CN106988125B - 具有聚酯型聚氨酯和聚碳酸酯型聚氨酯混合物制成的连续涂层的织物衬底 - Google Patents

具有聚酯型聚氨酯和聚碳酸酯型聚氨酯混合物制成的连续涂层的织物衬底 Download PDF

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CN106988125B
CN106988125B CN201611044841.8A CN201611044841A CN106988125B CN 106988125 B CN106988125 B CN 106988125B CN 201611044841 A CN201611044841 A CN 201611044841A CN 106988125 B CN106988125 B CN 106988125B
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R·凯沙瓦拉杰
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Abstract

一种涂层织物衬底，其包含具有内侧和外侧的织物衬底和在所述织物衬底至少一侧上的连续涂层。所述连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物。

Description

具有聚酯型聚氨酯和聚碳酸酯型聚氨酯混合物制成的连续涂 层的织物衬底
技术领域
本发明提供一种适于在气囊上使用的连续涂层成分、一种涂布有此种成分的气囊、一种制造此种气囊的方法、以及一种包括此种气囊的气囊模块。
背景技术
用于机动车的气囊已在客运车辆上普遍存在。这些气囊被安装在车辆乘客室的关键点处，在发生碰撞时，这些气囊迅速充气膨胀，以作为车中乘客与乘客室内表面(例如，方向盘、仪表盘或车窗)之间的能量吸收屏障。例如，侧帘式气囊通常安装在车辆的一个或多个柱子中，以在发生翻车或侧面冲击碰撞时提供保护。随着这种气囊的出现，制造商们开始在气囊织物上涂布涂层，以改变织物的透气性，使得由织物制成的气囊膨胀时间更长，并在发生碰撞期间提供保护。
目前有许多类型的涂层成分用于生产这种涂层织物，但是特别受欢迎的一类涂层成分是聚合物在适当介质(例如，水介质)中的分散体。尽管这些分散型体系非常受欢迎，但是它们并非没有缺点和不同于溶剂型体系的困难。
二次撞击或翻车侧帘应用情况所需的涂层与正面气囊相比需要有更高水平的性能，在发生翻车时，这些侧帘需要保持气体5秒以上。在此类应用中通常使用高涂层重量的硅树脂基弹性体，其中涂层重量介于65到125GSM。已证明可通过高模量涂层减小涂层重量，高模量涂层可通过小心选择材料而在老化之后仍然保持性能。在此类实施例中，需要将聚碳酸酯二醇制成的聚氨酯作为软链段，以在老化之后维持物理特性。已出现其他体系，其中通过用两种二醇(即，聚碳酸酯和聚醚)制成混合聚氨酯克服了与聚碳酸酯基聚氨酯相关的僵硬。尽管后者体系满足了性能要求，但仍需要降低聚氨酯的成本，并进一步改善如硬度、附着力等特性。
发明内容
一种涂层织物衬底，其包含具有内侧和外侧的织物衬底以及至少在织物衬底的外侧上的连续涂层。该连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物。
一种气囊，其包括：织物衬底，其具有内侧和外侧，以及在所述织物衬底的至少一侧上的连续涂层，其中所述连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物。
一种气囊模块，包括：气囊，所述气囊包围内部空间，并包括：织物衬底，其具有内侧和外侧；以及，在所述织物衬底的至少一侧上的连续涂层，其中所述连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物；气体发生器，所述气体发生器连接至所述气囊；以及盖子，其至少部分地包围所述气囊和所述气体发生器。
一种用于形成涂层织物的方法，其包括水性聚碳酸酯型聚氨酯分散体和水性聚酯型聚氨酯分散体。所述聚碳酸酯型聚氨酯分散体包括多个聚碳酸酯型聚氨酯颗粒和水溶液，且所述聚碳酸酯型聚氨酯颗粒具有小于约1微米的平均粒径。所述聚酯型聚氨酯分散体包括多个聚酯型聚氨酯颗粒和水溶液，且所述聚酯型聚氨酯颗粒具有小于5微米的平均粒径。
将所述聚碳酸酯型聚氨酯分散体和聚酯型聚氨酯分散体混合在一起，形成物理混合物，其中该物理混合物含有约5到35重量％的聚碳酸酯型聚氨酯分散体以及约65到95重量％的聚酯型聚氨酯分散体。该物理混合物被涂布到具有内侧和外侧的织物衬底上，其中该涂层至少覆盖该织物的一侧。
使用热来干燥涂层织物，其中所述热可干燥所述物理混合物的水成分的至少一部分，使聚碳酸酯型聚氨酯颗粒和聚酯型聚氨酯颗粒至少部分地熔融并相互结合，形成连续涂层。
具体实施方式
为了织物衬底上的气体保持涂层，已有许多不同的聚氨酯被开发和测试。使用聚酯二醇形成的聚氨酯比聚碳酸酯二醇或聚醚二醇更便宜，但是在高温高湿环境中性能较差。聚酯主链在此种环境中容易发生降解，因为高温和水解作用会对其造成自由基攻击。酯链的水解会使涂层的分子量降低，导致涂层性能降低。另一方面，聚碳酸酯二醇基聚氨酯因其出色的强度、水解稳定性和抗氧化性而闻名。然而，这种石油衍生的多元醇的商业应用仍然是有限的和小范围的，因为与聚醚二醇和聚酯二醇相比其相对成本较高。
已发现，通过将较软的聚酯型聚氨酯与硬得多的聚碳酸酯型聚氨酯混合，可制成更软的、强度同样更高的、延长率相似的聚氨酯。还发现，通过适当地选择聚酯二醇结合聚碳酸酯二醇，可改善聚酯型聚氨酯总体的老化性能。
在一个实施方案中，本发明提供一种气囊。该气囊可适于用作机动车中的任何气囊，例如正面碰撞气囊(例如，驾驶员或乘客侧正面碰撞气囊)或侧面碰撞气囊(例如，侧帘气囊或侧面躯干气囊)。气囊包含织物衬底和位于该织物衬底的至少一部分上的涂层。气囊也可被配制成包围内部空间。例如，气囊可包含至少两个独立的织物衬底，这两个独立的织物衬底被缝纫、缝合、或以其他方式结合在一起，使其包围起一个可以充气膨胀的内部空间。作为另一种选择，该气囊可以是一件式编织气囊，主要包括织物衬底，该织物衬底具有两层区域和单层区域，其中这两层被编织到一起，以包围可充气膨胀的内部空间。这种一件式编织气囊及其适合的结构例如在美国专利7,543,609、7,409,970、7,069,961、6,595,244和6,220,309中有所描述。
(在某些实施方案中的气囊的)织物衬底可以是任何具有内侧和外侧的适当织物衬底。优选地，织物衬底是编织衬底。这种编织衬底包括多个以适当编织图案交错的纱线，例如平纹梭织、斜纹编织或缎纹组织。优选地，织物衬底是以平纹梭织构成的编织织物。编织织物可由任何适当的纱线或纱线组合构成。优选地，织物衬底是包括多个合成纱线的编织织物。合成纱线可包含任何合适的合成纤维。优选地，合成纱线包括选自以下组中的纤维：聚酰胺纤维(例如尼龙6纤维，尼龙6,6纤维)、聚酯纤维(例如，聚对苯二甲酸乙二醇酯纤维、聚对苯二甲酸丙二醇酯纤维、聚对苯二甲酸丁二醇酯纤维)、聚烯烃纤维及上述纤维的混合物。在更优选的实施方案中，合成纱线包括选自以下组中的纤维：聚酰胺纤维、聚酯(PET)纤维、聚烯烃纤维、聚对苯二甲酸丙二醇酯纤维(PTT)及上述纤维的混合物。
用于制作织物衬底的纱线可具有任何适当的线密度。优选地，纱线具有约100dtex或更高，或者约110dtex或更高的线密度。优选地，纱线具有约1500dtex或更低，或者约700dtex或更低的线密度。用于制作织物衬底的纱线优选地是复丝纱线，这意味着每根纱线包含多个细丝或纤维，例如上文中提到的那些纤维。在这种复丝纱线中，细丝或纤维优选地具有约7dtex或更低，或者约5dtex或更低(例如，约4.5dtex或更低)的线密度。
织物衬底在该织物衬底的至少一侧上具有连续涂层。连续涂层是聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物。这种混合物是两种聚合物的物理混合物(分别形成，然后混合)，不是包含聚酯型聚氨酯和聚碳酸酯型聚氨酯的单聚合物主链。
形成涂层织物的过程，首先分别形成聚酯型聚氨酯的分散体和聚碳酸酯型聚氨酯的分散体。所形成的聚酯型聚氨酯分散体是多个聚酯型聚氨酯颗粒在水溶液中的分散体。聚酯型聚氨酯颗粒优选地具有小于5微米、更优选地小于3微米的平均粒径。在一个实施方案中，聚酯型聚氨酯分散体包含约40至75重量％的聚酯型聚氨酯颗粒。
所形成的聚碳酸酯型聚氨酯颗粒分散体是多个聚碳酸酯型聚氨酯颗粒在水溶液中的分散体。聚碳酸酯型聚氨酯颗粒优选地具有小于约1微米、更优选地约100到800纳米的平均粒径。在一个实施方案中，聚碳酸酯型聚氨酯分散体包含约25至60重量％的聚碳酸酯型聚氨酯颗粒。
两种聚氨酯分散体，聚碳酸酯型聚氨酯分散体和聚酯型聚氨酯分散体混合在一起形成物理混合物，其中该物理混合物包含约5至35重量％的聚碳酸酯型聚氨酯和65到95重量％的聚酯型聚氨酯。在另一实施方案中，该物理混合物包含大于约50重量％的聚酯型聚氨酯，更优选地大于约70重量％的聚酯型聚氨酯。在另一实施方案中，该物理混合物包含少于约50重量％的聚碳酸酯聚氨酯，更优选地少于约30重量％的聚碳酸酯聚氨酯。在一个实施方案中，该物理混合物包含约20到30重量％的聚碳酸酯型聚氨酯和约70到80重量％的聚酯型聚氨酯。
然后，将物理混合物涂布到织物衬底上，使得物理混合物的涂层至少覆盖织物衬底的至少一侧。所用涂布方法可为任何合适的涂布方法，包括但不限于凹面涂布、刮刀涂布、印刷以及转移涂布。
使用热来干燥涂层织物衬底，使形成干燥涂层的物理混合物涂层的水成分的至少一部分干燥。所述热使得物理混合物形成干燥涂层，并使聚碳酸酯型聚氨酯颗粒和聚酯型聚氨酯颗粒的至少一部分熔融并彼此结合在一起，以形成连续涂层。
在一个实施方案中，干燥的连续涂层具有小于约100克每平方米，更优选地小于约50克每平方米的单位面积重量。
涂层织物衬底可用于任何适当的目的，尤其是在良好环境老化下要求气阻的应用。气囊可用于任何适当的目的。在一个实施例中，气囊是气囊模块的一部分，其中气囊包围内部空间，且该模块还包括连接到气囊的气体发生器和至少部分包围气囊和气体发生器的盖子。此气囊和/或气囊模块可用于任何合适的装置，例如轿车、卡车、SUV或飞机等运载工具。
实施例：
测试了不同多元醇基聚氨酯的各种组合在高温高湿老化条件后的拉伸保留率％、100％模量和伸长性能。已发现聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物中聚酯型聚氨酯为少数成分，某些常规聚酯基聚氨酯的材料性能的保留率％可提高至100％聚碳酸酯基聚氨酯的水平。
该物理混合方法避免了常规方法中首先要通过酯基转移反应将两种二元醇聚合，以制成聚酯-聚碳酸酯二元醇杂化物(hybrid)。其还允许通过常规的预聚物路径或丙酮脱离路径分别合成聚酯基聚氨酯和聚碳酸酯基聚氨酯。
优选聚氨酯中使用的聚酯二醇是常规的己二酸/新戊二醇/1,6-己二醇聚酯二醇，其含有少量的环氧乙烷/环氧丙烷聚醚，以实现热稳定。除了已知能提高抗水解性能的HDO(己二醇)，这种特别的聚氨酯在暴露于70℃/95％RH(相对湿度)仅1周之后便会失去大于50％的最终抗拉强度，在同样条件下持续两周之后仅保留原始的6％。这表明了这些材料暴露在这种特别的应用中的测试条件的恶劣性。
聚氨酯的聚碳酸酯侧被制成杂化物，聚碳酸酯相对于聚酯多醇的比例为80:20。加入后者是为了帮助减少聚碳酸酯树脂的100％模量，从而降低涂层织物的硬度。在这种情况下，两种多元醇都是在预聚物合成的反应阶段加入的。完全反应的纯聚碳酸酯型聚氨酯和聚酯型聚氨酯的混合在材料性能或硬度减小方面不会产生相同的结果。据信后一种现象是因为在混合时，完全反应的产物存留的两个不同的域从来没有产生期望的特性。
将上述两种聚氨酯以各种比例混合，并使每种混合制成的膜在各种老化条件下老化。测量每个体系的膜的拉伸保留率％、伸长率和100％模量。首先，分别评估聚酯基聚氨酯和聚碳酸酯基聚氨酯中的每一者，以了解性能，然后选择进行混合的最后两个候选物质。根据在其他应用中改善的水解稳定性能选择两种不同类型的聚酯基PUD。用每个候选物质铸造两组自由膜，使其中一组膜在85℃/95RH条件下老化17天。老化的膜在与未老化的膜同时测试之前调整处理24小时。结果发现，该混合物在老化之后保留上述三种特性的80％，而且与100％聚碳酸酯成分非常相似。
商业上可买到的常规的己二酸/新戊二醇/1,6-己二醇聚酯二醇基聚酯型聚氨酯具有6000Psi的极限抗拉强度、578Psi的100％模量和610％的极限伸长率，选择将其与比例为80:20的聚碳酸酯:聚酯型聚氨酯混合，该聚氨酯的极限抗拉强度为4263Psi、867Psi的100％模量和344％的极限伸长率。将选定的混合物涂布到OPW气囊上，发现在老化部署和未老化部署中气囊保持压力峰值的至少25％达6秒钟。该性能被认为足够在发生翻车型事故时约束车内乘客。
本文引用的所有参考文献，包括出版物、专利申请和专利均以参考方式并入本文，犹如分别并具体指明每个参考文献均以参考方式并入本文，并在本文中对其进行整体描述。
除非本文中另外指明或者上下文明显矛盾，在描述本申请主题的上下文中(尤其是在下列权利要求书的上下文中)使用的词语“一”、“一个”、以及“所述”和类似指代词应被解释为涵盖单数形式和复数形式。除非另外指明，词语“包含”、“具有”、“包括”和“含有”应被解释为开放性词语(即，意思是“包括但不限于”)。除非本文另外指明，本文中数值范围的详述目的仅作为单独参考该范围内每个独立数值的简单表达方法，而且每个独立数值被并入本说明书，犹如其单独在本文中引用。除非本文中另外指明或者上下文明显矛盾，本文所述所有方法均可以任何适当的顺序执行。除非另外指明，本文中使用的任何和所有实例或者举例性语言(例如，“例如”)目的仅在于更好地说明本申请的主题，并非对主题范围进行限制。本说明书中的所有语言都不应被解释为用来说明本文所述主题实践中所必须的任何非权利保护的元素。
本文描述了本申请主题的优选实施例，包括发明人所知的用于执行所保护主题的最佳模式。本领域的普通技术人员在阅读上述说明书时，这些优选实施例的变型可变得显而易见。发明人期望技术人员适当利用这些变型，且发明人希望本文所述的主题可通过除本文具体描述以外的方法实施。因此，本公开包括适用法律允许的随附权利要求书中所引用主题的所有修改和等效内容。此外，除非本文中另外指明或者上下文明显矛盾，本公开包括上述元素在所有可能变型中的任何组合。

Claims (21)

1.一种涂层织物衬底，包括：
织物衬底，其具有内侧和外侧；以及
在所述织物衬底的至少一侧上的连续涂层，其中所述连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物；其中该混合物是通过以下方法制备的：
a.形成水性聚碳酸酯型聚氨酯分散体，其中所述聚碳酸酯型聚氨酯分散体包括多个聚碳酸酯型聚氨酯颗粒和水溶液，其中所述聚碳酸酯型聚氨酯颗粒具有小于1微米的平均粒径；
b.形成水性聚酯型聚氨酯分散体，其中所述聚酯型聚氨酯分散体包括多个聚酯型聚氨酯颗粒和水溶液，其中所述聚酯型聚氨酯颗粒具有小于5微米的平均粒径；以及
c.将所述聚碳酸酯型聚氨酯分散体和所述聚酯型聚氨酯分散体混合在一起形成物理混合物，其中所述物理混合物含有5到35重量％的聚碳酸酯型聚氨酯分散体和65到95重量％的聚酯型聚氨酯。
2.如权利要求1所述的涂层织物衬底，其中所述连续涂层具有小于50克每平方米的单位面积重量。
3.如权利要求1所述的涂层织物衬底，其中所述涂层包含大于70重量％的聚酯型聚氨酯。
4.如权利要求1所述的涂层织物衬底，其中所述涂层包含少于30重量％的聚碳酸酯型聚氨酯。
5.一种气囊，其包括：
织物衬底，其具有内侧和外侧，以及
在所述织物衬底的至少一侧上的连续涂层，其中所述连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物；其中该混合物是通过以下方法制备的：
a.形成水性聚碳酸酯型聚氨酯分散体，其中所述聚碳酸酯型聚氨酯分散体包括多个聚碳酸酯型聚氨酯颗粒和水溶液，其中所述聚碳酸酯型聚氨酯颗粒具有小于1微米的平均粒径；
b.形成水性聚酯型聚氨酯分散体，其中所述聚酯型聚氨酯分散体包括多个聚酯型聚氨酯颗粒和水溶液，其中所述聚酯型聚氨酯颗粒具有小于5微米的平均粒径；以及
c.将所述聚碳酸酯型聚氨酯分散体和所述聚酯型聚氨酯分散体混合在一起形成物理混合物，其中所述物理混合物含有5到35重量％的聚碳酸酯型聚氨酯分散体和65到95重量％的聚酯型聚氨酯。
6.如权利要求5所述的气囊，其中所述连续涂层具有小于50克每平方米的单位面积重量。
7.如权利要求5所述的气囊，其中所述涂层包含大于70重量％的聚酯型聚氨酯。
8.如权利要求5所述的气囊，其中所述涂层包含少于30重量％的聚碳酸酯型聚氨酯。
9.一种交通工具，包括如权利要求5所述的气囊。
10.一种气囊模块，包括：
(a)气囊，所述气囊包围内部空间，并包括：
织物衬底，其具有内侧和外侧；以及，
在所述织物衬底的至少一侧上的连续涂层，其中所述连续涂层包括聚酯型聚氨酯和聚碳酸酯型聚氨酯的混合物；其中该混合物是通过以下方法制备的：
i.形成水性聚碳酸酯型聚氨酯分散体，其中所述聚碳酸酯型聚氨酯分散体包括多个聚碳酸酯型聚氨酯颗粒和水溶液，其中所述聚碳酸酯型聚氨酯颗粒具有小于1微米的平均粒径；
ii.形成水性聚酯型聚氨酯分散体，其中所述聚酯型聚氨酯分散体包括多个聚酯型聚氨酯颗粒和水溶液，其中所述聚酯型聚氨酯颗粒具有小于5微米的平均粒径；以及
iii.将所述聚碳酸酯型聚氨酯分散体和所述聚酯型聚氨酯分散体混合在一起形成物理混合物，其中所述物理混合物含有5到35重量％的聚碳酸酯型聚氨酯分散体和65到95重量％的聚酯型聚氨酯；
(b)气体发生器，所述气体发生器连接至所述气囊；以及，
(c)盖子，其至少部分地包围所述气囊和所述气体发生器。
11.如权利要求10所述的气囊模块，其中所述涂层含有少于30重量％的聚碳酸酯型聚氨酯。
12.一种交通工具，包括如权利要求10所述的气囊模块。
13.一种用于形成涂层织物的方法，包括：
a.形成水性聚碳酸酯型聚氨酯分散体，其中所述聚碳酸酯型聚氨酯分散体包括多个聚碳酸酯型聚氨酯颗粒和水溶液，其中所述聚碳酸酯型聚氨酯颗粒具有小于1微米的平均粒径；
b.形成水性聚酯型聚氨酯分散体，其中所述聚酯型聚氨酯分散体包括多个聚酯型聚氨酯颗粒和水溶液，其中所述聚酯型聚氨酯颗粒具有小于5微米的平均粒径；
c.将所述聚碳酸酯型聚氨酯分散体和所述聚酯型聚氨酯分散体混合在一起形成物理混合物，其中所述物理混合物含有5到35重量％的聚碳酸酯型聚氨酯分散体和65到95重量％的聚酯型聚氨酯；
d.将所述物理混合物涂布到具有内侧和外侧的织物衬底上，其中所述涂层至少覆盖所述织物的一侧；以及
e.使用热来干燥所述涂层织物，其中所述热干燥所述物理混合物的水成分的至少一部分，并使所述聚碳酸酯型聚氨酯颗粒和所述聚酯型聚氨酯颗粒至少部分地熔融并相互结合，形成连续涂层。
14.如权利要求13所述的方法，其中所述聚碳酸酯型聚氨酯分散体包含25到60重量％的聚碳酸酯型聚氨酯颗粒。
15.如权利要求13所述的方法，其中所述聚酯型聚氨酯分散体包含40到75重量％的聚酯型聚氨酯颗粒。
16.如权利要求13所述的方法，其中所述聚碳酸酯型聚氨酯颗粒具有100到800纳米的平均粒径。
17.如权利要求13所述的方法，其中所述聚酯型聚氨酯颗粒具有小于3微米的平均粒径。
18.如权利要求16所述的方法，其中所述连续涂层具有小于50克每平方米的单位面积重量。
19.如权利要求13所述的方法，其中所述涂层包含大于70重量％的聚酯型聚氨酯。
20.如权利要求13所述的方法，其中所述涂层包含少于30重量％的聚碳酸酯型聚氨酯。
21.通过如权利要求13所述的方法形成的涂层织物。
CN201611044841.8A 2015-12-17 2016-11-24 具有聚酯型聚氨酯和聚碳酸酯型聚氨酯混合物制成的连续涂层的织物衬底 Active CN106988125B (zh)

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