
| MX (1) | MXPA01002571A (zh) |
| NZ (1) | NZ510591A (zh) |
| PL (1) | PL190701B1 (zh) |
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| WO (1) | WO2000015067A1 (zh) |
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-
1999
- 1999-09-10 PL PL99346621A patent/PL190701B1/pl not_active IP Right Cessation
- 1999-09-10 ID ID20010815A patent/ID28637A/id unknown
- 1999-09-10 JP JP2000569660A patent/JP4597373B2/ja not_active Expired - Lifetime
- 1999-09-10 CN CNB998123544A patent/CN1210147C/zh not_active Expired - Lifetime
- 1999-09-10 NZ NZ51059199A patent/NZ510591A/xx not_active IP Right Cessation
- 1999-09-10 HU HU0103729A patent/HUP0103729A2/hu unknown
- 1999-09-10 MX MXPA01002571A patent/MXPA01002571A/es active IP Right Grant
- 1999-09-10 KR KR1020017003183A patent/KR100573611B1/ko not_active IP Right Cessation
- 1999-09-10 AU AU59182/99A patent/AU752631B2/en not_active Expired
- 1999-09-10 WO PCT/US1999/020819 patent/WO2000015067A1/en active IP Right Grant
- 1999-09-10 DE DE1999633878 patent/DE69933878T2/de not_active Expired - Lifetime
- 1999-09-10 BR BR9914489A patent/BR9914489A/pt not_active IP Right Cessation
- 1999-09-10 CA CA 2343816 patent/CA2343816C/en not_active Expired - Lifetime
- 1999-09-10 AT AT99946869T patent/ATE343939T1/de not_active IP Right Cessation
- 1999-09-10 US US09/786,831 patent/US6582786B1/en not_active Expired - Lifetime
- 1999-09-10 EP EP19990946869 patent/EP1109468B1/en not_active Expired - Lifetime
- 1999-12-10 TW TW88115766A patent/TW523463B/zh not_active IP Right Cessation
-
2002
- 2002-03-27 HK HK02102337.6A patent/HK1040595B/zh not_active IP Right Cessation
-
2003
- 2003-05-23 US US10/445,100 patent/US6846534B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| KR100573611B1 (ko) | 2006-04-26 |
| WO2000015067A1 (en) | 2000-03-23 |
| US6846534B2 (en) | 2005-01-25 |
| EP1109468B1 (en) | 2006-11-02 |
| AU5918299A (en) | 2000-04-03 |
| KR20010075056A (ko) | 2001-08-09 |
| DE69933878D1 (de) | 2006-12-14 |
| DE69933878T2 (de) | 2007-09-06 |
| HK1040595A1 (en) | 2002-06-21 |
| CN1324222A (zh) | 2001-11-28 |
| EP1109468A4 (en) | 2005-05-11 |
| AU752631B2 (en) | 2002-09-26 |
| NZ510591A (en) | 2003-03-28 |
| ID28637A (id) | 2001-06-21 |
| HUP0103729A2 (hu) | 2002-01-28 |
| HK1040595B (zh) | 2006-02-17 |
| BR9914489A (pt) | 2001-06-26 |
| US20040013834A1 (en) | 2004-01-22 |
| TW523463B (en) | 2003-03-11 |
| ATE343939T1 (de) | 2006-11-15 |
| CA2343816A1 (en) | 2000-03-23 |
| MXPA01002571A (es) | 2002-04-08 |
| PL190701B1 (pl) | 2005-12-30 |
| EP1109468A1 (en) | 2001-06-27 |
| CA2343816C (en) | 2009-04-14 |
| PL346621A1 (en) | 2002-02-25 |
| JP4597373B2 (ja) | 2010-12-15 |
| JP2002524317A (ja) | 2002-08-06 |
| US6582786B1 (en) | 2003-06-24 |
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