CN1108916C - 包括一层使用了聚酯多元醇的阻挡层的阻挡隔膜 - Google Patents

包括一层使用了聚酯多元醇的阻挡层的阻挡隔膜 Download PDF

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CN1108916C
CN1108916C CN00126086A CN00126086A CN1108916C CN 1108916 C CN1108916 C CN 1108916C CN 00126086 A CN00126086 A CN 00126086A CN 00126086 A CN00126086 A CN 00126086A CN 1108916 C CN1108916 C CN 1108916C
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barrier membrane
barrier
layer
thermo
plastic polyurethane
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CN00126086A
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CN1285269A (zh
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H·W·邦科
D·戈德瓦泽
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Siyuan Plastic Co Ltd
Nike International Ltd
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Siyuan Plastic Co Ltd
Nike International Ltd
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Abstract

本发明涉及一种包括一阻挡层的阻挡隔膜，该阻挡层包括由聚酯多元醇形成的一种或多种热塑性聚氨酯。特别是，隔膜包括一个含有由一种或多种聚酯多元醇型热塑性聚氨酯和一种或多种乙烯与乙烯醇的共聚物组成的掺合物的阻挡层。该阻挡隔膜有广泛应用且既可用作单层也可用作多层层压制品。

Description

包括一层使用了聚酯多元醇 的阻挡层的阻挡隔膜
本申请是1996年5月29日提交的申请号为96111033.3的发明名称为“包括一层使用了聚酯多元醇的阻挡层的阻挡隔膜”的分案申请。
本发明涉及一种阻挡隔膜，尤其涉及在某些实施中用来有选择地控制气体通过该隔膜扩散的阻挡隔膜。另外，在某些实施中，该隔膜不仅有选择地控制气体通过隔膜的扩散，而且还可以用来使正常容纳于大气中的气体有控制地扩散。
为了更进一步理解本发明的范围，可参见美国专利申请流水号No.08/299,287，1994年8月31日申请的名称为“带有改进的弹性阻挡隔膜的缓冲装置”美国专利申请流水号No 08/299,286，1994年8月31日申请的名称为“层压弹性可挠阻挡隔膜”；和美国专利申请流水号No 08/475276，与本申请同时申请共同所有并转让的名称为“具有一层使用了脂族热塑性聚氨酯的阻挡层的阻挡隔膜”。上述每一项专利申请都清楚地结合在此作为参考。
以受控的方式用于保存流体，包括液体和/或气体的十分有用的阻挡隔膜已经在广泛的不同制品中使用了许多年，其使用范围从对可充气物体，例如包括车辆轮胎和体育产品，十分有用的软外壳，直到用于重型机械的蓄压器以及在鞋袜制品中十分有用的缓冲装置。不考虑预期的用途，所需的阻挡隔膜通常必须具有弹性，抗环境引起的老化并能极佳控制对气体的传递。然而，经常地，表现出合格弹性的材料往往会具有不合格的低级的抗气体渗透性。相反，表现出合格的抗气体渗透性的材料往往会具有不合格的较差的弹性。
为了能同时考虑到弹性和抗气体渗透性，1991年6月30日授权的Moreaux的美国专利No 5036110中描述了适用于气水蓄压器的弹性隔膜。根据Moreaux′110，公开的隔膜包括由接枝聚合物形成的一层膜，该接枝聚合物是芳族热塑聚氨基甲酸乙酯和乙烯与乙烯醇的共聚物的反应产物，该膜位于两层热塑聚氨基甲酸乙酯之间以形成层压制品。当Moreaux′110试图产生对涉及弹性和抗气体渗透性的领域的关注时，Moreaux的一个明显缺点是所述的膜不能利用普通片材挤塑技术加工处理。这样，本发明目的在于具有弹性，良好的抗气体传递性，以及在某些实施  中可以利用具有很高的抗脱层性的普通片挤压技术加工成层压制品的阻挡隔膜。
可是在考虑下列说明书和权利要求书后对本领域普通技术人员来说应该理解本发明的阻挡薄膜具有广泛的应用范围，包括但不限于用于可充气物体如足球，蓝球，英式足球和内胎的软外壳；用于食品包裹的膜；以及燃料管线和燃料储存箱的生产，还可以列举出其它一些应用。例如，本发明的阻挡隔膜的一非常理想的应用包括用于形成工作在高压环境下的蓄压器，例如下面详细讨论的液力蓄压器。
为了方便，但并不限制，本发明的阻挡隔膜下面主要根据或者蓄压器或者另一理想应用即用于鞋袜制品的缓冲装置来加以描述。为了充分讨论关于鞋袜制品的缓冲装置的阻挡隔膜的实用性，相信很有必要总体上对鞋袜制品加以说明。
鞋袜制品，或者更精确地说，鞋一般包括两个主要部分即，鞋面和鞋底。鞋面主要作用是温暖舒适地包裹住脚。理想地，鞋面应由有吸引力地，高耐久性但舒适的材料或复合材料制成。也可由一种或多种耐久材料制成的鞋底主要设计用来在使用时拖拉与地摩擦，保护使用者的脚和身体，并与鞋的设计协调一致。在体育运动时产生的很大的力，要求运动鞋的鞋底对穿用者的脚、踝和腿，提供更强的保护与冲撞的吸收。例如，跑步时产生的冲击可产生多达人体重量的2-3倍的力。而其它一些运动例如打蓝球已经知道可以产生多达人体重量的约6-10倍的力。因此，许多鞋尤其是许多运动鞋现在采用了一些型式的弹性，冲撞吸收材料或者冲撞吸收组件在使用者进行紧张的体育运动时起缓冲作用。这种弹性，冲撞吸收材料或组件现在在制鞋行业中开始用作鞋底中层。
因此力图设计鞋底中层成为制鞋行业的焦点，这种鞋底中层设计可以获得包括恰当地考虑了充分的冲撞吸收和弹性的有效冲击反应。这种弹性，冲撞吸引材料或组件还可用在鞋垫部，该鞋垫部一般定义为直接在脚底面下的鞋上表面部分。
制鞋工业的特别焦点在于力图设计出适合容纳流体，或者呈液体状态或者呈气体状态或两种状态都有的鞋底中层或夹层结构来。在鞋底内使用的充气结构的实施例表示在1908年10月13日授权的Miller的美国专利No 900867，名称为“鞋袜制品缓冲器”；1913年7月29日授权的Guy的No 1069001，名称为“鞋的缓冲鞋底和鞋跟”；1919年5月27日授权的Spinney的No 1304915，名称为“充气鞋垫”；1924年11月4日授权的Schopf的No 1514468名称为“拱形缓冲器”；1937年5月18日授权的Gilbert的No2080469名称为“充气脚撑”；1953年7月21日授权的Towne的No 2645865名称为“鞋的缓冲鞋垫”；1954年5月11日授权的，Reed的No2677906，名称为“鞋的缓冲鞋垫及其制造方法”；1980年1月15日授权的Rudy的No 4183156名称为“鞋袜制品的鞋垫构造”；1980年9月2日授权的Rudy的No 4219945名称为“鞋袜制品”；1988年2月2日授权的Huang的Nos 4722131名称为“鞋底空气缓冲器”；和1989年9月12日授权的Horovitz的No 4864738名称为“鞋袜制品的鞋底构造”。本领域的普通技术人员会认识到，在制鞋工业中这种充气结构一般指“软外壳”，它通常分成两大种类，即(1)“永久”充气系统，例如在美国专利Nos 4183156和4219945中所公开的和(2)泵和阀调节系统，例如美国专利No.4722131中作了举例说明。作为另一个例子，在美国专利No 4182156中公开的包括“永久”充气软外壳型式的运动鞋以“Air Sole”商标和其它商标由俄勒冈州Reaverton市的耐克公司成功地销售。至今千百万双这种运动鞋已经售往整个美国和全世界。
永久充气软外壳一般通过使用弹性热塑材料并向其中充入大分子低溶解度系数的气体也就是行业中称之为“超级气体(Supergas)”例如SF6的方法来制得。作为一个实例，1982年7月20日授权的属于Rudy的美国专利No.4340626，名称为“扩散泵送装置自充气设备”，清楚地引入本申请中作为参考。它公开了膜的一对弹性可选择地渗透的片，该膜构成一软外壳，然后向该软外壳中充入一种气体或气体的混合物直至最好高于大气压的预定压力。利用的气体理想地具有较低的扩散率，它通过选择的可渗透软外壳扩散至外部环境中，而含于大气层中具有较高扩散率的气体例如氮，氧和氩能够渗透进软外壳内。通过将来自大气的氮、氧和氩的分压增加至最初注入软外壳内的保留气体的分压中，这使软外壳内的总压力提高。这种单向增加气体以扩大软外壳的总压力现在称为“扩散泵送”。
在扩散泵送系统中，在达到内部压力的稳定状态之前存在着一段时间，它由使用的软外壳材料和选择的容纳气体决定。例如，氧往往很快地扩散进入软外壳，效果是内部气压增加约2.5磅/平方英寸(17.225千帕，1磅/平方英寸＝6.89千帕，下同)。相反，在许多周的期间内，氮气逐渐地扩散至软外壳内结果使压力增至约12磅/平方英寸。软外壳压力逐渐增加通常引起软外壳壳壁的张力增加，由于拉伸导致体积增加。这种效果行业内一般称为“拉伸松驰”或“蠕变”。这样，选择用于软外壳的材料和选择用来首先充入软外壳内的封存空气混合物，以便得到在所需内部气压下基本上永久充气的和在期望的一段时间内保持所需的内部气压的软外层，是极其重要的。
就在推广AirsoleTM运动鞋之前和之后不久，在制鞋工业内部对于使用的这套系统，许多鞋底中层软外壳只包括单层气体阻挡型膜，所述膜由聚偏二氯乙烯为基础的材料例如Saran(Dow化学有限公司的注册商标)制成，就其本质而言是硬塑料，具有较差的挠曲疲劳，热封性和弹性。而且，通过例如层压和涂覆技术制成的包括一层或多层阻挡材料与弹性软外壳材料(例如不同的热塑塑料)结合的软外壳膜潜在存在着许多待解决的问题。复合结构的这些困难包括分层，剥离，在熔接界面气体扩散或毛细管作用，导致充气制品起皱褶的低度伸长，终饰软外壳显得模糊，较低的抗刺穿性和抗撕裂强度，抵抗通过吹塑法和/或热封和R-F熔接的成形，高生产成本，和具有泡沫包封和粘接困难等。
而前面公知的软外壳存在的另一问题是在准备层压制品时使用了粘接层或粘接剂。这些粘接层或粘接剂的应用通常可在制品回收成形为有用制品过程中，阻止任何废料重碎和回收，因此这样还带来制造成本提高和相对浪费。已有技术的这些和其它缺点在美国专利NOS 4340626；4936029和5042176中作了详细的描述。所有这些都清楚地也包括在这里作为参考。
随着一些制品例如Air SoleTM鞋的广泛商业成功，消费者已经可以喜欢具有较长使用寿命，较强冲撞吸收性和弹性，合理的花费，和充气稳定性，无需借助泵和阀的制品。这样，通过使用可长期使用的充气软外壳而取得显著的市场认可和成功，非常希望在涉及这些制品领域取得进步和发展。所以目标就是提供弹性的，“永久”充气的，充有气体的鞋缓冲组件，该缓冲组件可达到，且希望能超过由耐克公司提供的例如Air SoleTM运动鞋的制品所具有特性。
潜在进步的一个关键方面来自于认识到并非是在′156，′945和′738专利中所用的大分子，低溶解系数“超级空气”的封存空气可由低花费的和可能更有利于环境的气体所代替。例如，美国专利NOS 4936029和5,042,176特别提出一种生产弹性软外壳膜的方法，该弹性软外壳通过使用氮气作为封存空气基本上保持了永久充气。在美国专利NO.4906502中作了进一步的描述，也在这里提出以作参考。许多在′029和′176专利中提出的明显问题通过将具有机械阻挡层结晶材料加到弹性材料例如织物，丝，麻布和网中加以解决。使用了′502专利中所述的技术由耐克公司以商标TensileAirTM销售的鞋袜制品也已取得巨大的商业成功。其中使用的软外壳一般包括热塑性聚氨酯，该热塑性聚氨酯层压在芯织物为三维双杆Raschel编接尼龙织物上，SF6作为封存空气纳入软外壳内。
通过实施例，按ASTM D-1434-82规定的程序提出一种测量不同膜材料的相关的渗透，渗透率和扩散的可接受的方法。根据ASTMD-1434-82，渗透，渗透率和扩散按下述公式测算：
渗透
Figure C0012608600101
渗透率
Figure C0012608600102
扩散
通过利用上面列出的公式，气体传递率与压力差和膜厚结合可利用来定义气体在特殊条件下的运动。在这方面，在力图满足由于剧烈和反复的冲击而提出的抗疲劳性的严格要求的运动鞋构件中，软外壳的优选气体传递率(GTR)的值约为10.0或低于10，最好GTR值为2.0或更小，该软内壳的平均厚度约为508微米。
除上述之外，’029和’176专利还讨论一个前述企图使用用作氧阻挡层的塑料材料的，共层压混合物而遇到的问题。在这方面，主要关注的是阻挡层缺乏抗疲劳性。如’176专利所述，聚偏二氯乙烯(例如Saran)和聚氨酯高弹体的良好的共层压制品需要一中间粘合剂。在这种构造下，就需要相对复杂且昂贵的工艺控制例如严格的时间-温度关系和使用热压板和压力，并与在压力下冷压将材料凝结在一起相结合。另外，使用粘结剂粘接各层或以足够高的含量将晶体成分加入弹性膜中，以便气体传递率达到或小于10，并减少膜的弹性。
已经知道专门取消了粘接层的缓冲装置特别易于沿接缝和边分开或脱层。这样，发展不使用粘接层从而理想地减少或消除了脱层的发生的缓冲装置成为本行业的最新焦点。在这方面，在共同待审的美国专利申请NO 08/299286和08/299287中公开的缓冲装置通过提供一种隔膜取消了粘接层，该隔膜包括热塑性聚氨酯第一层和包括乙烯和乙烯醇的共聚物的第二层，这里氢键键接发生在隔膜的第一层和第二层之间的一节段。尽管美国专利申请NO.08/299287中公开的缓冲装置和美国专利申请No 08/299286中公开的层压弹性阻挡隔膜相信在本技术领域取得了显著的进展，根据本发明的教导又取得更进一步的进展。
因此，本发明的首要目的是提供具有提高了的弹性，耐久性和抗流体通过隔膜的不良传递的阻挡隔膜。
本发明的又一目的是提供阻挡隔膜，它基本上永久地充有氮气或其它环境适合的气体或混合气体，这里阻挡隔膜在平均厚度为508微米时的气体传递率为10或小于10。
本发明的再一目的是提供阻挡隔膜且特别是用作具有改进的渗透度和密度的缓冲装置的阻挡隔膜。
本发明的另一目的是提供能形成层压制品例如缓冲装置或蓄压器并且该层压制品能抗剥离，在阻挡层和弹性层之间不需粘接层的阻挡隔膜。
本发明的又一目的是提供可再加工的阻挡层。
本发明的另一目的是提供利用不同的技术包括但不限于如吹塑法，管塑法，片材挤塑法，真空成形法，热封法和RF熔接法来成形的阻挡隔膜。
本发明的再一目的是提供阻止气体沿层压实施例的各层界面逸出特别是沿接缝通过毛细管作用逸出的阻挡隔膜。
本发明的又一目的是提供便于实施普通鞋袜生产工艺例如在可成形材料内包胶的阻挡隔膜。
前述目的为本发明的阻挡隔膜的可能应用提供了指导，本领域的普通技术人员应认识到列举的目的并没有举尽或起限定作用。
为了达到上述目的，本发明提供阻挡隔膜，它具有(1)适合程度的弹性(或刚性)；(2)适合程度的抗潮湿引起的老化和(3)合格的抗液体渗透性，该液体主要依赖制品的设计用途确定呈气体，液体或二者兼有的形式；和(4)用在多层结构时高度抗剥离性。不考虑阻挡隔膜实施方案，根据本发明的教导的每个阻挡隔膜包括一阻挡层，该阻挡层至少部分包括由至少一由聚酯多元醇形成的聚氨酯和至少一乙烯与乙烯醇的共聚物组成的掺合物，所述聚酯多元醇由线性二羧酸和二醇的化合制成，这里二羧酸和二醇的化合物的碳原子总数为8或小于8。
使用的聚酯多元醇型聚氨酯，如果市场上见不到，一般可由下列的反应产物形成(a)一种或多种线性二羧酸与一种或多种二醇；(b)至少一种双官能增量剂(c)至少一种异氰酸酯和/或二异氰酸酯；和(d)可任选一种或多种加工助剂。
这里使用的名称“线性二羧酸”优选指与二醇反应时碳原子不超过6个的羧酸，这里二羧酸与二醇的反应产物的原子总数不超过8个。
这里使用的名称“二醇”希望优先指与线性二羧酸反应时具有不超过6个碳原子的聚酯二醇。这里二羧酸和二醇的反应产物具有不超过8个碳原子。
这里使用的名称“聚酯二醇”试图优先指具有分子量在约300至约4000的范围内，较好在从约400到约2000，而最好在约500至约1500之间的聚酯二醇。
这里使用的名称“热塑性”最好指在特性温度范围内能受热变软受冷变硬，且在软化状态时利用多种技术可形成多种制品的材料。
名称“双官能增量剂”对本领域的普通技术人员仅指普通常识上的意义，它包括二元醇，二胺，氨基醇等，它们的分子量一般在从约60至约300范围内。
理想地，根据本发明的教导使用的弹性阻挡材料应能在较长一段时间保留封存空气。在一优选实施例中，例如，阻挡隔膜在两年时间内不应损失初始充气压力的20％以上。换句话说，初始充气至20至22磅/平方英寸稳定状态压力的制品其压力应维持在约16至18磅/平方英寸范围内。
另外，使用的阻挡隔膜应有弹性，比较柔顺还应有高度的抗疲劳性和一般通过RF焊接或热封能够焊接形成有效的接缝。特别是当使用的阻挡隔膜厚度在5密耳至约50密耳时，阻挡材料还应能够承受周期性荷载而无破损。阻挡隔膜的另一个重要特性是采用大规模生产技术时应能加工成不同形状。本领域公知的技术有挤压法，吹塑法，注塑法，真空模塑法，旋转模塑法，压铸法和压力成形法。本发明的阻挡隔膜应最好通过挤压技术成形。例如通过管挤压或片挤压，特别在足够高的温度下包括挤压吹塑以达到下面将详细描述的适合的“粘接”或“化学”键接。这些前述生产工艺应生产出横截面尺寸可变化的制品来。
如前引述，本发明的阻挡隔膜的一个显著特征是，在形成打算充气的制品的实施例中(例如鞋袜的缓冲装置)，它具有控制游离气体通过隔膜进行扩散和保持封存气体留在隔膜内的能力。据本发明，由于阻挡层的性能不仅超级气体可用作封存空气，氮气也可用作封存空气。提供封存气体为氮气的阻挡隔膜对于保护地球臭氧层和防止地球变暖带来显著的实际效果。
在本发明中，如果阻挡隔膜形成制品例如缓冲装置，隔膜可首先充入氮气或氮气与一或多种超级气体的混合气体或充入空气。如果充入氮气或氮气与一或多种超级气体的混合气体，压力增量的增大来自于氧气较快速度扩散进入隔膜内，因为封存气体基本上保留在隔膜内。这实际上等于在初始充气压力基础上增加不超过2.5磅/平方英寸的压力并产生隔膜体积在1至5％之间适度地增加，增加值依赖于初始压力。然而，如果空气用作封存气体，氧气倾向于从隔膜扩散出来，而氮气留下作为封存气体。在这种情况下，氧气从隔膜向外扩散和封存空气的滞留导致在初始充气压力基础上稳定状态压力的增量减少。
本发明的另一个特征是增强在相邻层间产生的键接，这样取消了粘接层。这一般通过使用普通技术将第一和第二层层压在一起来实现，这样，本发明的层压阻挡隔膜其特征在于在第一层和热塑性聚氨酯第二层之间产生显著的氢键键接，所述第一层由至少一脂族聚酯多元醇型聚氨酯和乙烯与乙烯醇的共聚物组成的掺合物形成。除了产生氢键键接以外，特别当较少量的乙烯与乙烯醇共聚物用于第一层且第一和第二层的热塑性聚氨酯具有相同的官能度时，理论上在第一和第二层之间一般有一定数量的共价键。
本发明的另一特征是应用至少一聚酯多元醇型聚氨酯和乙烯及乙烯醇的共聚物组成的掺合物的单层阻挡隔膜具有极佳的气体传递率。
考虑到本发明的多种形式和实施方案，本发明还具有许多其它更明显的优点。而且，附图中的实施方案仅仅是利用本发明的阻挡隔膜的实施方案的说明，应明白该阻挡隔膜具有更广泛用途的可能性，为了图解本发明一般原理下面将详述许多范例，而不应考虑其为限定意义上的描述。
图1是根据本发明的运动鞋的侧视图，其中部分鞋底中层切开露出横截面；
图2是图1的运动鞋的底面的仰视图，其中部分切开露出另一横截面；
图3是沿图1 3-3线的截面图；
图4是根据本发明的管状两层缓冲装置的一实施方案的局部侧透视图；
图5是图4的沿4-4线的截面图；
图6是根据本发明的管状三层缓冲装置的第二个实施方案的局部侧透视图；
图7是图6的沿6-6线的截面图；
图8是根据本发明的另选隔膜实施方案的透视图
图9是图8所示隔膜的侧视图；
图10是根据本发明的一另选膜的实施方案的透视图；
图11是具有据本发明的一另选隔膜实施方案的运动鞋的侧视图；
图12是图11的隔膜的透视图；
图13是图11和12的隔膜的俯视图；
图14是具有据本发明的另一另选隔膜实施方案的运动鞋的侧视图；
图15是图14的隔膜的透视图；
图16是图14和15的隔膜的俯视图；
图17是据本发明宗旨的一另选隔膜实施方案的透视图；
图18是图17的隔膜的侧视图；
图19是据本发明的宗旨由层压隔膜形成的制品的透视图；
图20是据本发明的宗旨由层压隔膜形成的又一制品的透视图；
图21是片材共挤塑装置的侧视图；
图22是图21中片材共挤出装置的集流腔部分的横截面图；且
图23是管材共挤塑装置和侧视图。
参见图1-5，表示的是运动鞋，包括鞋底结构和缓冲装置，这是根据本发明的宗旨应用阻挡隔膜的实施例。鞋10包括与鞋底14连接的鞋面12。鞋面12由多种普通材料包括但不限于如皮革，乙烯树脂，尼龙和其它普通纺织纤维材料形成。一般，鞋面12在位于绕鞋趾尖部16，系带孔部18，鞋顶峰部20和沿鞋跟区22设有加强层。如同大多数运动鞋，鞋底14通常从鞋趾尖部16通过弓形区24向后直至鞋跟区22如此在鞋10的整个长度上伸展。
鞋底结构14根据本发明可包括一或多个可选择性渗透的阻挡隔膜28，该阻挡隔膜最好布置在鞋底结构的中层呈H形。根据实施例，本发明的阻挡隔膜28形成可具有不同几何形状例如许多相互隔开布置，在鞋底中层26的鞋跟区22内互相平行的管件，图1-5中已表示。管件经密封以容纳注入的封存空气。特别是，形成的每一个阻挡隔膜28包括一阻挡层，该阻挡层允许游离气体通过而扩散，但抵制或防止封存空气扩散。隔膜28的这些预定的扩散特性是由内部阻挡层30提供，该内部阻挡层位于沿热塑外层32的内表面。这两层隔膜最好参见图4和5。如前所述，本发明的阻挡隔膜28可形成不同的轮廓或形状。例如，另选的隔膜28B可形成如图8和9所示的鞋跟座垫形状。图8和9表示的带有鞋跟座垫的运动鞋已经由俄勒岗州贝灵顿(Beaverton)市的耐克公司以商标Air HealthWalker PlusTM在商业上使用并销售。图8和9中的鞋跟座垫外形已记录在美国外观设计专利申请NO 007934中，它于1933年4月20日申请。类似的，具有基本上与图10表示的隔膜实施例28C相同的形状的鞋跟座垫已经由耐克公司以商标Airstructure IITM使用在运动鞋中并销售。图10的鞋跟座垫外形已记录在1994年1月25日授权的美国外观设计专利NO 343504中。通过另外的实施例，如图11-13所示的另选隔膜28D也由耐克公司所有并以商标Air Max2TM和Air Max2CBTM使用在运动鞋中并销售，根据本发明的宗旨亦可形成该隔膜。该隔膜外形还记录在1994年8月23日授权的美国外观设计专利NO 349804以及1994年8月30日授权的美国外观设计专利NO 350016中。而另一可选隔膜28E表示在图14-16中。隔膜28E由耐克公司以商标AirMaxTM通常使用在运动鞋中并销售。该隔膜外形记录在1992年6月12日申请的美国外观设计专利申请NO 897966中。还有其它由标号28F指定的隔膜外形表示在图17和18中。应该明白这一点，本发明的阻挡隔膜外形(无论管形，细长垫形或其它类似形状)，可全部或者部分包封在鞋类物品的鞋底中层或鞋底的靠外层内。
再参见图1-5，根据本发明宗旨所提供的阻挡隔膜28的形式为缓冲装置，如图示，隔膜28具有复合结构，它包括由受到气体压力时能够抵制隔膜膨胀超过预定的最大体积的易弯弹性材料制成的外层32，还包括由便于受控扩散泵送或自增压的阻挡材料制成的内层30。
外层32最好由能提供强热密封性，抗挠疲劳强度，适合的弹性模量，抗拉和抗撕裂强度以及耐磨强度的材料或材料组合而形成。在具有这些性质的现有材料中发现聚氨酯种类的热塑高弹性，在这里指热塑性聚氨酯或者简单地为TPUs为最佳材料，这是因为它们的良好加工性的缘故。
在用于形成外层32的大量热塑性聚氨酯中，聚氨酯例如PELLETHANETM 2355-85ATP和2355-95AE(Midland，Michigan的Dow化学公司的商标产品)、ELASTOLLAN(BASF公司的注册商标)和ESTANE(B.F.Goodrich公司的注册商标)。所有上述产品中或者是基于酯或者是基于醚的，均被证明十分有效。其它聚酯，聚醚，聚己内酯，聚氧化丙烯和聚碳酸酯多聚二元醇型热塑性聚氨酯可以使用。通常，用于形成外层32的热塑性聚氨酯本质上是芳香族化合物。
内层30是主要担负控制空气渗透的主要阻挡部分，它由一种或多种热塑性聚氨酯的掺合物或组合物制成，所述热塑性聚氨酯由聚酯多元醇和一种或多种乙烯及乙烯醇的共聚物制成。用于内阻挡层的聚酯多元醇型热塑性聚氨酯，如果在市场上见不到，一般可通过下列之中至少其一的反应产物而制得：(a)聚酯多元醇；(b)双官能增量剂，(c)异氰酸酯和/或二异氰酸酯；以及(d)任选的加工助剂。如前所述，理想地，形成的聚酯多元醇为线型二羧酸与二元醇的反应产物，这里二羧酸与二元醇的反应产物的碳原子的总数小于或等于八。在最佳实施方案中，用在形成了层压隔膜的阻挡层内中使用的聚酯多元醇本质上是脂族的。
在形成本发明的聚酯多元醇型聚氨酯时被认为十分有用的线型二羧酸中，例如己二酸，戊二酸，丁二酸，丙二酸和乙二酸特别有用。
在根据本发明形成聚酯多元醇型聚氨酯时被认为十分有用的二元醇中，象1，2-乙二醇，丙二醇，丁二醇，戊二醇和己二醇被认为特别有用。
在最佳实施例中，根据本发明的宗旨，用在既可应用单层亦可应用多层层压形成阻挡层时聚酯多元醇型热塑性聚氨酯包括己二酸乙二醇酯。在这方面，某些市场上见得到的己二酸乙二醇酯例如从Witco Chemical获得的FOMREZ22-112和22-225被认为十分有用。
根据本发明的宗旨应用的双官能增量剂一般择自一增量剂集合，它包括1，2-乙二醇，1，3-丙二醇，1，2-丙二醇，1，4-丁二醇，1，2-己二醇，新戊二醇等以及二羟烷基化芳族化合物例如对苯二酚的双(2-羟乙基)醚；间苯二酚的双(2-羟乙基)醚；α-α′对苯二甲醇；α，α′-对苯二甲醇的双(2-羟乙基)醚；α-α′-间苯二甲醇及其双(2-羟乙基)醚。代表二胺增量剂的是芳香二胺例如对苯二胺，间苯二胺，联苯胺，4，4′-亚甲基二苯氨，4，4′-亚甲基双(2-氯苯胺)等。代表氨基醇的是乙醇胺，丙醇胺，丁醇胺等。
优选的增量剂包括1，2-乙二醇，1，3-丙二醇，1，4-丁二醇，1，2-己二醇等
一般地，聚酯多元醇(即己二酸乙二醇酯)与增量剂的比值主要依赖于最终聚氨酯高弹体的所需硬度而可在较大范围内变化。因此，聚酯多元醇与增量剂的当量比例应在1∶1至1∶12的范围内，尤其应在从1∶1至1∶8范围内。
在根据本发明宗旨使用的异氰酸酯特别是二异氰酸酯中，其中异佛尔酮二异氰酸酯(IPDI)，亚甲基双4-环己基异氰酸酯，环己基二异氰酸酯(CHDI)，六亚甲基二异氰酸酯(HDI)，四甲基间-二甲苯二异氰酸酯(m-TMXDI)，四甲基对-二甲苯二异氰酸酯(p-TMXDI)以及亚二甲苯二异氰酸酯(XDI)被认为十分有用，特别有用的是亚甲基双苯基异氰酸酯。一般地，使用的异氰酸酯定量配料以便异氰酸酯的当量与含活性氢材料的当量的整体比在0.95∶1至1.10∶1的范围内，最好在0.98∶1至1.04∶1的范围内。
掺合阻挡层30一般包括重量百分比至多50％的聚酯多元醇型热塑性聚氨酯，但最好包括重量百分比在约1％至约30％之间的聚酯多元醇型热塑性聚氨酯。在优选实施例中，构成阻挡层30的聚酯多元醇型热塑性聚氨酯的重量百分比在约5％至约25％之间。
在用于形成阻挡层30的掺合物里使用的乙烯和乙烯醇的共聚物中，其中在市场上见得着的产品例如可从纽约的NipponGohsei有限公司获得的SOARNOLTM，以及从Eval Compang ofAmerica，Lisle，Illinois获得的EVAL证明十分有用。最佳的市场可见的乙烯和乙烯醇的共聚物例如EVALLCF101A一般地其平均乙烯摩尔百分含量在约25％至约48％之间。一般地，乙烯含量越高结果热塑性聚氨酯和乙烯-乙烯醇共聚物的各层间的粘着为越强。
关于使用所谓的加工助剂，使用了少量现有技术中的抗氧化剂，紫外稳定剂，脱模剂和不粘剂，这里这种加工助剂的总构成的重量百分比含量一般小于3％。
为制备本发明的组合物，在反应混合物中希望还能包括催化剂。任何一种在本技术领域中常规使用以促使异氰酸酯与含活性氢的化合物发生反应的催化剂可用于此目的。例如参见，Saunder等，Po1yurethanes，Chemistry and Technology，第一部分，InterScience，纽约，1963，第228-232页；还可参见，Britain等，J.Applied Polymer Science，4，207-211，1960。这些催化剂包括铋，铅，锡，铁，锑，铀，镉，钴，钍，铝，汞，锌，镍，铈，钼，钒，铜，锰，锆的无机和有机酸盐和其有机金属衍生物，以及磷化氢和有机叔胺。典型的有机锡催化剂有辛酸亚锡，油酸亚锡，二辛酸二丁锡，二月桂酸二丁锡等。典型的有机叔胺催化剂有三乙胺，三亚乙基二胺，N，N，N′，N′-四甲基乙二胺，N，N，N′，N′-四乙基乙二胺，N-甲基吗啉，N-乙基吗啉，N，N，N′，N′-四甲基胍和N，N，N′，N′-四甲基-1，3-丁二胺。
无论使用催化剂与否，如果使用，这种材料的重量百分比占聚酯多元醇型热塑性聚氨酯反应混合物的总重量的不到0.5％。
对于某些实施例，在掺合阻挡层30中包括少量的至少一种芳族热塑性聚氨酯作为粘度调节剂还是很有用的。在那些使用至少一种芳族热塑性聚氨酯的例中，其总量的重量百分比一般在3％或更低，基于阻挡层成分的100％。这样，掺合阻挡层的组合物可概括为包括：(1)乙烯和乙烯醇的至少一种共聚物其重量百分比占50％至约97％(2)至少一种脂族热塑性聚氨酯其重量百分比占3％至约50％，且(3)重量百分比占至多约3％的一种或多种芳族热塑性聚氨酯，这里阻挡层的全体组分总重量等于百分之百。芳族热塑性聚氨酯还可择自包括聚酯，聚醚，聚己内酯，聚氧化丙烯和聚碳酸酯多聚二元醇型材料及其混合物的集合中。
如前所述，这里公开的阻挡隔膜可通过不同的加工技术形成，包括但不仅限于挤压法，吹塑法，注塑法，真空模塑法和管及板挤出膜材料的热封或RF熔接。优选地，下面全面地加以描述，本发明的隔膜是通过外层的热塑性聚氨酯材料与内层的聚酯多元醇型热塑性聚氨酯和乙烯及乙烯醇的共聚物的掺合物一起共挤形成的膜制得以便有效地制造多层膜材料，最终阻挡隔膜即由此材料制成。接着，在制得多层膜材料后，膜材料经热封或通过RF熔接以形成具有高弹性和扩散泵送能力的可充气阻挡隔膜。
参见图6和7，图中表示了多层成分的细长管形的另选阻挡隔膜实施方案28A。除了邻接并沿阻挡层30的内层表面设置有第三层34不同外，变型的阻挡隔膜28A基本上与图1-5所示的组成结构相同，使得阻挡层30夹在外层32与最内层34之间。最内层34优选由热塑性聚氨酯材料制成，以加大保护防止阻挡层30由于潮湿而引起水解。除了有助于增强保护以防阻挡层30老化外，层34还有助于提供使缓冲装置产生三维形状的高质量熔接。
图1-7所示的缓冲装置最好由多层挤出管制造。共挤出管长度范围在一英尺到至多五英尺的盘绕，共挤管充气至所需初始充气压力，范围在0磅/平方英寸至100磅/平方英寸，优选范围在5至50磅/平方英寸，此时封存空气最好为氮。节段管通过RF焊接或热封至所需长度。制造的单独缓冲装置通过在相邻缓冲装置间的熔接区切断而分开。还应注意到缓冲装置还可通过公知的所谓的挤出吹塑制管法来制得，这样内部形状熔接入管中。
由于掺合的包括一种或多种聚酯多元醇型聚氨酯和一种或多种乙烯和乙烯醇的共聚物的第一层和包括热塑性聚氨酯的第二层通过单独的流道流向挤压机的出口端，一旦它们靠近挤压机机头口，熔化物流经混合并一般都分层漂浮，当它们进入模型体内时形成层流流动。理想地这些材料在温度华氏300度至约450度之间(148.9至约223.3℃，℃＝5/9(°F-32)，下同)压力至少约200磅/平方英寸时结合以达到最佳湿润以便各层30，32和34的邻接部分间粘接最牢。而且，对于多层层压件，形成阻挡层时使用的聚酯多元醇最好本质上是脂族的，因为发现脂族聚氨酯利用普通片材挤压技术即可很容易地加工。
参见图6和7对此进行详细的说明，根据图6和7，隔膜28A包括三层，第一层的阻挡材料30夹在第二层32和第三层34之间，第二层和第三层为热塑性聚氨酯。
在最佳实施例中，两层热塑性聚氨酯层和掺合阻挡层在一温度下共挤，该温度引起至少沿阻挡隔膜的一预定段产生氢键键接形式的接触反应，这样便不需要中间的粘合层或结合层。
为此目的，认为极强的键接是由于以下原因产生的，即有效氢分子通过沿层压隔膜的长度方向的乙烯-乙烯醇的共聚物的乙烯醇基和羟基和聚氨酯羧基或者仅仅是聚氨酯的有效极性基团来供给的。
当为了粘接而根据本发明方法相接触时，本发明的优选组成和方法唯一地依赖于下述物质的固有特性，即第二和第三层的热塑性聚氨酯和包括聚酯多元醇型热塑性聚氨酯及一种或多种乙烯与乙烯醇的共聚物的掺合阻挡层。
在基本横贯隔膜28A的整个预期的接触表面区域内产生的层32和34与层30之间的表面键接的理论上的化学反应可概括为下式：
Figure C0012608600251
这里R是
且R′是短链二元醇例如(CH2)4
除了前述理论上的氢键键合外，在一更有限的范围内，认为在第二和第三层32和34之间分别与第一阻挡层30形成一定量的共价键。而且其它因素也会对热塑性聚氨酯和主阻挡层的相邻层之间的键能产生影响，该因素例如是取向力和诱导力，换句话说是公知的范德华力，它们是由存在于任何两个分子之间的色散力和存在于极性分子间的偶极-偶极力产生的。
本发明的热塑性聚氨酯层和阻挡层之间的氢键键合与已有技术实施方案相反，在已有技术中一般使用结合层粘结剂例如Bynel来提高和保持热塑性聚氨酯和乙烯乙烯醇的不同层间的粘合，而没有认识到上述键合的存在和/或潜在。
还应该注意到填料例如无极性聚合物材料和无机填料或增量剂例如滑石，硅石，云母等也有对热塑性聚氨酯和掺合层的键接产生负面影响的趋势，所述掺合层包括一聚酯多元醇型聚氨酯和至少一乙烯和乙烯醇的共聚物。这样，在加工层30，32和34时，如果使用，填料的使用必须受到严格的限制。
参见图12-16，图中表示了通过吹塑法制作的气囊形式的阻挡隔膜，这里也称其为缓冲装置。为形成气囊，如图21-23所示首先共挤出两层型胚，或者优选三层膜，然后，通过采用普通吹塑技术吹制形成胚，接着在图12和15中最佳表示的制成的气囊充入所需封存空气至优选初始充气压力并且通过RF熔接将充气口(如充气口38)密封。
图8-10表示由阻挡隔膜形成的另一气囊实施方案。两层共挤片或膜，或者优选三层膜首先成形，共挤片或膜的厚度范围对于阻挡层30一般在12.7至254微米，对于热塑性聚氨酯层32和34一般在127至2540微米。两片多层膜相互叠层并沿择定位置使用普通热封技术或RF熔接技术熔接在一起。未充气的气囊通过一成形充气口充气至所需初始充气压力，该充气压力范围从0磅/平方英寸至100磅/平方英寸，优选从5至50磅/平方英寸。如前所述，优选封存空气为氮。
图17和18又表示另一由本发明的阻挡隔膜形成的气囊实施方案。该气囊是通过形成共挤的两层和三层制管技术制得，横切各层得到的所述共挤管的管壁的厚度范围对于阻挡层30在12.7至254微米之间对于热塑性聚氨酯层32和34在127至2540微米之间，该管压至平置形状并在选定部位和在每一管端使用普通热接技术或RF焊接将相对的管壁焊接在一起。然后通过成形的充气口38给气囊充气至所需充气压力，该压力范围从0磅/平方英寸左右至100磅/平方英寸，优选从5至50磅/平方英寸，优选封存空气为氮。
图中描述和图示的不同产品设计用作鞋袜制品尤其是运动鞋的底中部。在本申请中，可充气的隔膜可用在下列任一不同的实施方案中(1)完全包封在合适的鞋底中层泡沫材料中，(2)只包封在单元的顶部以填充和整平不平坦的表面从而增添脚下的舒适度，(3)包封在底部有助于与鞋底外部的连接，(4)包封在顶和底部但由于美学和市场的原因需暴露周边，(5)包封在顶部和底部但仅暴露单元侧面选定部分，(6)通过一模制“鞋床”包封在顶部，且(7)与任何泡沫材料使用，不包封。
如上所述，除了本发明的阻挡隔膜用作缓冲垫或气囊外，本发明的阻挡隔膜的另一个极需的应用是用在如图19和20所示的蓄压器。
参见图19和20，表示了由本发明的阻挡隔膜材料形成的两个可选蓄压器实施方案。根据图19，表示了液力蓄压器形式的软外壳，该软外壳用在车辆悬挂系统，车辆制动系统，工业液力蓄压器或在两种可能不同的液体介质间具有不同压力的任何蓄压器。软外壳124将液力蓄压器分成两个室或隔间，其中一个充有空气例如氮，而另一个装有液体。软外壳124包括一环形颈圈126和一弹性间壁128。环形颈圈126适合周边固定在球形蓄压器的内表面上以便间壁128将蓄压器分成两个单独的腔。弹性间隔128在球形蓄压器内一般在直径方向上移动且在任何给定时间其位置由一侧的气体压力以及相对的一侧的液体压力来决定。
根据又一个例子，图20表示使用阻挡隔膜110的结合制成的产品，该阻挡隔膜包括一种或多种聚酯多元醇形成的热塑性聚氨酯和一种或多种乙烯和乙烯醇的共聚物经组合或掺合得到的组合物或掺合物而形成的阻挡层114和热塑性聚氨酯制成的外层116。在沿制品某些节段的层离趋势普遍较高的情况下希望可以利用这些所谓的间断构造。一种这样的布置就是沿用于液力蓄压器的软外壳或隔膜的环形颈圈128。这样，应该认识到这里描述的阻挡隔膜110可以包括那些不包括一层或多层乙烯乙烯醇共聚物的节段。
最好，在努力使两层间产生交联或普通共价键接的过程中，使用的聚酯多元醇型热塑性聚氨酯和乙烯乙烯醇共聚物不要改性，任何粘接层或使用的粘合剂也不要改性。当根据本发明的方法导致接触反应时，本发明的优选组成和方法唯一依赖于聚酯多元醇型热塑性聚氨酯和乙烯及乙烯醇的共聚物的固有特性，即极大化和从根本上依靠各层间存在的氢键键接。
根据本发明的宗旨成形的阻挡隔膜110，可以使用许多不同的工艺，包括但不限于如使用连续压挤的共挤吹塑法，利用了(1)往复式螺杆输送系统(2)活塞型蓄压器系统(3)及蓄压器压头系统的间歇挤出法，共注延展吹塑，或共挤片、吹膜、管或多种外形。已经发现多层生产工艺例如管、片、膜挤塑、采用共挤出的吹塑生产的产品似乎证实了在各热塑性聚氨酯层和包括聚酯多元醇型热塑性聚氨酯与乙烯和乙烯醇的共聚物的掺合物的层之间具有显著的氢键键接。
例如，根据本发明的宗旨为了通过多层生产工艺生产如液力蓄压器软外壳或隔膜的制品，例如吹塑制品，一般采用许多市场上见得到的吹塑机如型号为NO BKB95-3B1(未示出)的共挤头的BekumBM502或使用型号为No VW60/35共挤头(未示出)的Krup KEB-5中任一种按照下列步骤进行生产。
现在主要介绍多层生产工艺技术。首先，包括热塑性聚氨酯的树脂材料和阻挡材料先按照生产厂技术规范进行干燥(如果需要)并送入挤压机内，所述阻挡材料包括至少一种优选是脂肪族的聚酯多元醇型热塑性聚氨酯和至少一种乙烯与乙烯醇的共聚物的掺合物。一般，材料是根据各层已布置好的顺序送入挤压机，例如TPU在挤压机外侧，聚酯多元醇型TPU和EVOH的掺合物在挤压机中部，而TPU在挤压机内侧。挤压机经调节热分布用来最佳处理单独的材料。然而，建议在每个挤出机的出口位置温度差不超过20华氏度。当材料向前压送入每个挤压机时，调节热分布以获得最佳熔融物质。热分布一般在华氏温度从300至约450度之间调节，进料区为最低设置点且所有其它设置点以华氏10度的增量逐渐增加直到获得所需熔化物。一旦离开挤压机，有时候用一段管来将该材料导向条层压头(即三层或多层压头)。在这一点进行任何差别的调整。挤压机的泵送作用不仅迫使材料进入单独的压头通道或流路而且决定了每层的厚度，举个例子，如果第一挤压机直径为60mm，第二挤压机为35毫米直径，第三挤压机的直径为35毫米，如果要求在预定的26秒的周期时间内制造1.3升软外壳或隔膜，要求外层TPU厚2毫米、阻挡层厚76.2微米且内层TPU厚2毫米时的速度，那么第一挤压机其螺杆旋转速度为10转/分，第二挤压机速度约为5转/分，对于第三挤压机速度约为30转/分。一旦进入压头通道或流路，热度一般保持恒定或减少以调整材料的熔融强度。单独的压头通道或流路在将熔融物向下导入型胚模型内时使该熔融物间保持隔离。
就在进入下部模具或衬套与下部型芯之前，材料压头通道或流路通过现在的整体流道表面区域产生的压力，在下部衬套和型芯之间的缝隙和由各挤压机作用在单元层上的压力而汇集在一起。这个压力必须至少200磅/平方英寸且一般在所述条件下可超过800磅/平方英寸。在材料汇集在一起的位置，形成一型胚，该型胚为包括一层热塑性聚氨酯的三层组成的层压制件，第一层包括至少一聚酯多元醇型热塑性聚氨酯和至少一种乙烯和乙烯醇的共聚物组成的掺合物，而第二和第三热塑性聚氨酯层位于沿第一层相对的两侧。压力的上限基本上只受压头的物理强度所限。在离开压头后，层压制品由两半模在每一端密封，气体例如空气注入模内使得层压型胚吹胀顶住模，并保持这个样子直到发生充分冷却(即对于前述实样约16秒)，这时排出气体。然后将部件从模中移出，并进一步冷却一段充足的时间以便部件修边或者当一些部件需要时可以进一步处理。对于普通技术人员现在应理解到各层必须保持分隔直至完全熔融并预制成形一中空管，此时它们在这里描述的热度和压力下靠所述的化学键接。
那些精通制塑工业的人应认识到，吹塑成型机的三个主要部件，即挤压机，模头和夹具，具有许多不同尺寸和配置以适应用户生产率计划和尺寸的要求。
公知的片材挤塑多层生产工艺包括通过一单独模具同时挤压两种或多种聚合物的挤压技术，这里聚合物连接在一起以便形成具有不同的，良好键接层的单挤出制品，根据本发明，典型层结构如下定义：A-B
包括两种树脂的两层不同层。A-B-A
包括两种或三种树脂的三层不同层。A-B-A-B-A
包括二，三，四或五种树脂的五层不同层。
其中A为一层热塑性聚氨酯，而B为由一种树脂形成的至少一层，该树脂包括由至少一聚酯多元醇型热塑性聚氨酯和至少一乙烯与乙烯醇的共聚物组成的掺合物。
制作共挤片所需的设备包括用于每种型式树脂的一挤压机，该挤压机与一如图21和23所示的共挤进料装置相连，它可从许多不同的市场来源包括得克萨斯州Orange的Cloreon公司和威斯康星州Ean Claire的Production Components有限公司以及其它公司获得。
共挤进料装置150包括三段。第一段152是与单独挤压机相连并将圆条状树脂流导向程序段154的进料口段。程序段154接着将每一树脂流整形为长方形且其尺寸与希望的单独层厚成比例。渐变段156将分开的单独长方形层组合成一方形口，TPU A层的熔融温度应在华氏约300度至约450度，为了优化TPU A层和掺合的聚酯多元醇型的TPU和EVOH共聚物的B层之间的粘合，每个熔融流的实际温度应作调整以使每个熔融流的粘度几乎相匹配。混合层熔融流接着在片状模158内模塑成一单独的矩形挤制熔体，该片状模最好设计有如图22所示的在制塑工业中常用“外套支架”。然后，挤出物冷却并通过铸或压延工艺利用辊160形成刚性片。
类似于片材挤塑，制作共挤管所需的设备包括一用于每种形式树脂且与普通的多支管模相连接的挤压机。聚合物熔体从每个挤压机流入例如图23所示的支管模中，并分别流进用于热塑性聚氨酯和掺合的聚酯多元醇型热塑性聚氨酯与乙烯和乙烯醇的共聚物的独立的环形流道172A和172B中，所述支管模可从包括乔治亚洲亚特兰大市Canterberry工程有限公司，佛罗里达州Clear water的Genca公司以及其它公司购得。流道形状为环形，其尺寸与每层希望的厚度成比例。接着，各独立的熔体就在模入口174之前经混合形成一共同的熔体流。然后熔体流经由在圆柱型芯180的外表面178和圆柱模壳184的内表面182之间的环形部形成的通道176。管形挤出物离开模壳，然后通过许多普通的管标准方法冷却成管状。图23表示两个组合管，对本领域的普通技术人员来说应能理解穿过单独的流道增加附属层。
不考虑使用的塑料成形工艺，在层压制品的期望长度或节段上达到层间所需的大范围的氢键键接的相容熔体，这是最重要的，所述相容熔体是指热塑性聚氨酯树脂和掺合的聚酯多元醇型热塑性聚氨酯和乙烯乙烯醇的共聚物的熔体。这样，使用的多层生产工艺对于热塑性聚氨酯和聚酯多元醇型热塑性聚氨酯和乙烯乙烯醇共聚物的掺合物来说应该在华氏温度从约300度至约450度的保持温度下执行。而且，在各层接合且保持足够量的氢键键接的位置保持至少200磅/平方英寸的足够压力是十分重要的。
如前所述，除了本发明的层压阻挡隔膜获得了极佳的键接外，特别相对于用作鞋袜的缓冲装置的阻挡隔膜来说，另一目的是提供能保留封存气体达希望的一般时间的阻挡隔膜。一般，对于508微米厚度根据ASTM D-1434-82规定的程序测得的气体传递率值等于或小于10的阻挡层隔膜，对于期望的使用期是一种可接受的选择。在这方面是由于聚酯多元醇型聚氨酯和乙烯与乙烯醇的共聚物组成的掺合物在弹性，尤其是抗潮湿引起的老化和抗不良的气体传递等方面所具有的优良性质决定的。本发明的阻挡隔膜既可作用多层层压制品或上述阻挡层材料制造的单层构造。
为了准备如表I提出的市场上买不到的样品以便分析气体传递率性质，通过向2000毫升反应瓶中添加一种或多种下列成分来首先制备羟基组分：(1)聚酯多元醇(即所述的线性二羧酸和二元醇的工业产品或反应制品)；(2)双官能增量剂；和(3)加工助剂例如蜡和抗氧化剂。然后羟基组分加热至约95℃-115℃之间(由组成来决定)并搅拌使各成分均匀溶解。接着，在持续搅拌下施加小于0.2毫米汞柱的真空以控制起泡沫。在起泡结束后，排除瓶内气体约30分钟直至实际上整个起泡终止。
接下来，通过将二异氰酸酯放在250ml聚丙烯烧杯内并将该二异氰酸酯放在炉上加热至约50-65℃之间来制备异氰酸酯组分。在温度达到约50-65℃之间后，所需量的异氰酸酯经称量并如果有催化剂的话在恒定搅拌下将其加至异氰酸酯组分中。
一旦催化剂加入并充分搅拌，将预定量的羟基组分加入异氰酸酯组分中以实现聚合。当聚合开始时粘度增加(一般在加入后约7-12秒)，反应物倒入涂有所需隔离剂的盘中并使之充分冷却。
冷却后，新形成的聚合物切成小颗粒并在85-100℃之间干燥约2-4小时。然后将表1中提出的不同样品铸造成片状用来进行涉及气体传递性能的分析。
如表2所示，样品1-8中任一个的气体传递率结果证实均好于由市场上买得到的热塑性聚氨酯树脂形成的对比样品9-10，而且，涉及到聚己二酸乙二醇酯型聚氨酯的样品2-8证实其气体传递率值好于样品1的聚己二酸丁二醇酯型聚氨酯的气体传递率。
由于使用乙烯及乙烯醇的共聚物和聚酯多元醇型热塑性聚氨酯的掺合物理论上其气体传递率低于聚酯多元醇型热塑性聚氨酯的气体传递率，样品2-8表明对于单层以及多层阻挡隔膜它都是极佳的选择，因为气体传递率值显然符合或接近目标值10或更低。
上面详细描述了本发明的优选实施例，应该理解在不超出附加的权利要求书的范围和事实的情况下本发明允许作修改、变化和变更。
                                              表I*单层制品气体传递率
    组成     样品1   样品2   样品3   样品4   样品5     样品6   样品7     样品8     样品9     样品10
    聚己二酸丁二醇酯(a)2000m.w.1     43.12
    (b)700m.w.2     15.09
    己二酸乙二醇酯(a)1000m.w.3   61.11   62.29   49.18   60.63     49.60   30.26     16.39
    (b)500m.w.4   61.11   62.29   49.18   60.63   22.69     32.77
    1，2-乙二醇   4.25
    二丙二醇     0.58
    丁基卡必醇     0.21
    1，4丁二醇     7.37   6.05   9.96   6.00     8.93   6.81     7.37
    H12MDI5     41.07   39.84
    MDI6     33.04   32.5   40.52     43.15
    MDI/llq.MDI7   33.12   33.03
    Irganaox 10108     0.125   0.15   0.15   0.15   0.15     0.15   0.15     0.15
    Advawax 2809     0.125   0.15   0.15   0.15   0.15     0.15   0.15     0.15
    Wax10     0.30
    催化剂11     0.04   0.04   0.04   0.04   0.04     0.10   0.10     0.02
    Pellethane 2355-85 ATP12     100.0
    Pellethane 2355-95 AE13     100.0
    总重量百分比     100.0   100.0   100.0   100.0   100.0     100.0   100.0     100.0     100.0     100.0
*表1中所有值均为重量百分比(WT％)
1.FOMREZTM 44-56，出自Witco化学公司
2.FOMREZTM 44-160，出自Witco化学公司
3.FOMREZTM 22-112，出自Witco化学公司
4.FOMREZTM 22-225，出自Witco化学公司
5.DESMUDAR W(m.w 262)，出自BAYER AG(美国)
6.ISONATETM 125M，出自Dow化学有限公司
7.80％的IONATETM 125M和20％的IONATETM 143L的掺合物，出自Dow化学有限公司。
8.IRGANOXTM 1010，出自Ciba-Gigy化学公司
9.ADVAWAXTM 280，出自
10.Montan脂蜡
11.50％的辛酸亚锡和50％的邻苯二甲酸二辛酯的掺合物
12.PELLETHANETM 2355-85 ATP，出自
Dow化学公司
13.PELLETHANETM 2355-95AE，出自Dow化学公司
                              表II
  样品号 平均厚度   GTR(cc/m2*大气压*天)     GTR(cc/m2*大气压*天)校正至20密耳厚度
  1 16.25密耳   30.95     25.15
  2 15.2密耳   11.71     8.9
  3 17.13密耳   9.13     7.82
  4 18.49密耳   6.58     6.08
  5 17.54密耳   7.07     6.19
  6 19.93密耳   9.22     9.19
  7 19.93密耳   6.19     6.17
  8 18.31密耳   1.20     1.10
  9 19.95密耳   36.42     36.33
 10 18.25密耳   24.12     22.01

Claims (16)

1.一种具有改进的抗不良的气体渗透性的阻挡隔膜，它包括：
包括乙烯与乙烯醇的至少一种共聚物和至少一种由聚酯多元醇形成的热塑聚氨酯组成的掺合物的第一阻挡层，所述聚酯多元醇由下列的反应产物形成(a)具有六个或小于六个碳原子的线性二羧酸(b)具有六个或小于六个碳原子的二元醇，这里反应产物的碳原子总数为八或小于八，其中所述阻挡隔膜被密封和永久充气，并且所述阻挡隔膜对充入的气体的气体传递率为10或小于10。
2.如权利要求1所述的阻挡隔膜，其中线性二羧酸选自包括己二酸，戊二酸，丁二酸，丙二酸和草酸的组中。
3.如权利要求1所述的阻挡隔膜，其中二元醇选自包括乙二醇，丙二醇，丁二醇，戊二醇和己二醇的组中。
4.如权利要求1所述的阻挡隔膜，其中第一层包括重量百分比至多50％的由一种或多种聚酯多元醇形成的热塑聚氨酯。
5.如权利要求4所述的阻挡隔膜，其中所述第一层包括重量百分比在1％至30％之间的由一种或多种聚酯多元醇形成的热塑聚氨酯。
6.如权利要求5所述的阻挡隔膜，其中所述第一层包括重量百分比在5％至25％之间的由一种或多种聚酯多元醇形成的热塑聚氨酯。
7.如权利要求1所述的阻挡隔膜，其中所述乙烯与乙烯醇的共聚物选自包含的乙烯摩尔百分比含量在25％至48％之间的共聚物。
8.如权利要求1所述的阻挡隔膜，其中所述第一层还包括芳族热塑聚氨酯。
9.如权利要求1所述的阻挡隔膜，其中所述第一层包括：
(a)重量百分比在50％至97％的至少一种乙烯与乙烯醇的共聚物；
(b)重量百分比在3％至50％的由聚酯多元醇形成的至少一种热塑聚氨酯，及
(c)重量百分比至多3％的一种或多种芳族热塑聚氨酯，
这里第一层的构成成分总的重量百分比等于100％。
10.如权利要求9所述的阻挡隔膜，其中所述至少一种热塑聚氨酯是脂族的。
11.如权利要求10所述的阻挡隔膜，其中还包括具有层压在所述第一层上的包括热塑聚氨酯的第二层，以便沿所述阻挡隔膜的一段在所述第一和第二层之间产生氢键键接形式的接触反应。
12.如权利要求11所述的阻挡隔膜，其中所述热塑聚氨酯的第二层选自聚酯，聚醚，聚己内酯，聚氧化丙烯和聚碳酸酯多聚二醇型材料及其混合物。
13.如权利要求11所述的阻挡隔膜，其中所述第一层的平均厚度在0.5密耳至10密耳之间且热塑聚氨酯的第二层的平均厚度在5密耳至100密耳之间，该第一层包括乙烯与乙烯醇的至少一种共聚物和至少一种由聚酯多元醇形成的热塑聚氨酯组成的掺合物。
14.如权利要求1所述的阻挡隔膜，其中所述至少一种聚酯多元醇包括己二酸乙二醇酯。
15.具有改进的抗不良气体渗透的一种阻挡隔膜，其中包括：
一个阻挡层，它包括由1，2-乙二醇与己二酸的反应产物形成的至少一种热塑聚氨酯，其中所述阻挡隔膜被密封和永久充气，并且所述阻挡隔膜对充入的气体的气体传递率为10或小于10。
16.包含如权利要求1至15任一项的阻挡隔膜的软外壳，它是液力蓄压器或可充气物体的形式。
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Families Citing this family (310)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6490730B1 (en) 1989-09-20 2002-12-10 Robert M. Lyden Shin-guard, helmet, and articles of protective equipment including light cure material
US5952065A (en) 1994-08-31 1999-09-14 Nike, Inc. Cushioning device with improved flexible barrier membrane
US6599597B1 (en) * 1995-06-07 2003-07-29 Nike, Inc. Barrier membranes including a barrier layer employing aliphatic thermoplastic urethanes
US6013340A (en) 1995-06-07 2000-01-11 Nike, Inc. Membranes of polyurethane based materials including polyester polyols
CA2222097C (en) * 1995-06-07 2009-03-24 Nike International Ltd. Membranes of polyurethane based materials including polyester polyols
DE69935561T2 (de) * 1998-03-30 2007-07-19 Nisshinbo Industries, Inc. Verwendung eines gegenstandes aus einer polyamidharz-zusammensetzung
US7334350B2 (en) * 1999-03-16 2008-02-26 Anatomic Research, Inc Removable rounded midsole structures and chambers with computer processor-controlled variable pressure
US6601042B1 (en) 2000-03-10 2003-07-29 Robert M. Lyden Customized article of footwear and method of conducting retail and internet business
US7752775B2 (en) * 2000-03-10 2010-07-13 Lyden Robert M Footwear with removable lasting board and cleats
US6449878B1 (en) 2000-03-10 2002-09-17 Robert M. Lyden Article of footwear having a spring element and selectively removable components
US6681403B2 (en) 2000-03-13 2004-01-27 Robert M. Lyden Shin-guard, helmet, and articles of protective equipment including light cure material
US6457262B1 (en) 2000-03-16 2002-10-01 Nike, Inc. Article of footwear with a motion control device
US6402879B1 (en) * 2000-03-16 2002-06-11 Nike, Inc. Method of making bladder with inverted edge seam
US6385864B1 (en) * 2000-03-16 2002-05-14 Nike, Inc. Footwear bladder with controlled flex tensile member
US6374514B1 (en) * 2000-03-16 2002-04-23 Nike, Inc. Footwear having a bladder with support members
US6571490B2 (en) 2000-03-16 2003-06-03 Nike, Inc. Bladder with multi-stage regionalized cushioning
US6430843B1 (en) 2000-04-18 2002-08-13 Nike, Inc. Dynamically-controlled cushioning system for an article of footwear
US20020069731A1 (en) * 2000-09-14 2002-06-13 Soucy Alan J. Vibration dampening apparatus
US7229518B1 (en) 2000-11-02 2007-06-12 Nike, Inc. Process for improving interfacial adhesion in a laminate
US6281149B1 (en) * 2000-11-28 2001-08-28 3Tex, Inc. Ballistic protective wear for female torso
US6846532B1 (en) * 2001-02-15 2005-01-25 Sonoco Development, Inc. Laminate packaging material
US6879885B2 (en) * 2001-11-16 2005-04-12 Goodrich Pump & Engine Control Systems, Inc. Rotor torque predictor
US20050167029A1 (en) 2001-11-26 2005-08-04 Nike, Inc. Method of thermoforming a fluid-filled bladder
CA2417485C (en) 2002-01-29 2010-08-17 Kuraray Co., Ltd. Thermoplastic polyurethane composition and process for producing the same
US6848201B2 (en) * 2002-02-01 2005-02-01 Heeling Sports Limited Shock absorption system for a sole
US6790391B2 (en) * 2002-03-07 2004-09-14 Nike International, Ltd. Composition for clear gas barrier laminates
JP3808389B2 (ja) * 2002-03-25 2006-08-09 富士写真フイルム株式会社 反応性固相担体及びｄｎａ断片検出用具
KR100508137B1 (ko) * 2002-03-26 2005-08-10 주식회사 에이스테크놀로지 휴대용 전화기 안테나 커버용 조성물 및 이를 포함하는휴대용 전화기 안테나 커버 제조방법
US7426792B2 (en) * 2002-05-09 2008-09-23 Nike, Inc. Footwear sole component with an insert
US6796056B2 (en) 2002-05-09 2004-09-28 Nike, Inc. Footwear sole component with a single sealed chamber
US20040044404A1 (en) * 2002-08-30 2004-03-04 Stucke Sean M. Retention coatings for delivery systems
US20040155400A1 (en) * 2003-02-06 2004-08-12 Paul Perkins Pool game ball
US7128796B2 (en) * 2003-07-16 2006-10-31 Nike, Inc. Footwear with a sole structure incorporating a lobed fluid-filled chamber
US7707744B2 (en) * 2003-07-16 2010-05-04 Nike, Inc. Footwear with a sole structure incorporating a lobed fluid-filled chamber
US7000335B2 (en) * 2003-07-16 2006-02-21 Nike, Inc. Footwear with a sole structure incorporating a lobed fluid-filled chamber
US7707745B2 (en) * 2003-07-16 2010-05-04 Nike, Inc. Footwear with a sole structure incorporating a lobed fluid-filled chamber
US20050031816A1 (en) * 2003-08-04 2005-02-10 Yihua Chang Membranes with fluid barrier properties and articles containing such membranes
US20050118370A1 (en) * 2003-08-18 2005-06-02 Medtronic Vascular, Inc. Hyper-elastic, high strength dilatation balloon made from multi-block copolymers
US7597946B2 (en) * 2003-08-29 2009-10-06 Nike, Inc. Gel reduction in blends of thermoplastic polyurethane and hydroxyl functional polymers
US7448522B2 (en) * 2003-11-11 2008-11-11 Nike, Inc. Fluid-filled bladder for use with strap
US7076891B2 (en) 2003-11-12 2006-07-18 Nike, Inc. Flexible fluid-filled bladder for an article of footwear
CN100556328C (zh) 2003-12-23 2009-11-04 耐克国际有限公司 具有强化结构的流体充注囊
US7156787B2 (en) * 2003-12-23 2007-01-02 Nike, Inc. Inflatable structure and method of manufacture
US7086179B2 (en) * 2003-12-23 2006-08-08 Nike, Inc. Article of footwear having a fluid-filled bladder with a reinforcing structure
US7399509B2 (en) * 2003-12-23 2008-07-15 Kari Virtanen Thin polyethylene pressure sensitive labels
US7562469B2 (en) 2003-12-23 2009-07-21 Nike, Inc. Footwear with fluid-filled bladder and a reinforcing structure
US7556846B2 (en) * 2003-12-23 2009-07-07 Nike, Inc. Fluid-filled bladder with a reinforcing structure
US7141131B2 (en) * 2003-12-23 2006-11-28 Nike, Inc. Method of making article of footwear having a fluid-filled bladder with a reinforcing structure
US7086180B2 (en) * 2003-12-23 2006-08-08 Nike, Inc. Article of footwear having a fluid-filled bladder with a reinforcing structure
US7100310B2 (en) * 2003-12-23 2006-09-05 Nike, Inc. Article of footwear having a fluid-filled bladder with a reinforcing structure
US7763341B2 (en) 2004-01-23 2010-07-27 Century-Board Usa, Llc Filled polymer composite and synthetic building material compositions
KR100880832B1 (ko) * 2004-02-10 2009-01-30 삼성전자주식회사 코-디버깅 기능을 지원하는 반도체 집적회로 및 반도체집적회로 테스트 시스템
US20050197480A1 (en) * 2004-03-05 2005-09-08 Temple Rodger G. Barrier coating comprising a polyurethane dispersion and elastomeric material
US7316559B2 (en) 2004-06-24 2008-01-08 Century-Board Usa, Llc Continuous forming apparatus for three-dimensional foam products
US7794224B2 (en) 2004-09-28 2010-09-14 Woodbridge Corporation Apparatus for the continuous production of plastic composites
US8256147B2 (en) 2004-11-22 2012-09-04 Frampton E. Eliis Devices with internal flexibility sipes, including siped chambers for footwear
WO2006060737A2 (en) * 2004-12-03 2006-06-08 Takeda San Diego, Inc. Mitotic kinesin inhibitors
US20060262120A1 (en) * 2005-05-19 2006-11-23 Outland Research, Llc Ambulatory based human-computer interface
US7309252B2 (en) * 2005-02-22 2007-12-18 Tyco Electronics Corporation Low profile surface mount connector
US20060253210A1 (en) * 2005-03-26 2006-11-09 Outland Research, Llc Intelligent Pace-Setting Portable Media Player
US7513066B2 (en) 2005-04-14 2009-04-07 Nike, Inc. Fluid-filled bladder for footwear and other applications
US7401369B2 (en) 2005-04-14 2008-07-22 Nike, Inc. Fluid-filled bladder for footwear and other applications
US20060248750A1 (en) * 2005-05-06 2006-11-09 Outland Research, Llc Variable support footwear using electrorheological or magnetorheological fluids
US7622014B2 (en) * 2005-07-01 2009-11-24 Reebok International Ltd. Method for manufacturing inflatable footwear or bladders for use in inflatable articles
CN101228248B (zh) * 2005-07-22 2012-05-09 株式会社普利司通 密封用材料、其制造方法以及使用密封用材料的密封垫
WO2007037058A1 (ja) * 2005-09-28 2007-04-05 Clarion Co., Ltd. 車載用音響装置
US7533477B2 (en) 2005-10-03 2009-05-19 Nike, Inc. Article of footwear with a sole structure having fluid-filled support elements
US7586032B2 (en) * 2005-10-07 2009-09-08 Outland Research, Llc Shake responsive portable media player
KR100960402B1 (ko) * 2005-10-17 2010-05-28 폴리원 코포레이션 열가소성 폴리우레탄 분말 조성물 및 용도
US7806389B2 (en) 2005-10-26 2010-10-05 Parkson Corporation Flexible aeration panel and methods of use
US7555851B2 (en) 2006-01-24 2009-07-07 Nike, Inc. Article of footwear having a fluid-filled chamber with flexion zones
US7752772B2 (en) 2006-01-24 2010-07-13 Nike, Inc. Article of footwear having a fluid-filled chamber with flexion zones
US8138234B2 (en) * 2006-03-24 2012-03-20 Century-Board Usa, Llc Polyurethane composite materials
US20070261208A1 (en) * 2006-05-15 2007-11-15 Ishai Alon B Cushioned handle
US7685743B2 (en) * 2006-06-05 2010-03-30 Nike, Inc. Article of footwear or other foot-receiving device having a fluid-filled bladder with support and reinforcing structures
US7749100B2 (en) * 2006-07-11 2010-07-06 Nike, Inc. Golf clubs and golf club heads having fluid-filled bladders and/or interior chambers
US7611547B2 (en) * 2006-10-30 2009-11-03 Nike, Inc. Airbag dyeing compositions and processes
US20080138552A1 (en) * 2006-12-12 2008-06-12 Swei Mu Wang Colorful air cushion structure
US7810255B2 (en) 2007-02-06 2010-10-12 Nike, Inc. Interlocking fluid-filled chambers for an article of footwear
US7699911B2 (en) * 2007-05-03 2010-04-20 Honeywell International Inc. Ozone resistant O2/N2 separation membranes
US7950169B2 (en) 2007-05-10 2011-05-31 Nike, Inc. Contoured fluid-filled chamber
US7811100B2 (en) 2007-07-13 2010-10-12 Fci Americas Technology, Inc. Electrical connector system having a continuous ground at the mating interface thereof
US7941941B2 (en) 2007-07-13 2011-05-17 Nike, Inc. Article of footwear incorporating foam-filled elements and methods for manufacturing the foam-filled elements
US7591919B2 (en) 2007-08-13 2009-09-22 Nike, Inc. Fluid-filled chambers with foam tensile members and methods for manufacturing the chambers
US8266826B2 (en) * 2007-10-09 2012-09-18 Nike, Inc. Article of footwear with sole structure
WO2009048630A1 (en) * 2007-10-12 2009-04-16 Memsic, Inc. Electronic shoe wear indicator
US8978273B2 (en) 2007-10-19 2015-03-17 Nike, Inc. Article of footwear with a sole structure having fluid-filled support elements
US8863408B2 (en) 2007-12-17 2014-10-21 Nike, Inc. Article of footwear having a sole structure with a fluid-filled chamber
US8178022B2 (en) 2007-12-17 2012-05-15 Nike, Inc. Method of manufacturing an article of footwear with a fluid-filled chamber
US8241450B2 (en) 2007-12-17 2012-08-14 Nike, Inc. Method for inflating a fluid-filled chamber
US8341857B2 (en) 2008-01-16 2013-01-01 Nike, Inc. Fluid-filled chamber with a reinforced surface
US8572867B2 (en) 2008-01-16 2013-11-05 Nike, Inc. Fluid-filled chamber with a reinforcing element
ITPD20080079A1 (it) * 2008-03-11 2009-09-12 A P I Applicazioni Plastiche Industriali Spa Compound elastomerico biodegradabile
US8151486B2 (en) 2008-05-20 2012-04-10 Nike, Inc. Fluid-filled chamber with a textile tensile member
US20090295021A1 (en) * 2008-05-27 2009-12-03 Century-Board Usa, Llc Extrusion of polyurethane composite materials
US8210973B2 (en) 2008-06-27 2012-07-03 Nike, Inc. Sport ball bladder
US8852039B2 (en) 2011-06-28 2014-10-07 Nike, Inc. Sport ball casing with integrated bladder material
US8708847B2 (en) 2008-06-27 2014-04-29 Nike, Inc. Sport ball casing and methods of manufacturing the casing
US8182379B2 (en) 2008-06-27 2012-05-22 Nike, Inc. Sport balls and methods of manufacturing the sport balls
US8087187B2 (en) * 2008-11-06 2012-01-03 Nike, Inc. Article of footwear with support assemblies
US8943709B2 (en) * 2008-11-06 2015-02-03 Nike, Inc. Article of footwear with support columns having fluid-filled bladders
MY164930A (en) 2008-11-14 2018-02-15 Molex Inc Connector with terminals forming differential pairs
CN102318143B (zh) 2008-12-12 2015-03-11 莫列斯公司 谐振调整连接器
US9277649B2 (en) 2009-02-26 2016-03-01 Fci Americas Technology Llc Cross talk reduction for high-speed electrical connectors
US8366485B2 (en) 2009-03-19 2013-02-05 Fci Americas Technology Llc Electrical connector having ribbed ground plate
US8877865B2 (en) * 2009-03-30 2014-11-04 Kuraray Co., Ltd. Resin composition and multilayered structure
US7950432B2 (en) 2009-06-24 2011-05-31 Nike, Inc. Method of customizing an article and apparatus including an inflatable member
US8578534B2 (en) 2009-06-24 2013-11-12 Nike, Inc. Inflatable member
US9107479B2 (en) 2009-06-24 2015-08-18 Nike, Inc. Adjustable last
US8650775B2 (en) 2009-06-25 2014-02-18 Nike, Inc. Article of footwear having a sole structure with perimeter and central elements
US8846776B2 (en) 2009-08-14 2014-09-30 Boral Ip Holdings Llc Filled polyurethane composites and methods of making same
US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
US8267721B2 (en) 2009-10-28 2012-09-18 Fci Americas Technology Llc Electrical connector having ground plates and ground coupling bar
US9119439B2 (en) * 2009-12-03 2015-09-01 Nike, Inc. Fluid-filled structure
US9894959B2 (en) 2009-12-03 2018-02-20 Nike, Inc. Tethered fluid-filled chamber with multiple tether configurations
US8479412B2 (en) 2009-12-03 2013-07-09 Nike, Inc. Tethered fluid-filled chambers
US9420848B2 (en) 2013-02-21 2016-08-23 Nike, Inc. Article of footwear incorporating a chamber system and methods for manufacturing the chamber system
US8991072B2 (en) 2010-02-22 2015-03-31 Nike, Inc. Fluid-filled chamber incorporating a flexible plate
US8808357B2 (en) 2010-04-06 2014-08-19 Poly-Med, Inc. Radiopaque iodinated and iodide-containing crystalline absorbable aliphatic polymeric materials and applications thereof
US8381418B2 (en) 2010-05-10 2013-02-26 Nike, Inc. Fluid-filled chambers with tether elements
US8782924B2 (en) 2010-05-11 2014-07-22 Nike, Inc. Article of footwear having a sole structure with a framework-chamber arrangement
US8464439B2 (en) 2010-05-12 2013-06-18 Nike, Inc. Contoured fluid-filled chamber with a tensile member
US8470113B2 (en) 2010-05-12 2013-06-25 Nike, Inc. Method of manufacturing a contoured fluid-filled chamber with a tensile member
US8689467B2 (en) 2010-08-20 2014-04-08 Nike, Inc. Sole structure with visual effects
US8661717B2 (en) 2010-08-20 2014-03-04 Nike, Inc. Article of footwear with slots and method of making
US8732986B2 (en) 2010-08-20 2014-05-27 Nike, Inc. Sole structure comprising a fluid filled member with slots
US8572786B2 (en) 2010-10-12 2013-11-05 Reebok International Limited Method for manufacturing inflatable bladders for use in footwear and other articles of manufacture
US9161592B2 (en) 2010-11-02 2015-10-20 Nike, Inc. Fluid-filled chamber with a stacked tensile member
US9144268B2 (en) 2010-11-02 2015-09-29 Nike, Inc. Strand-wound bladder
US9055784B2 (en) 2011-01-06 2015-06-16 Nike, Inc. Article of footwear having a sole structure incorporating a plate and chamber
US9021720B2 (en) 2011-03-16 2015-05-05 Nike, Inc. Fluid-filled chamber with a tensile member
US10010136B2 (en) 2011-03-16 2018-07-03 Nike, Inc. Footwear sole structure incorporating a plurality of chambers
US8789294B2 (en) 2011-03-16 2014-07-29 Nike, Inc. Contoured fluid-filled chamber with tensile structures
US8869430B2 (en) 2011-03-16 2014-10-28 Nike, Inc. Method of manufacturing a contoured fluid-filled chamber with tensile structures
US8857076B2 (en) 2011-04-06 2014-10-14 Nike, Inc. Article of footwear with an adaptive fluid system
US8844165B2 (en) 2011-04-06 2014-09-30 Nike, Inc. Adjustable bladder system with external valve for an article of footwear
US9060564B2 (en) * 2011-04-06 2015-06-23 Nike, Inc. Adjustable multi-bladder system for an article of footwear
US8813389B2 (en) 2011-04-06 2014-08-26 Nike, Inc. Adjustable bladder system for an article of footwear
US8839530B2 (en) 2011-04-12 2014-09-23 Nike, Inc. Method of lasting an article of footwear with a fluid-filled chamber
US8672784B2 (en) 2011-05-04 2014-03-18 Nike, Inc. Sport ball with an inflation-retention bladder
US8771115B2 (en) 2011-05-04 2014-07-08 Nike, Inc. Sport ball with an inflation-retention bladder
WO2012165441A1 (ja) * 2011-05-31 2012-12-06 株式会社クラレ 空気入りタイヤ用インナーライナー、その製造方法及び空気入りタイヤ
US8677653B2 (en) 2011-06-01 2014-03-25 Nike, Inc. Interchangeable insert system for footwear
EP2714393B1 (de) * 2011-06-03 2015-07-15 Hogg, Hermann Mehrlagige fassadenfolie
US8709332B2 (en) 2011-07-20 2014-04-29 Nike, Inc. Thermoforming sheet loading apparatus and method
US9392836B2 (en) 2011-08-04 2016-07-19 Nike, Inc. Footwear with interchangeable bootie system
US9745224B2 (en) 2011-10-07 2017-08-29 Boral Ip Holdings (Australia) Pty Limited Inorganic polymer/organic polymer composites and methods of making same
WO2013074197A1 (en) 2011-11-15 2013-05-23 Hoffman James P Mechanical edge setting system and method for setting tiles and tuning lippage
US9179733B2 (en) 2011-12-23 2015-11-10 Nike, Inc. Article of footwear having an elevated plate sole structure
US9491984B2 (en) 2011-12-23 2016-11-15 Nike, Inc. Article of footwear having an elevated plate sole structure
US9750300B2 (en) 2011-12-23 2017-09-05 Nike, Inc. Article of footwear having an elevated plate sole structure
US9408436B2 (en) 2012-01-11 2016-08-09 Nike, Inc. Heatable and coolable inserts for footwear
EP2624034A1 (en) 2012-01-31 2013-08-07 Fci Dismountable optical coupling device
US8919015B2 (en) 2012-03-08 2014-12-30 Nike, Inc. Article of footwear having a sole structure with a flexible groove
US9609912B2 (en) 2012-03-23 2017-04-04 Nike, Inc. Article of footwear having a sole structure with a fluid-filled chamber
EP3112003B1 (en) 2012-03-30 2020-05-27 NIKE Innovate C.V. Sport ball casing with integrated bladder material
US8747593B2 (en) 2012-04-10 2014-06-10 Nike, Inc. Methods for manufacturing fluid-filled chambers incorporating spacer textile materials
US9375049B2 (en) 2012-04-10 2016-06-28 Nike, Inc. Spacer textile materials and methods for manufacturing the spacer textile materials
USD727852S1 (en) 2012-04-13 2015-04-28 Fci Americas Technology Llc Ground shield for a right angle electrical connector
US9257778B2 (en) 2012-04-13 2016-02-09 Fci Americas Technology High speed electrical connector
USD727268S1 (en) 2012-04-13 2015-04-21 Fci Americas Technology Llc Vertical electrical connector
USD718253S1 (en) 2012-04-13 2014-11-25 Fci Americas Technology Llc Electrical cable connector
US9089188B2 (en) 2012-05-18 2015-07-28 Nike, Inc. Strap assembly for carrying a bag
JP6021442B2 (ja) * 2012-05-28 2016-11-09 横浜ゴム株式会社 空気入りタイヤ
DK2671912T3 (en) * 2012-06-05 2015-07-27 Rhein Chemie Rheinau Gmbh Process for stabilizing polymers containing ester groups
USD751507S1 (en) 2012-07-11 2016-03-15 Fci Americas Technology Llc Electrical connector
US9510646B2 (en) 2012-07-17 2016-12-06 Nike, Inc. Article of footwear having a flexible fluid-filled chamber
US10631593B2 (en) 2012-08-21 2020-04-28 Levi J. Patton Fluid-filled chamber with a stabilization structure
US9066558B2 (en) 2012-12-17 2015-06-30 Nike, Inc. Electronically controlled bladder assembly
US9380832B2 (en) 2012-12-20 2016-07-05 Nike, Inc. Article of footwear with fluid-filled chamber lacking an inflation channel and method for making the same
US9375048B2 (en) 2012-12-28 2016-06-28 Nike, Inc. Article of footwear having adjustable sole structure
USD745852S1 (en) 2013-01-25 2015-12-22 Fci Americas Technology Llc Electrical connector
US9981437B2 (en) 2013-02-21 2018-05-29 Nike, Inc. Article of footwear with first and second outsole components and method of manufacturing an article of footwear
US9970155B2 (en) 2013-03-05 2018-05-15 Nike, Inc. Acid dyeing of polyurethane materials
US9974362B2 (en) 2013-03-08 2018-05-22 NIKE, Inc.. Assembly for coloring articles and method of coloring
US9668538B2 (en) 2013-03-08 2017-06-06 Nike, Inc. System and method for coloring articles
US20140250720A1 (en) 2013-03-08 2014-09-11 Nike, Inc. Multicolor Sole System
US10806214B2 (en) 2013-03-08 2020-10-20 Nike, Inc. Footwear fluid-filled chamber having central tensile feature
US9603414B2 (en) 2013-03-15 2017-03-28 Nike, Inc. Fluid-filled chamber with a tensile element
USD720698S1 (en) 2013-03-15 2015-01-06 Fci Americas Technology Llc Electrical cable connector
US9339080B2 (en) 2013-03-15 2016-05-17 Nike, Inc. Method of manufacturing a fluid-filled chamber with a tensile element
WO2014168633A1 (en) 2013-04-12 2014-10-16 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
US9456651B2 (en) 2013-04-23 2016-10-04 Nike, Inc. Holding assembly with locking systems for articles
US9402445B2 (en) 2013-04-23 2016-08-02 Nike, Inc. Holding assembly for articles
US9301576B2 (en) 2013-04-23 2016-04-05 Nike, Inc. Method of printing onto an article
US9730487B2 (en) 2013-07-12 2017-08-15 Nike, Inc. Contoured fluid-filled chamber
US9427043B2 (en) 2013-10-31 2016-08-30 Nike, Inc. Fluid-filled chamber with stitched tensile member
US10463106B2 (en) 2014-02-13 2019-11-05 Nike, Inc. Sole assembly with textile shell and method of manufacturing same
US20150265000A1 (en) 2014-03-19 2015-09-24 Nike, Inc. Sole assembly with bladder element having a peripheral outer wall portion and method of manufacturing same
US20150264999A1 (en) 2014-03-19 2015-09-24 Nike, Inc. Sole assembly with thermoplastic polyurethane component thereon and and method of manufacturing same
US10005231B2 (en) 2014-05-23 2018-06-26 Nike, Inc. Method of manufacturing contoured objects by radio frequency welding and tooling assembly for same
US9427048B2 (en) 2014-06-09 2016-08-30 Nike, Inc. Polymeric component with injected, embedded ink and apparatus and method for manufacturing same
WO2016018226A1 (en) 2014-07-28 2016-02-04 Crocco Guy The use of evaporative coolants to manufacture filled polyurethane composites
WO2016022103A1 (en) 2014-08-05 2016-02-11 Amitabha Kumar Filled polymeric composites including short length fibers
US9737114B2 (en) 2014-08-06 2017-08-22 Nike, Inc. Articles of footwear with upper incorporating chamber element
US9423328B2 (en) 2014-08-27 2016-08-23 Nike, Inc. Apparatus and method for testing cushioning components
EP3415310B1 (en) 2014-09-12 2021-12-01 NIKE Innovate C.V. Membranes and uses thereof
US9516919B2 (en) 2014-09-16 2016-12-13 Nike, Inc. Sole structure with bladder for article of footwear and method of manufacturing the same
EP3179876B1 (en) 2014-10-31 2020-04-08 NIKE Innovate C.V. Article of footwear with a midsole assembly having a perimeter bladder element, a method of manufacturing and a mold assembly for same
CN106998852B (zh) 2014-11-12 2019-12-10 耐克创新有限合伙公司 一种鞋类制品以及制造该鞋类制品的方法
CN106998843B (zh) 2014-12-02 2019-09-27 耐克创新有限合伙公司 用于鞋类制品的具有空心聚合物元件的鞋底结构以及制造该鞋底结构的方法
WO2016118141A1 (en) 2015-01-22 2016-07-28 Boral Ip Holdings (Australia) Pty Limited Highly filled polyurethane composites
US10624417B2 (en) 2015-03-09 2020-04-21 Nike, Inc. Article of footwear with outsole bonded to cushioning component and method of manufacturing an article of footwear
US10238175B2 (en) 2015-04-08 2019-03-26 Nike, Inc. Article with a cushioning assembly having inner and outer bladder elements with interfitting features and method of manufacturing an article
CN107404977B (zh) 2015-04-08 2021-03-09 耐克创新有限合伙公司 具有在图像上固定到囊状元件的覆盖物的物品和制造该物品的方法
WO2016164549A1 (en) 2015-04-08 2016-10-13 Nike Innovate C.V. Article including a bladder element with an image and method of manufacturing the article
US10448703B2 (en) 2015-04-08 2019-10-22 Nike, Inc. Footwear sole structure with compliant membrane
US9854870B2 (en) 2015-04-08 2018-01-02 Nike, Inc. Method of manufacturing a bladder element with an impression of etched area of mold assembly and article having bladder element with impression
US9974360B2 (en) 2015-04-08 2018-05-22 Nike, Inc. Method of manufacturing a bladder element with an etched feature and article having a bladder element with an etched feature
CN107404975B (zh) 2015-04-08 2020-11-10 耐克创新有限合伙公司 具有包括内囊元件和外囊元件以及加强元件的缓冲组件的物品及制造物品的方法
WO2016172169A1 (en) 2015-04-21 2016-10-27 Nike Innovate C.V. Bladder element formed from three sheets and method of manufacturing a bladder element
CN107404974B (zh) 2015-04-24 2020-06-16 耐克创新有限合伙公司 具有带有一体的鞋外底的囊的鞋类的鞋底结构
EP3088179A1 (en) * 2015-04-30 2016-11-02 Impact Protection Technology AG Multilayer polyurethane protective films
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread
WO2016191593A1 (en) * 2015-05-28 2016-12-01 Nike, Inc. Athletic activity monitoring device with energy capture
CN107847780B (zh) 2015-05-28 2019-11-01 耐克创新有限合伙公司 能够捕获能量的体育运动监测设备
EP3302727A1 (en) * 2015-05-28 2018-04-11 Nike Innovate C.V. Athletic activity monitoring device with energy capture
EP3733063A1 (en) 2015-05-28 2020-11-04 Nike Innovate C.V. Athletic activity monitoring device with energy capture
US10411066B2 (en) 2015-05-28 2019-09-10 Nike, Inc. Athletic activity monitoring device with energy capture
WO2016196995A1 (en) 2015-06-04 2016-12-08 Nike Innovate C.V. Mold apparatus, mold system, and method for molding sole component of article of footwear
WO2016195717A1 (en) 2015-06-05 2016-12-08 Boral Ip Holdings (Australia) Pty Limited Filled polyurethane composites with lightweight fillers
US10306726B2 (en) 2015-06-19 2019-05-28 Nike, Inc. Method of illuminating an article
US20160366972A1 (en) 2015-06-19 2016-12-22 Nike, Inc. Article Incorporating an Illumination Device
US10327515B2 (en) 2015-08-06 2019-06-25 Nike, Inc. Footwear with compressible fluid-filled chamber
US10512301B2 (en) 2015-08-06 2019-12-24 Nike, Inc. Cushioning assembly for an article of footwear
US10070691B2 (en) 2015-11-03 2018-09-11 Nike, Inc. Article of footwear including a bladder element having a cushioning component with a single central opening and a cushioning component with multiple connecting features and method of manufacturing
US10905194B2 (en) 2015-11-03 2021-02-02 Nike, Inc. Sole structure for an article of footwear having a bladder element with laterally extending tubes and method of manufacturing a sole structure
US9775407B2 (en) 2015-11-03 2017-10-03 Nike, Inc. Article of footwear including a bladder element having a cushioning component with a single central opening and method of manufacturing
US10750821B2 (en) 2015-11-03 2020-08-25 Nike, Inc. Article of footwear with spaced cushioning components attached to a ground-facing surface of an upper and method of manufacturing an article of footwear
WO2017079254A1 (en) 2015-11-03 2017-05-11 Nike Innovate C.V. Article of footwear including a bladder element having a cushioning component with a single central opening and a cushioning component with multiple connecting features and method of manufacturing
US20170267585A1 (en) 2015-11-12 2017-09-21 Amitabha Kumar Filled polyurethane composites with size-graded fillers
MX2018011115A (es) * 2016-03-15 2018-11-09 Nike Innovate Cv Estructura de suela para articulo de calzado.
KR102486219B1 (ko) 2016-03-15 2023-01-09 나이키 이노베이트 씨.브이. 제1 및 제2 겉창 구성요소를 갖는 신발류 물품 및 신발류 물품의 제조 방법
WO2017160729A1 (en) 2016-03-15 2017-09-21 Nike Innovate C.V. Article of footwear and method of manufacturing an article of footwear
JP2019522573A (ja) 2016-06-29 2019-08-15 ナイキ イノヴェイト シーヴィーＮｉｋｅ Ｉｎｎｏｖａｔｅ Ｃ．Ｖ． 多層構造体及びその使用
US10524538B2 (en) 2016-09-08 2020-01-07 Nike, Inc. Flexible fluid-filled chamber with tensile member
US11026475B2 (en) 2016-09-08 2021-06-08 Nike, Inc. Flexible fluid-filled chamber with tensile member
EP3544461B1 (en) 2016-11-22 2021-04-14 NIKE Innovate C.V. Sole structure for an article of footwear with extended plate
CN110430776B (zh) 2017-02-27 2021-11-26 耐克创新有限合伙公司 包括填充流体囊腔的可调节足部支撑系统
EP3624627A1 (en) 2017-05-18 2020-03-25 Nike Innovate C.V. Articulated cushioning article with tensile component and method of manufacturing a cushioning article
JP2020519343A (ja) 2017-05-18 2020-07-02 ナイキ イノベイト シーブイ 引張コンポーネントを用いたクッション製品およびクッション製品の製造方法
US10766202B2 (en) * 2017-05-18 2020-09-08 Nike, Inc. System and method for welding a chamber
KR102328385B1 (ko) 2017-05-23 2021-11-18 나이키 이노베이트 씨.브이. 등급화된 응답을 갖는 중창 시스템
KR102360537B1 (ko) 2017-05-23 2022-02-09 나이키 이노베이트 씨.브이. 단계화된 압축 강도를 갖는 돔형 중창
WO2018217560A1 (en) 2017-05-23 2018-11-29 Nike, Inc. Midsole with graded response
WO2019036190A1 (en) 2017-08-18 2019-02-21 Nike Innovate C.V. LUMINESCENT VESSIES, LUMINESCENT ARTICLES, METHODS OF MANUFACTURING LUMINESCENT VESSIES, AND METHODS OF MAKING LUMINESCENT ARTICLES
KR102147920B1 (ko) 2017-09-29 2020-08-26 나이키 이노베이트 씨.브이. 구조색을 갖는 물품 및 구조색을 갖는 물품을 제조하고 사용하는 방법
CN114698897A (zh) 2017-10-27 2022-07-05 耐克创新有限合伙公司 包括包覆的纤维的物品以及制造包覆的纤维和物品的方法
US11452334B2 (en) * 2018-01-31 2022-09-27 Nike, Inc. Airbag for article of footwear
US10149513B1 (en) 2018-01-31 2018-12-11 Nike, Inc. Sole structure for article of footwear
KR102614471B1 (ko) 2018-04-20 2023-12-14 나이키 이노베이트 씨.브이. 플레이트들 및 개재된 유체 충전 블래더를 구비하는 솔 구조체 및 제조 방법
US11044964B2 (en) 2018-05-30 2021-06-29 Nike, Inc. Footwear sole structure with bladder
KR20230014884A (ko) 2018-05-31 2023-01-30 나이키 이노베이트 씨.브이. 블래더와 인장 구성요소를 구비한 신발류 스트로벨 및 제조 방법
US11318684B2 (en) 2018-05-31 2022-05-03 Nike, Inc. Fluid-filled cushioning article with seamless side walls and method of manufacturing
US11241063B2 (en) 2018-05-31 2022-02-08 Nike, Inc. Footwear strobel with bladder having grooved flange and method of manufacturing
CN112135543B (zh) 2018-05-31 2022-09-27 耐克创新有限合伙公司 带有囊和楦鞋部件的鞋类中底布和制造方法
CN108785024A (zh) * 2018-07-14 2018-11-13 苏州源欣江碳纤维科技有限公司 带下支撑的脚掌骨架
US10524540B1 (en) 2018-07-17 2020-01-07 Nike, Inc. Airbag for article of footwear
US11026476B2 (en) 2018-07-17 2021-06-08 Nike, Inc. Airbag for article of footwear
US11678722B2 (en) * 2018-08-30 2023-06-20 Asics Corporation Shoe and method of manufacturing shoe
WO2020055528A1 (en) 2018-09-13 2020-03-19 Nike Innovate C.V. Multi-layered structures and uses thereof
CN112218555A (zh) 2018-10-19 2021-01-12 耐克创新有限合伙公司 具有复合元件的鞋类鞋底结构及用于制造其的方法
CN115153151A (zh) 2018-11-20 2022-10-11 耐克创新有限合伙公司 鞋类囊系统
WO2020106432A1 (en) 2018-11-20 2020-05-28 Nike Innovate C.V. Footwear bladder system
WO2020112624A1 (en) 2018-11-29 2020-06-04 Nike Innovate C.V. Sports ball and method of manufacture
US11401396B2 (en) 2018-12-06 2022-08-02 Nike, Inc. Methods of manufacturing articles utilizing foam particles
CN113195197A (zh) * 2018-12-21 2021-07-30 宝利诺沃生物材料有限公司 定向生物可降解聚氨酯
CN113260271B (zh) 2018-12-28 2022-08-19 耐克创新有限合伙公司 具有竖直延伸的鞋跟稳定器的鞋类
US20220061464A1 (en) 2019-02-27 2022-03-03 Nike, Inc. Articles, bladders and methods of making articles and bladders
CN113574122B (zh) 2019-03-18 2024-03-26 耐克创新有限合伙公司 着色剂溶剂体系、使用方法和物品
EP4239019A1 (en) 2019-03-27 2023-09-06 NIKE Innovate C.V. Recyclable structurally-colored structures and articles, and methods of recycling structures and articles
CN113631059A (zh) 2019-03-27 2021-11-09 耐克创新有限合伙公司 结构着色的物品以及用于制造和使用结构着色的物品的方法
US11140941B2 (en) 2019-05-03 2021-10-12 Nike, Inc. Footwear upper with unitary support frame
CN110141020B (zh) * 2019-06-22 2021-03-09 安徽益健鞋材科技有限公司 一种无胶竹炭鞋垫
US11597996B2 (en) 2019-06-26 2023-03-07 Nike, Inc. Structurally-colored articles and methods for making and using structurally-colored articles
EP3963376A1 (en) 2019-07-26 2022-03-09 Nike Innovate C.V. Structurally-colored articles and methods for making and using structurally-colored articles
EP4273596A3 (en) 2019-07-26 2024-02-14 Nike Innovate C.V. Structurally-colored articles and methods for making and using structurally-colored articles
US11259593B2 (en) 2019-07-31 2022-03-01 Nike, Inc. Sole structure with tiered plate assembly for an article of footwear
CN114423586A (zh) 2019-09-19 2022-04-29 耐克创新有限合伙公司 用于热成形聚合物囊的模块化模具组件和制造可穿戴物品的方法
WO2021076599A1 (en) 2019-10-15 2021-04-22 Nike, Inc. Structurally-colored articles and methods for making and using structurally-colored articles
WO2021076439A1 (en) 2019-10-18 2021-04-22 Nike Innovate C.V. Lock for an adjustment cord of a wearable article
WO2021076440A1 (en) 2019-10-18 2021-04-22 Nike Innovate C.V. Easy-access article of footwear with cord lock
WO2021080913A1 (en) 2019-10-21 2021-04-29 Nike, Inc. Structurally-colored articles
WO2021194727A1 (en) 2020-03-26 2021-09-30 Nike Innovate C.V. Encased strobel with cushioning member and method of manufacturing an article of footwear
EP4157472A1 (en) 2020-05-26 2023-04-05 NIKE Innovate C.V. Inflatable sports ball with restriction structure
WO2021242372A1 (en) 2020-05-27 2021-12-02 Nike Innovate C.V. Footwear with fluid-filled bladder
CN115551720A (zh) 2020-05-29 2022-12-30 耐克创新有限合伙公司 结构着色的物品以及用于制造和使用结构着色的物品的方法
US11633012B2 (en) 2020-05-31 2023-04-25 Nike, Inc. Post production laser modification of an article of footwear
EP4185628A1 (en) 2020-07-24 2023-05-31 Basf Se Multilayered structure and a process for preparing the same
US11889894B2 (en) 2020-08-07 2024-02-06 Nike, Inc. Footwear article having concealing layer
US11241062B1 (en) 2020-08-07 2022-02-08 Nike, Inc. Footwear article having repurposed material with structural-color concealing layer
US11129444B1 (en) 2020-08-07 2021-09-28 Nike, Inc. Footwear article having repurposed material with concealing layer
WO2022115834A2 (en) 2020-11-25 2022-06-02 Nike, Inc. Structurally-colored articles and methods for making and using structurally-colored articles
TW202236993A (zh) 2020-12-30 2022-10-01 荷蘭商耐克創新有限合夥公司 用於鞋件鞋底結構的囊袋
USD929723S1 (en) * 2021-01-13 2021-09-07 Nike, Inc. Cushioning device for footwear
USD929726S1 (en) * 2021-01-13 2021-09-07 Nike, Inc. Cushioning device for footwear
USD929725S1 (en) * 2021-01-13 2021-09-07 Nike, Inc. Cushioning device for footwear
USD929724S1 (en) * 2021-01-13 2021-09-07 Nike, Inc. Cushioning device for footwear
USD929100S1 (en) * 2021-01-13 2021-08-31 Nike, Inc. Cushioning device for footwear
US11820890B2 (en) 2021-04-01 2023-11-21 Stratasys Inc Pulverulent thermoplastic polymer blends
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EP4322789A1 (en) 2021-04-12 2024-02-21 NIKE Innovate C.V. Article of footwear having articulating strobel with bladder and tensile component
US20230172308A1 (en) 2021-12-03 2023-06-08 Nike, Inc. Article of footwear with extended plate for toe-off
US20230204822A1 (en) 2021-12-29 2023-06-29 Nike, Inc. Structurally-colored articles and methods for making and using structurally-colored articles
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WO2024026233A1 (en) 2022-07-28 2024-02-01 Nike Innovate C.V. Article of footwear with bladder at foot-facing surface of foam midsole layer
US20240074533A1 (en) 2022-09-01 2024-03-07 Nike, Inc. Article of footwear with stacked forefoot bladders

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410595A (en) * 1979-03-08 1983-10-18 Asahi Kasei Kogyo Kabushiki Kaisha Laminate of thermoplastic resinous composition
US4639471A (en) * 1985-02-12 1987-01-27 Kuraray Co., Ltd. Process for producing polyester polyurethane
US5036110A (en) * 1988-09-20 1991-07-30 Automobiles Peugeot Impervious resilient membrane and hydropneumatic accumulator fitted with that membrane
US5069946A (en) * 1987-12-29 1991-12-03 Kuraray Co., Ltd. Multilayered packaging materials having high gas barrier property

Family Cites Families (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4731289Y1 (zh) * 1969-10-20 1972-09-20
US3718494A (en) * 1971-03-04 1973-02-27 Du Pont Sheet-like alpha aluminum oxide
GB1489635A (en) * 1975-03-03 1977-10-26 Toyo Seikan Kaisha Ltd Packaging materials
JPS5917672B2 (ja) 1975-12-05 1984-04-23 三井・デュポン ポリケミカル株式会社 ナンシツタソウシ−ト ノ セイゾウホウホウ
US4340626A (en) * 1978-05-05 1982-07-20 Rudy Marion F Diffusion pumping apparatus self-inflating device
US4257176A (en) * 1979-03-09 1981-03-24 Scholl, Inc. Insole with material released under foot loads
US4429076A (en) * 1979-06-13 1984-01-31 Asahi Kasei Kogyo Kabushiki Kaisha Thermoplastic polymer composition
ATE18292T1 (de) * 1979-11-28 1986-03-15 Wirsbo Bruks Ab Gasundurchlaessiger artikel.
US5059245A (en) * 1979-12-28 1991-10-22 Flex Products, Inc. Ink incorporating optically variable thin film flakes
US4731289A (en) * 1980-02-14 1988-03-15 Ppg Industries, Inc. Abrasion resistant polyurethane coatings for rigid plastics
US4423185A (en) * 1980-03-03 1983-12-27 Asahi Kasei Kogyo Kabushiki Kaisha Thermoplastic resinous composition
DE3030056A1 (de) * 1980-08-08 1982-03-25 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von mit metalloxiden beschichteten schuppenfoermigen glimmerpigmenten
US4731266A (en) * 1981-06-03 1988-03-15 Rhone-Poulenc, S.A. Water-resistant polyvinyl alcohol film and its application to the preparation of gas-impermeable composite articles
JPS5822163A (ja) * 1981-07-31 1983-02-09 株式会社クラレ ガスバリヤ−性積層物
EP0103695A1 (en) * 1982-07-16 1984-03-28 Showa Denko Kabushiki Kaisha Vulcanized olefin-based rubber composition
JPS59116145A (ja) * 1982-12-22 1984-07-04 Sumitomo Electric Ind Ltd 光伝送用ガラスフアイバの被覆方法
US4513085A (en) 1982-10-07 1985-04-23 Eli Lilly And Company Functionally independent cloning vectors for use in streptomyces
JPS59196706A (ja) * 1983-04-22 1984-11-08 Dainippon Ink & Chem Inc 不均質膜およびその製造方法
JPS6024947A (ja) * 1983-07-21 1985-02-07 マツダ株式会社 塗装を施した繊維強化ウレタン成形品
DE3426875C2 (de) * 1983-07-21 1993-12-16 Kuraray Co Verfahren zur Herstellung von Polyurethanen mit überragender Hydrolysebeständigkeit
BR8305086A (pt) * 1983-09-19 1984-03-20 Antonio Signori Dispositivo de amortecimento aplicavel a calcados em geral
US4513058A (en) * 1984-04-17 1985-04-23 Wilson Sporting Goods Co. Impact resistant high air retention bladders
US4536425A (en) * 1984-06-08 1985-08-20 Continental Can Company Method for preparing polar thermoplastic resin compositions having improved gas barrier properties
DE3435233A1 (de) * 1984-09-26 1986-04-03 N.V. Cobelplast S.A., Lokeren Thermoverformbare, mehrschichtige kunststoffolie mit gasabdichteigenschaften
US4692361A (en) * 1984-09-28 1987-09-08 Baxter Travenol Laboratories, Inc. Film laminate with gas barrier for sterile flexible containers
US4670995A (en) * 1985-03-13 1987-06-09 Huang Ing Chung Air cushion shoe sole
JPS62116145A (ja) 1985-11-15 1987-05-27 川上産業株式会社 合成樹脂中空体
US4890822A (en) 1986-02-13 1990-01-02 Nhk Spring Co., Ltd. Car suspension system
GB8605997D0 (en) 1986-03-11 1986-04-16 Edeco Holdings Ltd Plastics films
JPS62253428A (ja) 1986-04-25 1987-11-05 Okura Ind Co Ltd 車両用多層チユ−ブ
GB8617535D0 (en) * 1986-07-17 1986-08-28 Du Pont Canada Gas barrier structures
GB2193966B (en) * 1986-08-01 1990-01-31 Nippon Synthetic Chem Ind Thermoplastic resin composition
US5036603A (en) * 1986-10-20 1991-08-06 Milliken Research Corporation Insole product and method of making same
ATE98449T1 (de) * 1987-07-09 1994-01-15 Hi Tec Sports Ltd Sport- oder freizeitschuh mit stossdaempfender sohle.
US4874670A (en) 1987-11-30 1989-10-17 The Goodyear Tire & Rubber Company Tire having cured photopolymer air barrier coating
US5036113A (en) 1987-11-30 1991-07-30 The Goodyear Tire & Rubber Company Tire having radiation cured air barrier coating
US4865738A (en) 1987-12-03 1989-09-12 Cuno, Incorporated Filter cartridge with truncated sawtooth projection assembly
US5300541A (en) * 1988-02-04 1994-04-05 Ppg Industries, Inc. Polyamine-polyepoxide gas barrier coatings
AU616730B2 (en) * 1988-02-29 1991-11-07 Kuraray Co., Ltd. Multilayered container
US5591798A (en) * 1988-04-11 1997-01-07 Advanced Elastomer Systems, L.P. High temperature stable, low solvent swelling thermoplastic elastomer compositions
DE3813335A1 (de) * 1988-04-21 1989-11-02 Basf Ag Metalloxidbeschichtete aluminiumpigmente
US4864738A (en) * 1988-07-19 1989-09-12 Zvi Horovitz Sole construction for footwear
US5089353A (en) * 1988-10-14 1992-02-18 Kuraray Co., Ltd. Multi-layer material having gas barrier properties
DE3835840A1 (de) * 1988-10-21 1990-05-31 Hoechst Ag Polyvinylacetalgruppen enthaltende pfropfpolymerisate auf polyurethanpfropfgrundlagen, verfahren zu ihrer herstellung und ihre verwendung
US4936029A (en) * 1989-01-19 1990-06-26 R. C. Bogert Load carrying cushioning device with improved barrier material for control of diffusion pumping
US5042176A (en) * 1989-01-19 1991-08-27 Robert C. Bogert Load carrying cushioning device with improved barrier material for control of diffusion pumping
FR2643823B1 (fr) * 1989-03-03 1992-05-15 Adidas Chaussures Ballons de sports ou de loisirs, comprenant une couche externe en mousse a peau integrale et leur obtention
CA2012141C (en) * 1989-03-17 1999-07-27 Daniel R. Potter Customized fit shoe and bladder and valve assembly therefor
CA2015416C (en) * 1989-04-27 1994-12-27 Yoshinori Takahashi Disc cartridge
US5003002A (en) * 1989-08-14 1991-03-26 Rampart Packaging Inc. Blends of amorphous nylon and ethylene vinyl alcohol copolymers and laminates and containers made therefrom
FR2651785B1 (fr) * 1989-09-14 1991-12-06 Atochem Alliages a base d'un copolymere ethylene alcool vinylique a propriete barriere aux gaz, thermoformable et/ou resistant a la flexion repetee.
US5632057A (en) * 1989-09-20 1997-05-27 Lyden; Robert M. Method of making light cure component for articles of footwear
EP0521877A1 (en) * 1990-03-23 1993-01-13 E.I. Du Pont De Nemours And Company Polymer foams containing gas barrier resins
US5096756A (en) * 1990-04-02 1992-03-17 Wilson Sporting Goods Co. Composite bladder for game balls
FR2662638B1 (fr) * 1990-05-31 1997-09-05 Nok Corp Feuille laminee resistante au froid et formant barriere aux gaz, vessie pour accumulateur et accumulateur la comprenant.
JP3049614B2 (ja) * 1990-09-26 2000-06-05 エヌオーケー株式会社 アキュムレータ用ブラダ
DE4030727A1 (de) * 1990-09-28 1992-04-02 Eckart Standard Bronzepulver Kunstharzbeschichtete metallpigmente, verfahren zu ihrer herstellung und ihre verwendung
EP0504433B1 (en) * 1990-10-09 1997-06-18 Daicel Chemical Industries, Ltd. Laminated film and production thereof
US5215124A (en) * 1990-10-23 1993-06-01 Honda Giken Kogyo Kabushiki Kaisha Accumulator
US5157082A (en) * 1990-11-13 1992-10-20 Synesis Corporation Thermoplastic compositions containing ground vulcanized rubber and polyolefin resin
JPH083121B2 (ja) 1990-11-16 1996-01-17 健 増本 塗料用アルミニウム合金粉末
DE69227367T2 (de) * 1991-04-26 1999-05-20 Ppg Industries Inc Unter druck setzbarer kunststoffbehälter mit einer aussenschicht aus polyurethan sowie verfahren zu dessen herstellung
IT1256693B (it) * 1992-03-10 1995-12-12 Novamont Spa Composizione polimerica amidacea filmabile, ed articoli sagomati, particolarmente film e foglie ottenibili da tale composizione, aventi elevato effetto barriera e procedimento relativo.
US5458935A (en) * 1991-12-24 1995-10-17 Abbott Laboratories Thermoplastic urethane elastomer
JP3185809B2 (ja) * 1992-03-19 2001-07-11 三菱瓦斯化学株式会社 ポリアセタール樹脂組成物
DE4217511A1 (de) * 1992-05-27 1993-12-02 Basf Ag Glanzpigmente auf der Basis von mehrfach beschichteten plättchenförmigen metallischen Substraten
EP0642550A1 (en) * 1992-05-29 1995-03-15 Ferro Corporation Radio frequency weldable polymer articles
JPH069832A (ja) * 1992-06-26 1994-01-18 Showa Denko Kk 接着性樹脂組成物
US5700560A (en) * 1992-07-29 1997-12-23 Sumitomo Chemical Company, Limited Gas barrier resin composition and its film and process for producing the same
US5429852A (en) * 1992-12-21 1995-07-04 Quinn; Raymond Transportable chair pad
US5436295A (en) * 1993-01-20 1995-07-25 Kuraray Company, Ltd. Thermoplastic elastomer composition
DE4315663A1 (de) 1993-05-11 1994-11-17 Wolff Walsrode Ag Flexible siegelfähige Mehrschichtfolie aus thermoplastischen Elastomeren mit innenliegender Sperrschicht
US5567489A (en) * 1993-09-16 1996-10-22 The Dow Chemical Company Multilayer halogen-free barrier film for ostomy and transdermal drug delivery applications
US5589252A (en) * 1993-09-30 1996-12-31 Toppan Printing Co., Ltd. Gas barrier laminated material
JP2811540B2 (ja) * 1993-10-20 1998-10-15 呉羽化学工業株式会社 ガスバリヤー性フィルム及びその製造方法
US5456787A (en) * 1993-12-01 1995-10-10 J. E. Miles, Inc. Method for making a hydropneumatic accumulator
US5648149A (en) * 1994-03-29 1997-07-15 Ppg Industries, Inc. Adhesion of thermoset polyurethane to rigid transparent substrates
DE4421933A1 (de) * 1994-06-23 1996-01-04 Basf Ag Glanzpigmente mit stickstoffhaltigen Metallschichten
US5952065A (en) 1994-08-31 1999-09-14 Nike, Inc. Cushioning device with improved flexible barrier membrane
JP3315271B2 (ja) * 1994-09-21 2002-08-19 呉羽化学工業株式会社 積層樹脂成形体
EP0718347A1 (en) * 1994-12-24 1996-06-26 Advanced Elastomer Systems, L.P. Method to adhere thermoplastic elastomer blends to polyester substrates
TW369499B (en) * 1995-05-12 1999-09-11 Sumitomo Chemical Co Formed hollow container and process
US5524961A (en) * 1995-05-15 1996-06-11 Howard; Charles R. Pneumatic bicycle saddle
CA2222097C (en) * 1995-06-07 2009-03-24 Nike International Ltd. Membranes of polyurethane based materials including polyester polyols
US6013340A (en) * 1995-06-07 2000-01-11 Nike, Inc. Membranes of polyurethane based materials including polyester polyols
US5562324A (en) * 1996-02-02 1996-10-08 Lear Seating Corporation Lumbar support actuation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410595A (en) * 1979-03-08 1983-10-18 Asahi Kasei Kogyo Kabushiki Kaisha Laminate of thermoplastic resinous composition
US4639471A (en) * 1985-02-12 1987-01-27 Kuraray Co., Ltd. Process for producing polyester polyurethane
US5069946A (en) * 1987-12-29 1991-12-03 Kuraray Co., Ltd. Multilayered packaging materials having high gas barrier property
US5036110A (en) * 1988-09-20 1991-07-30 Automobiles Peugeot Impervious resilient membrane and hydropneumatic accumulator fitted with that membrane

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