CN101346228B - 防水、可透水蒸气的多层膜 - Google Patents

防水、可透水蒸气的多层膜 Download PDF

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CN101346228B
CN101346228B CN200680049095XA CN200680049095A CN101346228B CN 101346228 B CN101346228 B CN 101346228B CN 200680049095X A CN200680049095X A CN 200680049095XA CN 200680049095 A CN200680049095 A CN 200680049095A CN 101346228 B CN101346228 B CN 101346228B
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CN101346228A (zh
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G·B·维特曼
H·J·M·范德文
A·A·基尔
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Sympatex Technologies GmbH
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Abstract

防水、可透水蒸气的多层膜，具有至少一个第一层和一个第二层，其中所有的层都由选自聚醚酯类、聚醚酰胺类或聚醚氨基甲酸酯类的热塑性聚合物构成，并彼此连接。该膜的特征在于相邻排列的层由不同类的热塑性聚合物制成。

Description

防水、可透水蒸气的多层膜
本发明涉及一种防水、可透水蒸气的多层膜，其具有至少一个第一层和一个第二层，其中所有的层均由选自聚醚酯类、聚醚酰胺类或聚醚聚氨酯类的热塑性聚合物制成，并连接在一起。
该膜可由例如EP 1,264,684 A1获知的。在这些膜中，第一层是通过用含有热塑性聚合物的溶液涂覆载体而制备的。然后，通过涂覆第一层而制备膜的第二层。在该公开的发明中指出，多层膜获得了必要的水蒸气可渗透性，原因是在用第二层的聚合物涂覆第一层之前，将相容的亲水性增塑剂加入其中。而且根据EP 1,264,684 A1，相邻的层应当使用相同或相似的聚合物。这是因为如果在相邻的层中使用不同类型的上述聚合物，则相邻层就只会不牢固地彼此连接，结果该多层膜在最轻微的负载下也将会分层，即，分成单独的层，并且将不再是多层膜或至少不再能够原样使用。
本发明的目的是提供另一种防水、可透水蒸气的多层膜。
使用本发明的防水、可透水蒸气的多层膜，实现了上述目的，该多层膜具有至少一个第一层和一个第二层，其中所有的层均由选自聚醚酯类、聚醚酰胺类或聚醚聚氨酯类的热塑性聚合物制成，并连接在一起，其特征在于相邻排列的层由不同类的热塑性聚合物制成。
事实上发现，通过选择性地选择聚合物，尽管聚合物不同，但多层膜也可以实现相邻层的可接受的粘附和连接，因此明显降低了分层的可能。连接相邻的聚合物层通常需要偶联剂。选择本发明聚合物可以不使用这些偶联剂。在此也不必添加增塑剂。因而本发明的膜的特征特别在于所有的层不含增塑剂和偶联剂。本发明膜的另一个优点是在所选类别的聚合物中，可以选择确保特殊应用所必需的水蒸气渗透性的那些聚合物。
尽管本发明的膜可通过所有已知的方法(如在EP1,264,684A1([0082])中所列方法)制备，但已经证实，如果以下述方式制备多层膜，则是特别有利的：膜的所有计划中的层都由熔体在用于释放聚合物的挤出模口一起挤出。通过在给出的类别中相应地选择聚合物，并通过相应地设置各层的厚度，可非常容易地实现希望的水蒸气渗透性。适于这样制备多层膜的设备是本领域技术人员公知的。
例如，可以使用已经公知的名称为“Pro Pak Conical Die”的来自EganDavis的挤出模具作为挤出模具。利用该模具，将第一层的熔体施用到模具壁上，并在压力下向上传送，然后将第二层的另一熔体施用到流动熔体，并可以在将熔体由位于壁端的环形狭缝一起挤出之前，将其它熔体施用到该第二层。通过相应地设置各熔体的流动量并设置离开模具后纵向和横向的牵引力，可以影响多层膜各层的厚度。同时将载体层(例如聚乙烯的)挤出作为最内层和/或最外层，且为了避免破坏膜，在完成膜后再剥除该载体层，这样也是有利的。
本发明的膜优选不含增塑剂，因此仅含通常用于膜中的添加剂，例如无机粒子、颜料、热稳定剂和/或氧化稳定剂、UV稳定剂、聚烯烃等，和/或防止膜在卷起时粘连的防粘连剂。原则上，相对于总重量，膜应当含有不超过15重量％的这些添加剂。
本发明膜的特征特别在于根据ASTM E 96-95、程序BW、水温30℃进行测量，水蒸气渗透率(WVTR)为3,000至65,000g/m2/24小时。
特别地，根据ASTM E 96-95、程序B、水温30℃进行测量，本发明膜的水蒸气渗透率(WVTR)为200至5,000g/m2/24小时。
本发明膜的特征还在于总厚度为2至100μm，优选5至50μm，其中各层具有相同的厚度，但优选具有不同的厚度。因此，根据本发明可利用不同类聚合物的优点。
例如，较厚的层可选自聚醚酯类，较薄的层可选自聚醚酰胺类，由此可以利用下述事实：聚醚酰胺比聚醚酯通常更耐UV辐射；出于此原因，在给出的组合中，由聚醚酰胺制成的层代表了由聚醚酯制成的层的保护层，从而可看出，低的厚度已足以实现该目的。在对于聚醚酰胺耐受的某些化学品的耐受性方面，也可以使用这种保护层。
如果一个外层由聚醚聚氨酯类形成，则该层增强了膜的可焊性。
本发明的膜优选由两层构成。另外，已经证实，各层具有不同的水蒸气渗透率的膜非常有效。
本发明的膜特别适于制备透气衣物。衣物在本文中应理解为穿在身上的所有织物。特别地，这还包括手套、帽子和鞋。本发明的膜特别适于此，甚至当根据DIN EN ISO 6330：2000在40℃洗涤5次后、优选洗涤10次后，或根据DIN EN ISO 3175-1：1998干燥清洁循环7次后、优选干燥清洁循环12次后，所述层至少大部分仍然彼此连接。特别是在洗涤时，大多数情形下可观察到只是在洗涤30次或更多次之后才发生分层。当膜总表面积的90％仍然表现为连接的层、而膜总表面积仅10％表现为分离的区域时，相邻的层至少大部分仍彼此连接。由分离本身表现为膜不清晰这一事实，可识别出分离区。
为了制造衣物，根据施用到织物的一侧或两侧而连接本发明的膜(通常通过以点状或线状施用粘附剂而进行)，由此形成层合体。适于此的织物是机织物或编织物、层织物、非织造织物、网，但也可以是2维经编物以及类似的织物。
在优选实施方案中，本发明的膜在其一个外层与织物连接，从而使得该织物直接与本发明的膜连接而无需额外使用粘合剂，即，本发明的膜与织物之间的连接仅由膜和/或织物的纤维实现。
这可通过例如热砑光进行。膜的外层由此轻微熔融，以使得织物部分地渗入膜的外层，并由此形成与本发明的连接。
在特别优选的实施方案中，织物由具有一部分低熔点聚合物和一部分高熔点聚合物的热塑性聚合物构成。通过暴露于热，所述低熔点部分如同本发明膜的外层那样轻微熔融，从而可通过物理或化学方式在膜和具有低熔点的织物部分之间形成稳定的连接。这类连接在膜和织物之间产生了优异的粘合，因而产生了非常高的耐分层性。本发明的膜与织物的结合特别适于制造衣物，因为织物的应用防止了膜和皮肤的直接接触，因而改善了含有本发明膜的衣物在皮肤上的感觉。因此不需要额外的内衬。
通过使用例如基本由具有一部分低熔点聚合物和一部分高熔点聚合物的共聚物构成的纤维，可以获得由具有一部分低熔点聚合物和一部分高熔点聚合物的热塑性聚合物构成的织物。该共聚物可以是嵌段共聚物或接枝共聚物。所述机织物或编织物、层织物、非织造织物、网式织物、网状织物或网眼织物形式的织物是本领域技术人员已知的。它们例如由
Figure GSB00000303597700041
Verbundtechnik或Protechnic提供，并通常用作两个织物之间的连接层。与本发明膜结合的织物优选由共聚酯、共聚酰胺或共聚氨基甲酸酯制成。
还可以使用基本上由双组分纤维(其包含一部分低熔点聚合物和一部分高熔点聚合物)构成的、呈机织物或编织物、层织物、非织造织物、网式织物、网状织物或网眼织物形式的织物，其中，已经证实芯/外壳双组分纤维(具有低熔点外壳和高熔点芯)是特别合适的。
适于与本发明膜结合的织物本身可含有一部分由低熔点聚合物构成的纤维和一部分由高熔点聚合物构成的纤维。
还发现，经过加工形成层合体的本发明的膜特别适于制造睡袋、帐篷或油布。
基本包含下述组分的热塑性聚合物特别适于本发明的防水、可透水蒸气的多层膜。
●聚醚酯
聚对苯二甲酸丁二醇酯——70重量％
聚乙二醇(4000)——30重量％
●聚醚酯
聚对苯二甲酸丁二醇酯——50重量％
聚乙二醇(2000)——25重量％
聚四氢呋喃——25重量％
●聚醚酰胺
聚酰胺6——60重量％
聚乙二醇(2000)——20重量％
聚丙二醇(2000)——20重量％
●聚醚聚氨酯
二异氰酸甲酯——42重量％
丁二醇——8重量％
聚乙二醇——50重量％
参照下述实施例更为详细地解释本发明。
为制造下述膜，使用已经公知的名称为“Pro Pak Conical Die”的来自Egan Davis的挤出模具作为挤出模具。为制造膜，将第一聚合物熔融，并作为第一层施用到模具壁上，然后在压力下向上传送。然后将由第二层所用的第二聚合物熔融而获得的第二熔体施用到形成所述第一层的第一聚合物的流动熔体。然后将两种熔体一起通过位于壁端的直径约60cm的环形狭缝挤出。使用空气将通过冷却熔体而产生的两层膜充气，直至膜具有大约4m的圆周。然后将该膜放平并卷起。
膜的性质如下测量：
根据ASTM E 96-1995，使用“程序BW——倒置杯法”和“程序B——立式杯法”测量水蒸气渗透率，在两种情形下均将水温设置为30℃。两种测试方法均用由一种聚合物构成的膜层以及由面对水侧的另一聚合物构成的膜层进行。
在每种情形下，膜的洗涤根据DIN EN ISO 6330：2000在40℃的水温进行。膜的干燥清洁根据DIN EN ISO 3175-1：1998进行。
实施例1
用聚醚酯作为第一聚合物，聚醚酰胺作为第二聚合物。熔体的挤出量为40kg/小时的聚醚酯和54.5kg/小时的聚醚酰胺。所获膜的总厚度为17μm，其中聚醚酯层的厚度为7μm，而聚醚酰胺的厚度为10μm。
聚合物基本上包含下述组分：
  聚醚酯   聚醚酰胺
  聚对苯二甲酸丁二醇酯——70重量％   聚酰胺6——60重量％
  聚乙二醇(4000)——30重量％   聚乙二醇(2000)——20重量％
  聚丙二醇(2000)——20重量％
制得的两层膜的水蒸气渗透率具有下述值：
  水侧的聚醚酯   水侧的聚醚酰胺
  程序BW(g/m2/24小时)   23,800   27,500
  程序B(g/m2/24小时)   2,800   3,000
分别在38次洗涤后和45次干燥清洁循环以后，膜在小于12％的总表面积上显示出不清晰的分层的第一个信号。
实施例2
在将第一聚合物施用到模具壁上之前，首先将聚乙烯的熔体放在壁上作为载体。将聚醚聚氨酯作为第一聚合物、聚醚酯作为第二聚合物施用到该载体上。熔体的挤出量为47.4kg/小时的聚醚聚氨酯和37.1kg/小时的聚醚酯。在剥除聚乙烯载体层后，所获膜的总厚度为15.5μm，其中聚醚聚氨酯层的厚度为9μm，而聚醚酯的厚度为6.5μm。
聚合物基本上包含下述组分：
  聚醚聚氨酯   聚醚酯
  二异氰酸甲酯——42重量％   聚对苯二甲酸丁二醇酯——50重量％
  丁二醇——8重量％   聚乙二醇(2000)——25重量％
  聚乙二醇——50重量％   聚四氢呋喃——25重量％
制备的两层膜的水蒸气渗透率具有下述值：
  水侧的聚醚酯   水侧的聚醚酰胺
  程序BW(g/m2/24小时)   27,400   19,700
  程序B(g/m2/24小时)   2,970   2,850
分别在42次洗涤后和51次干燥清洁循环以后，膜在小于8％的总表面积上显示出不清晰的分层的第一个信号。
实施例3
使用聚醚酰胺作为第一聚合物，聚醚聚氨酯作为第二聚合物。熔体的挤出量为76.3kg/小时的聚醚酰胺和36.9kg/小时的聚醚聚氨酯。所获膜的总厚度为21μm，其中聚醚酰胺层的厚度为14μm，而聚醚聚氨酯层的厚度为7μm。
聚合物基本上包含下述组分：
  聚醚酰胺   聚醚聚氨酯
  聚酰胺6——60重量％   二异氰酸甲酯——42重量％
  聚乙二醇(2000)——20重量％   丁二醇——8重量％
  聚丙二醇(2000)——20重量％   聚乙二醇——50重量％
制备的两层膜的水蒸气渗透率具有下述值：
  水侧的聚醚酯   水侧的聚醚酰胺
  程序BW(g/m2/24小时)   25,400   30,700
  程序B(g/m2/24小时)   3,030   3,180
分别在45次洗涤后和53次干燥清洁循环以后，膜在小于9％的总表面积上显示出不清晰的分层的第一个信号。

Claims (18)

1.防水、可透水蒸气的多层膜，具有至少一个第一层和一个第二层，其中所有的层均由选自聚醚酯类、聚醚酰胺类或聚醚聚氨酯类的热塑性聚合物制成，并连接在一起，其中所述聚醚酯类基本包含70重量％的聚对苯二甲酸丁二醇酯和30重量％的聚乙二醇的聚醚酯类、或基本包含50重量％的聚对苯二甲酸丁二醇酯、25重量％的聚乙二醇和25重量％的聚四氢呋喃，所述聚醚酰胺类基本包含60重量％的聚酰胺、20重量％的聚乙二醇和20重量％的聚丙二醇，所述聚醚聚氨酯类基本包含42重量％的二异氰酸甲酯、8重量％的丁二醇和50重量％的聚乙二醇，其特征在于该膜不含增塑剂，且相邻排列的层由不同类的热塑性聚合物制成。
2.根据权利要求1的膜，其特征在于在根据ASTM E 96-95、程序BW、水温30℃测量时，所述膜的水蒸气渗透率为3,000至65,000g/m2/24小时。
3.根据权利要求1或2的膜，其特征在于在根据ASTM E 96-95、程序B、水温30℃测量时，所述膜的水蒸气渗透率为200至5,000g/m2/24小时。
4.根据权利要求1或2的膜，其特征在于膜的总厚度为2至100μm。
5.根据权利要求4的膜，其特征在于膜的总厚度为5至50μm。
6.根据权利要求1或2的膜，其特征在于所述层具有不同的厚度。
7.根据权利要求1或2的膜，其特征在于该膜由两个层构成。
8.根据权利要求1或2的膜，其特征在于所述层具有不同的水蒸气渗透率。
9.根据权利要求1或2的膜，其特征在于甚至在根据DIN EN ISO6330：2000但在40℃洗涤5次后，所述膜的层至少大部分仍彼此相连。
10.根据权利要求9的膜，其特征在于甚至在根据DIN EN ISO6330：2000但在40℃洗涤10次后，所述膜的层至少大部分仍彼此相连。
11.根据权利要求1或2的膜，其特征在于甚至在根据DIN EN ISO3175-1：1998干燥清洁循环7次后，所述膜的层至少大部分仍彼此相连。
12.根据权利要求11的膜，其特征在于甚至在根据DIN EN ISO3175-1：1998干燥清洁循环12次后，所述膜的层至少大部分仍彼此相连。
13.根据权利要求1或2的膜，其特征在于所述膜在其一个外层与织物连接。
14.根据权利要求13的膜，其特征在于膜与织物之间的连接仅通过膜和/或织物的纤维实现。
15.根据权利要求13的膜，其特征在于所述织物包含一部分低熔点聚合物和一部分高熔点聚合物。
16.根据权利要求1至15任一项的膜的用途，用于制造层合体。
17.根据权利要求1至15任一项的膜或由这些膜制得的层合体的用途，用于制造衣物。
18.根据权利要求1至15任一项的膜或由这些膜制得的层合体的用途，用于制造睡袋、帐篷或油布。
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