CN102049200A - 疏油性、可透气的及透气性复合膜 - Google Patents
疏油性、可透气的及透气性复合膜 Download PDFInfo
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Abstract
通过相关的方法提供了一种多孔性复合膜(10),所述多孔性复合膜包括第一材料的第一微孔性基材(12)。第二涂料(14)与所述第一微孔性基材连接,以与所述第一微孔性基材一起形成双组份安排。所述第二材料不同于所述第一材料。将第三涂料(16)施用于所述双组份安排。所述第三材料不同于所述第一材料和第二材料。所述第三材料延伸超过限定所述微孔的双组份安排的至少一部分表面。
Description
技术领域
总体而言,本发明涉及片材材料,所述片材材料可称为膜或薄膜,更具体地,本发明涉及具有如下品质的片材材料:抗透油性、抗透水性、可透水蒸汽、可透气和抗由于化学物质的存在而引起的显著的性能劣化。
背景技术
含氟聚合物和热塑性弹性体为已知的,且用于许多不同的应用,包括户外片材材料或薄膜。含氟聚合物层或热塑性弹性体层可用于提供一些期望的性能,例如可透水蒸汽和可透气(例如,透气性)或抗透水性。因此,已知提供一种透气性和耐水的片材材料。这种片材材料在实际的户外应用中非常有用。例如,这种片材材料可用于制备服装制品、户外齿轮、防护制品等等。但是,一些化学物质(例如驱虫剂)的存在可引起片材材料的至少一些性能(例如耐透水性水平)劣化。具体地,由于在片材材料上化学物质的存在,可增加片材材料允许水渗透/通过的倾向。这种允许水渗透/通过的增加的倾向可称为润湿。
发明内容
以下提供本发明的简化概述,用于提供对本发明的一些实施例方面的基本理解。该概述不是本发明的穷举的综述。此外,该概述不是要鉴别本发明的关键要素,也不是要描述本发明的范围。该概述的唯一目的为以简化的形式呈现本发明的一些概念,作为随后出现的更详细描述的前序。
根据一方面,本发明提供了一种多孔性复合膜,所述多孔性复合膜包括第一材料的第一微孔性基材。第二涂料与所述第一微孔性基材连接并且为第二微孔性基材,以与所述第一微孔性基材一起形成双组份安排。所述第二材料不同于所述第一材料。将第三涂料施用于所述双组份安排。所述第三材料不同于所述第一材料和第二材料。所述第三材料延伸超过限定所述微孔的双组份安排的至少一部分表面。
根据另一方面,本发明提供了一种提供所述多孔性复合膜的相关的方法。
附图说明
参考附图,在阅读以下描述后,本发明的以上和其他方面对于本发明所涉及领域的技术人员来说是显而易见的,其中:
图1为根据本发明的一方面的一个示例性防水、可透水蒸汽和可透气的片材材料的放大的示意侧视图;
图2为图1的材料的一部分的放大的示意图,并显示通过在结点连接的原纤限定的开放的显微孔隙;和
图3为图2的一部分的进一步的放大图,剖面显示片材材料的组成元件,该片材材料包括基材、在基材上含有层和涂层,它们不堵塞该材料的孔隙。
具体实施方式
在附图中描述和举例说明了结合本发明的一个或多个方面的示例性实施方案。这些举例说明的实施例不是要限制本发明。例如,本发明的一个或多个方面可用于其他实施方案,甚至其他类型的装置。此外,本文使用的某些术语仅为了方便,不应看作是限制本发明。再有,在附图中,相同的附图标记用于标示相同的要素。
参考图1,显示了根据本发明的一个方面的实例。具体地讲,该实例显示了一种防水的疏油性、可透气的和可透湿汽的复合膜片材材料10。术语“片材材料”包括膜或薄膜。在所示实例中,片材材料包括防水的多孔性聚合物基材12、与所述聚合物基材连接的多孔性热塑性层14、和与所述热塑性层材料和所述聚合物基材材料中至少一些连接的疏油性涂层16。值得注意的是,在图1中,提供了表示疏油性涂层16的描影。该描影仅允许识别/区别基材12和热塑性层14,不是用于说明剖面。应清楚地理解,图1为示意性表示。基材12、热塑性涂层14和疏油性涂层16可认为是片材材料10的组成部分,因此,提供的片材材料10具有疏油性、可透气、可透水蒸汽、防水、和抗由化学攻击剂(challenge agent)引起的变化。应理解,防水是指通常理解的在标准或环境条件下抗非蒸汽水的渗透。还应理解,在一个具体的实例中,防水可定义为在任何观察到的通过材料表面的渗透或渗漏之前,满足14.50psi(1000毫巴)水压滞留量(hold-up)的ISO811标准。但是,具体遵守ISO811标准是不必要的。
集中在多孔性基材12,该基材具有可透气、可透蒸汽和防水的特性。基材12的孔20为微孔。参见图2,其中许多孔中仅一些用附图标记20标注。在一些具体的实例中,多孔性基材12(图1)包括以下材料中的至少一种:基于氟的聚合物(含氟聚合物)、聚氨酯、纤维素聚合物、聚酰胺、聚酰亚胺、聚碳酸酯、磺化聚合物/聚砜、和共聚物。所述基于氟的聚合物包括聚四氟乙烯和聚偏二氟乙烯中的至少一种。所述共聚物包括至少一种共聚酯-聚醚和共聚醚-聚酰胺。多孔性基材12的其他具体的实例为膨胀的聚四氟乙烯(ePTFE)或微孔性膜。相对于位于其上的水滴的表面张力,由于基材较小的孔径、基材材料的表面能而使基材12耐水滴渗透。如所描述的,图2显示多孔性。在所示实例中,基材具有微观结构,该微观结构基于原纤22,该原纤22延伸并与结点24互连(仅一些用附图标记22、24鉴别)。原纤22和结点24限定孔20。在一些实例中,孔20的直径可为0.01微米至10微米。
集中在热塑性层14(参见图1),该层也为多孔性的。特别是,该孔为微孔。该多孔性提供可透气和可透水蒸汽的特性。相对于攻击剂的表面张力,由于其较小的孔径、基材12的材料表面能,层14耐化学攻击,并在其间接触。在一种定义中,层14可描述为具有耐化学性。具体地,层14抗将引起片材材料10以另外的方式失去防水特性的一种或多种化学物质的影响。作为一些实例,层14可为基于共聚物系统的热塑性聚氨酯(TPU)或热塑性弹性体(TPE),例如聚醚-聚酯或聚醚-聚酰胺共聚物。总的来说,该层的材料包括以下物质中的至少一种:聚氨酯、氟化丙烯酸酯、氟化甲基丙烯酸酯、基于硅氧烷的聚合物、聚丙烯酸、丙烯酰胺的共聚物。在一些具体的实例中,所述材料为热塑性或热固性的。另外,在一些具体的实例中,所述材料可交联。关于图1,总的来说,应理解,片材材料的尺寸(即,长、宽和厚度)可变化,并且在图中示意性示出的代表不用于尺寸、特性或性能的限制。
在本发明公开的一个实施方案中,在片材材料10上提供了热塑性层14,将层14加热至至少部分熔融。在至少部分熔融状态下,层材料流至基材12的孔中。涂层材料仅部分进入基材12。这种部分流入基材12通过附图标记12和14的括号区域的重叠而在图1中示意性示出。具体地讲,在该实施例中,在恰好基材12的相邻的第一部分或区段30处,层14延伸至孔中。这种热-流动填充使得基材12与层14粘结在一起。或者,换言之,将层14热层压于基材12,同时保持基材12和层14的开放的孔结构。
层14的材料粘附于基材12的材料的原纤22和结点24。图3示意性显示热塑性材料14在基材材料12的原纤22和结点24上的一种可能的连接。应理解,在图3实施例中所示的放大来自图1所示的重叠区域30。另外,应理解,图3的实施例表明,层14覆盖基材12的材料的原纤22和结点24的所有的表面。另外,应理解,图3的实施例表明,层14均匀且与基材12的材料的原纤22和结点24相比有点薄。应理解,层14可具有不同的厚度/薄度,该层可填充更多/更少的在基材中所提供的孔体积20,和/或可能不能完全覆盖基材的材料的原纤和结点的所有可用的表面。
在一个实例中,层14的加热在一系列加热步骤中进行。在一个具体的实例中,所述加热包括在第一温度下加热,随后在高于所述第一温度的第二温度下加热,再随后在高于所述第二温度的第三温度下加热。多-温度加热的一个具体的实例包括在80-90℃的第一温度下加热,随后在90-110℃的第二温度下加热,随后在110-150℃的第三温度下加热。
层14的加热可通过不同的方法完成。在一个实例中,与对片材材料施加压力结合完成所述加热。在一个具体的实例中,通过将中间-步骤片材材料10(即,含有已施用但还未加热的层14的基材12)通过加热的压辊可赋予加热和压力。如果片材材料10以伸长的网形式制造,则使用加热的辊的这种方法有用。可将片材材料的伸长的网移动,在加热的辊之间通过,网的速度使得可采用经济的方式生产大量的片材材料。关于在一系列步骤中提供加热的具体的实例,可通过一系列加热的辊完成加热,其中每个辊提供不同的加热水平。当然,也考虑其他形式的加热和施加压力,例如非动态加热和加压,且在本发明的范围内。
参考图1,基材12为疏水性的且还透气和可透水蒸汽。这些特征示意性示于图1。如所描述的,基材12的一种示例性材料为微孔性膨胀的聚四氟乙烯。含氟聚合物具有三维晶格类型的结构,该结构通过曲折的路径得到多个微孔性开孔,该曲折的路径限定足够小的孔,以防止水滴通过,但是孔足够大可以允许空气和蒸汽通过。作为参考,液体水滴比蒸汽状态的水的尺寸大约1000倍。
疏油性和疏水性涂层16与至少一些热塑性层材料14和聚合物基材材料12连接。具体地讲,疏油性涂层16以微孔隙率水平与热塑性层14的材料和聚合物基材12的材料连接。通过这种方式,疏油性涂层16不位于热塑性层14和/或聚合物基材12的外部。与此相反,疏油性涂层16渗透至热塑性层14的材料和聚合物基材12的材料中。再次参考图3的实例,疏油性涂层16在层14上。但是,应理解,疏油性涂层16也可位于不混合的基材12和/或层14的部分上(即,在重叠区域30之外,参见图1)。因此,疏油性涂层16可直接在基材12上和/或疏油性涂层16可在不延伸至基材12的孔隙中的层14上,因此在微观水平上不是基材的材料。另外,应理解,图3的实例表明,涂层16覆盖层14的所有表面,该层14在基材12的材料的所有原纤22和结点24上。另外,应理解,图3的实例表明,涂层16均匀,且与基材12的材料的原纤22和结点24相比有点薄。应理解,涂层16可具有不同的厚度/薄度,该涂层可填充更多/更少的在基材中所提供的孔体积20,和/或可能不能完全覆盖在基材12的材料的原纤22和结点24上的层14的所有可用的表面。
疏油性涂层16可为基于氟代丙烯酸酯或基于硅氧烷的聚合物或其他疏油性材料。总的来说,涂层16的材料包括以下物质中的至少一种:聚氨酯、氟化丙烯酸酯、氟化甲基丙烯酸酯、基于硅氧烷的聚合物、聚丙烯酸、丙烯酰胺的共聚物。所述材料可为热塑性或热固性的。在一个实例中,将疏油性涂料16以溶解状态引入片材材料10。另外,作为实例,在可认为流体允许运动/移动的条件下,将疏油性涂料16引入片材材料10中。在一个具体的实例中,在超临界条件下,通过二氧化碳的加压流体溶解疏油性涂料16,并且将疏油性涂料移动至多孔性基材12和/或多孔性层14中。通过将压力从超临界条件降低至非超临界条件,将疏油性涂层连接/沉积在多孔性基材12和/或多孔性层14中。
应理解,制备整个最终产物的方法可不同。例如,可通过各种技术施用涂层16的材料,包括在流体中分散、借助液体载体、和通过从超临界流体、液体或气体中沉淀来沉积。如果使用液体载体,所述载体可为有机溶剂或无机溶剂。应注意,使用超临界溶剂,所述溶剂可为流体、液体或气体状态的二氧化碳。因此,所述方法可包括许多不同的技术,例如利用化学蒸气沉积、等离子体、刮涂方法、转移涂布方法、丝网印刷方法和凹槽辊(gravure roll)印刷方法。甚至其他技术也是可能的且考虑使用。
最终处理过的(即,层状和涂布的)基材保持多孔性,使得片材材料10可透湿汽、透气、防水、持久、抗化学渗透和具有疏油性。在1,000帕斯卡差压下,最终的片材或膜的透气率为至少0.1cfm/平方英尺所述复合膜一侧的表面积。这部分是由于微孔小于100微米所致。对于不同的消费者、职业和工业应用,最终的片材材料可与任选的层(例如非织造和织造织物、纱、针织织物)组合。
在制备的片材材料10中,提供了防水性、可透水蒸汽性、透气性的特性。防水性为通常理解的术语,与防止非蒸汽水渗透片材材料的能力相关。可透水蒸汽性为允许水蒸汽通过片材材料的能力。透气性为允许空气通过片材材料的能力。透湿气率,也称为MVTR,为水蒸汽通过片材材料的度量,用克/平方米/天表示。透气率,用立方英尺/分钟表示,衡量在水通过样品的预定压降下,空气通过样品所需要的时间。由于汗和身体的热量通过膜并允许快速从身体相邻处移走,高MVTR和透气率导致良好的舒适性水平。
层14的材料和涂料16中的至少一种改变基材12的防油性能。特别是,增强了该性能。层14的材料和涂料16中的至少一种提高抗液体化学物质侵入或通过基材12的孔。根据本发明的一方面,提供了防水性、可透水蒸汽性、透气性,即使化学物质可能以另外的方式劣化片材材料10的抗透水性。该化学物质可认为是攻击剂。这种攻击剂对至少一种期望的特性至少可能引起不利的影响。在一个具体的实例中,攻击剂至少可能不利地影响防水特性。失去防水性与润湿和透水性相关。通过这种方式,可能出现浸湿,这样可允许非-蒸汽或液体水通过。因此,应理解,涉及化学物质可认为包括理解该化学物质为这样的攻击剂。抗化学物质(攻击剂)的劣化通过耐破度试验等级(ASTM D751)说明。
可引起片材材料10的抗非蒸汽水渗透性(即,防水性)劣化的一种广泛使用的示例性化学物质(即,攻击剂)为N,N-二乙基-间-甲苯甲酰胺,也称为DEET。可引起劣化的化学物质的其他实例包括存在的化学物质,包括发动机燃料(例如,航空、汽车、柴油机)和溶剂。还另外,也考虑其他化学污染物,例如多种酸。如所描述的,这种化学物质有时称为攻击剂,这是由于它们倾向于劣化材料期望的性能。当然,本发明不限制具体的化学攻击剂。如果存在于片材材料10上,这种化学物质可能以另外的方式引起基材12的微孔性材料允许水滴通过,但是,本发明的一方面防止这种不需要的事件发生(即,失去防水性),因此提供了此类化学物质的抗性。
DEET为驱虫剂中的常见的活性成分且具有较低的表面张力,可能使基材12和片材材料10“结垢”,并允许液体水通过。由于片材材料10可用于户外应用,例如用于手套、靴、帐篷,等等,对于片材材料10来说有益的是抗防水性能由于化学攻击剂(例如用于驱虫剂的DEET)的劣化。尽管存在化学物质,这种抗劣化使得片材材料10保持其防水、可透蒸汽和透气特性。另外,片材材料10可用于其中片材材料可能与发动机燃料(例如,柴油机燃料)接触的应用。同样,对于片材材料10来说有益的是抗防水性能由于化学攻击剂(例如发动机燃料)的劣化。
甚至在暴露于攻击剂许多小时之后,片材材料10仍可保持抗劣化。一些示例性片材材料的数据包括单独的ePTFE,用超临界CO2与含氟聚合物处理之前和之后,仅含有热塑性聚氨酯层的ePTFE(即,未用超临界CO2与含氟聚合物处理),并且根据本发明的两个实例(例如,涂有微孔性热塑性聚氨酯和用疏油性涂层处理的ePTFE)示于表1A-1C。因此,层14和涂层16的材料中的至少一种改变基材12的疏水性或防水性能。沿着这些线,层14和涂层16的材料中的至少一种改变基材12的摩擦系数。
表1A
表1B
表1C
最终的片材材料10在主要的表面之间可具有小于100微米或0.1毫米的厚度。当然,本发明不必局限于这种示例性尺寸。这种低厚度以及轻重量增加了片材材料10的舒适性水平。实际上,层14的材料和涂料16中的至少一种可增强聚合物基材12的机械性能。片材材料10还可在两侧与另一种织物层组合,用于构建外衣,例如手套、靴、帐篷,等等。实际上,层14的材料和涂料16中的至少一种可提供与另一种多孔性基材的界面粘合。片材材料10的示例性用途包括但不限于手套、帽子、外套、夹克、衬衫、裤子、内衣、鞋、靴、防护服、服装的各种其他制品、背包、睡袋、帐篷、各种其他户外齿轮,等等。
关于涉及人们穿戴用品的用途,应必须理解,当人们出汗时,在皮肤上产生水蒸汽和液体汗两者。在这种应用中,考虑涂层在朝向人的最里层,而基材12在远离人的最外层。高MVTR和透气率可使得这种水蒸汽和液体汗快速通过片材材料10。因此,所述片材材料非常适用于以上提及的涉及人们穿戴用品的示例性用途。当然,本发明不局限于这些用途,并且可考虑其他用途。另外,考虑片材材料可包括额外的层和/或片材材料可结合成为多层片材。这种对片材材料的添加和/或包括在多层片材中的片材材料的用途的一些实例包括使用织造织物、非织造织物、针织织物和纱中的至少一种。当然,也考虑其他材料和/或织物。
已经参考上述示例性实施方案描述了本发明。当阅读和理解本说明书后,可进行许多修改和变化。结合本发明的一个或多个方面的示例性实施方案将包括在它们落入所附权利要求范围内的限度的所有这些修改和变化。
Claims (17)
1.一种多孔性复合膜(10),所述多孔性复合膜包括:
第一材料的第一微孔性基材(12);
第二涂料(14),该第二涂料与所述第一微孔性基材(12)连接,以与所述第一微孔性基材(12)一起形成双组份安排,所述第二材料不同于所述第一材料;和
施用于所述双组份安排的第三涂料(16),所述第三材料不同于所述第一材料和第二材料,所述第三材料延伸超过限定所述微孔的双组份安排的至少一部分表面。
2.权利要求1的多孔性复合膜(10),其中在1,000帕斯卡差压下,所述膜(10)的透气率为至少0.1cfm/平方英尺所述复合膜一侧的表面积。
3.权利要求1的多孔性复合膜(10),其中所述微孔小于100微米。
4.权利要求1的多孔性复合膜(10),其中所述第一材料包括以下物质中的至少一种:基于氟的聚合物、聚氨酯、纤维素聚合物、聚酰胺、聚酰亚胺、聚碳酸酯、聚砜以及共聚物。
5.权利要求4的多孔性复合膜(10),其中所述基于氟的聚合物包括聚四氟乙烯和聚偏二氟乙烯中的至少一种。
6.权利要求1的多孔性复合膜(10),其中所述第二材料包括以下物质中的至少一种:聚氨酯、氟化丙烯酸酯、氟化甲基丙烯酸酯、基于硅氧烷的聚合物、聚丙烯酸、丙烯酰胺的共聚物。
7.权利要求1的多孔性复合膜(10),其中所述第三材料包括以下物质中的至少一种:聚氨酯、氟化丙烯酸酯、氟化甲基丙烯酸酯、基于硅氧烷的聚合物、聚丙烯酸、丙烯酰胺的共聚物。
8.权利要求1的多孔性复合膜(10),其中所述第二材料和第三材料中的至少一种增强所述第一微孔性基材的机械性能。
9.权利要求1的多孔性复合膜(10),其中所述第二材料和第三材料中的至少一种改变所述第一微孔性基材的防油性能。
10.权利要求1的多孔性复合膜(10),其中所述第二材料和第三材料中的至少一种改变所述第一微孔性基材的疏水性或防水性能。
11.权利要求1的多孔性复合膜(10),其中所述第二材料和第三材料中的至少一种改变所述第一微孔性基材的摩擦系数。
12.权利要求1的多孔性复合膜(10),其中所述第二材料和第三材料中的至少一种提供与另一种多孔性基材的界面粘合。
13.一种制备权利要求1的多孔性复合膜(10)的方法。
14.权利要求13的方法,其中通过以下方法中的至少一种施用所述第三材料:a)在流体中分散,b)借助液体载体,和c)通过从超临界流体、液体或气体中沉淀来沉积。
15.权利要求14的方法,其中所述液体载体包括有机溶剂和无机溶剂中的至少一种。
16.权利要求14的方法,其中所述超临界流体、液体或气体包括二氧化碳。
17.权利要求21的方法,其中通过以下方法中的至少一种使所述第二材料与所述第一微孔性基材连接:a)化学蒸气沉积,b)等离子体,c)刮涂方法,d)转移涂布方法,e)丝网印刷方法,和f)凹槽辊印刷方法。
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US12/603,740 US20110097571A1 (en) | 2009-10-22 | 2009-10-22 | Oleophobic, air permeable, and breathable composite membrane |
US12/603740 | 2009-10-22 |
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CN104334047A (zh) * | 2012-06-01 | 2015-02-04 | 耐克创新有限合伙公司 | 通风的运动包 |
CN104761017A (zh) * | 2015-03-13 | 2015-07-08 | 北京天恒盛通科技发展有限公司 | 具有水下超亲气性质的气/液分离装置的制备方法和用途 |
CN106606933A (zh) * | 2015-10-22 | 2017-05-03 | 财团法人工业技术研究院 | 水分离复合膜 |
CN108465383A (zh) * | 2017-02-23 | 2018-08-31 | 塞法尔股份公司 | 保护性通气件和制备保护性通气件的方法 |
CN109012238A (zh) * | 2018-08-13 | 2018-12-18 | 南京林业大学 | 一种高强度高通量的油水分离膜的制备方法及油水分离膜 |
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DE102010038273A1 (de) | 2011-05-12 |
GB2474753A (en) | 2011-04-27 |
US20110097571A1 (en) | 2011-04-28 |
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