CN101563499A - 特别是合成皮革的复合材料 - Google Patents

特别是合成皮革的复合材料 Download PDF

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CN101563499A
CN101563499A CNA2007800469760A CN200780046976A CN101563499A CN 101563499 A CN101563499 A CN 101563499A CN A2007800469760 A CNA2007800469760 A CN A2007800469760A CN 200780046976 A CN200780046976 A CN 200780046976A CN 101563499 A CN101563499 A CN 101563499A
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composite
weaving cloth
top layer
thermoplastic polyurethane
polyurethane
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CN101563499B (zh
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M·舒特
H·马尔茨
C·施马尔库切
J·韦泽尔
N·布斯托斯
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
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    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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Abstract

本发明涉及一种复合材料，其特征在于该复合材料以粘结形式包含：(i)基于塑性分散体的覆盖层，和(ii)选自由热塑性聚氨酯制成的箔片、由热塑性聚氨酯和/或聚氨酯泡沫制成的非织造布的载体层。

Description

特别是合成皮革的复合材料
本发明涉及一种复合材料，尤其是人造皮革，该复合材料以粘结形式包含：
(i)基于塑性分散体优选聚氨酯分散体的顶层，尤其是表面层，和
(ii)选自基于热塑性聚氨酯的膜、基于热塑性聚氨酯和/或聚氨酯泡沫的非织造布，优选基于热塑性聚氨酯的非织造布的基材层。
本发明还涉及生产复合材料尤其是人造皮革的方法，其中使用塑性水分散体，优选聚氨酯分散体，优选包含异氰酸酯交联剂的聚氨酯分散体制备顶层(i)，优选表面层，优选通过喷涂、刮涂、辊涂和/或浇注将顶层施用到基于硅橡胶的底层的结构表面上，底层的温度为80-90℃，并且然后基于热塑性聚氨酯的膜、基于热塑性聚氨酯和/或聚氨酯泡沫的非织造布，优选基于热塑性聚氨酯的非织造布作为基材层(ii)结合到顶层(i)的背离底层结构表面的表面上。
作为高质量材料的皮革应用在许多日常生活领域例如鞋、汽车座椅外套和家具部分及服饰中。尤其是，皮革材料具有广受欢迎的舒适的触觉性能和公认的皮革韧性即机械强度。然而，皮革的缺点是不太透气即例如排汗形式的水分不易于通过皮革层输送到外面。在皮革常见的许多应用中这限制了舒适性，例如在用于汽车座椅或者用于鞋子的情况下。已经尝试例如通过皮革穿孔避免或者至少降低这个差透气性缺点。然而，这降低了产品的不透水性，这在下雨时是一个主要缺点，例如在鞋子和各种服饰情况下以及在外罩皮革的座椅的情况下，因为水能通过皮革从而弄湿了泡沫装饰。
WO 2005/047549描述了制备基于例如皮革的基材，并在其可见侧提供了具有粒状结构的基于塑性分散体的表面层。其中所述基材材料(二层皮革或者微细纤维非织造布)的缺点是在许多应用中回弹性不够。结果抵消了回弹性顶层的优点。而且，皮革是仅可以有限程度(取决于动物)地大块使用的质量不断变化的天然产品，不能以缠绕在辊上的材料得到。而且，它只能通过相当昂贵的方法生产。在微细纤维非织造布的情况下通常使用聚丙烯、聚酯或聚酰胺纤维。在这些情况下只能通过额外应用粘合剂实现顶层到基材的充分粘合。中间的粘合剂层是额外的水蒸气阻隔层，从而常常导致复合材料水蒸气渗透性的显著降低。这些已知方案的另一个缺点是材料混合，这使得更难以对产品进行循环。
因此本发明的目的是提供一种用于表面层，例如WO 2005/047549中描述的表面层的基材，并且其具有皮革外观，该基材可以如下生产：
-容易地，
-经济地并且
-大面积地，优选连续地例如作为缠绕在辊上的材料，其
-直接与表面层粘合，或者可以直接在表面层上生产，
-其机械性能可以在广泛的肖氏硬度范围内变化，其
-具有良好的透气性，
-还具有良好的加工性能，并且如果合适，
-是不透水的。
-尤其是目的在于提供一种复合材料，优选与已知的人造皮革相比具有特别高的回弹性的人造皮革。
-待提供的产品应该有良好的加工和循环性能。
该目的可以通过最初提出的复合材料，尤其是根据本发明的基材层实现。
本发明复合材料，尤其是人造皮革的特点在于，本发明的基材使得可以获得可以是弹性的并且可以可逆拉伸的材料，并且其在拉伸后没有永久形变。因此可以显著地增加例如表示为可逆拉伸性的回弹性。而且本发明产品的优点是在材料方面包含一种类型的物质，可以更容易地以全PU方案循环。
而且，聚氨酯通常对其它材料具有优良的粘合性。在某些条件下，根据本发明使用聚氨酯可以因此省却粘合剂，从而可以省略昂贵且耗时的加工步骤。可以例如通过喷涂方法原位施用泡沫层。通过直接应用仍然热的、预固化的纤维复合材料可以实现应用TPU非织造布。可以想到通过直接挤出到顶层上进行TPU膜的粘合再应用。
基材优选是非织造布，因为其多孔结构提供了比膜更好的透气性。也优选使用开孔、微孔聚氨酯泡沫，其除了良好的透气性之外还具有的优点是它可以在连续的、无溶剂喷涂应用中加工。
下面描述了本发明复合材料的各种组分及其制备方法。
基于塑性分散体的顶层(i)
已知用于该目的的塑性分散体，优选聚氨酯分散体，例如WO2005/047549中第6页第8行至第7页第38行描述的那些通常可以用作顶层，但也可以指定为表面层。顶层优选是可见表面，即人造皮革的表面层。该层的可见表面优选具有粒状结构即皮革的外观。在顶层的制备中通过喷涂、刮涂、辊涂或者浇注通常将水分散体应用到包含硅橡胶的底层的结构表面上。优选通过加热设备加热底层以使底层的表面温度无论何处都为大约80℃。通常通过喷嘴将喷雾形式的聚氨酯分散体应用到该加热表面上。之后，通过除去水进行喷雾固化以在底层上形成具有毛细管的薄膜。膜干燥到可以触摸通常就施用基材材料。顶层优选由固化的具有高软化点的包含交联剂的聚氨酯分散体和固化的同样包含交联剂但具有低软化点的聚氨酯分散体(聚酯-聚氨酯)的结合物组成。两种分散体在交联之前都是热塑性的。为了改变顶层对水的表面张力从而提高该层的物理坚牢度，可以使用有机硅皮革手感剂。还可以使用颜料和异氰酸酯交联剂。因此顶层(i)优选是包含交联剂，优选包含异氰酸酯交联剂的聚氨酯水分散体的反应产物。在复合材料中，顶层(i)的厚度优选为20μm-100μm，特别优选为40-50μm。在本发明复合材料中，顶层(i)优选通过聚氨酯分散体粘结牢固结合到层(ii)上。
基于热塑性聚氨酯膜的基材层(ii)
通常已知并且可商购的膜可以用作基于热塑性聚氨酯的膜，本文中也称为TPU。优选使用水蒸气可渗透的TPU。优选使用基于热塑性聚氨酯的膜，该热塑性聚氨酯基于通过双官能引发剂的烷氧基化制备的聚醚二醇，所用的烯化氧为环氧乙烷，并且环氧乙烷基于所用烯化氧的总重量的重量比例为至少50重量％。该膜的厚度优选为10μm-2mm，特别优选10μm-1mm，尤其是10μm-0.3mm。可以优选使用厚度低于100μm，优选低于50μm，特别优选低于20μm的热塑性聚氨酯膜，根据DIN 53122-1的水蒸气渗透性优选大于1.5mg/cm2。而且优选基于反应性体系的紧密聚氨酯膜，例如US 5,521,273中描述的那些膜。
基于非织造布，优选基于热塑性聚氨酯的非织造布的基材层(ii)
非织造布理解为指通过摩擦和/或粘附和/或粘合方式加固的层、非织造布和/或包含取向或无规纤维的纤维网。
在本申请的上下文中，优选不将纸或已经使用卷绕的纱或长丝编织、针织、成束、缝编或者通过湿磨法缠结的产品作为非织造布处理。
在优选的实施方案中，在本申请的上下文中，当超过50质量％，尤其是60-90质量％的材料纤维组分由长径比超过300，尤其是超过500的纤维组成时，认为材料是“非织造布”。
在优选的实施方案中，非织造布各根纤维的直径为100μm-0.1μm，优选50μm-0.5μm，尤其是10μm-0.5μm。
在优选的实施方案中，根据ISO 9073-2测量的非织造布厚度为0.01-5毫米(mm)，更优选0.1-2mm，尤其优选0.15-1.5mm。
在优选的实施方案中，根据ISO 9073-1测量的非织造布每单位面积质量为20-1000g/m2，尤其优选50-500g/m2，特别优选100-350g/m2。
还可以另外机械加固非织造布。机械加固可以是一侧或者两侧机械加固，优选两侧机械加固。
还可以另外化学加固非织造布。在化学加固中，通过添加化学助剂例如添加粘合剂加固非织造布。
除了上面描述的机械和化学加固，还可以另外热加固非织造布。可以例如通过用热空气处理非织造布进行热加固。
如果加固非织造布，则优选热加固。
下面描述了在优选实施方案中所用非织造布(ii)具有的4个参数(P1-P4)。
P1)在一个实施方案中，所用非织造布在生产方向上的拉伸强度为5牛顿(N)/5cm-1000N/5cm，优选40N/5cm-1000N/5cm，尤其是100N-1000N/5cm(根据DIN EN 12127测量)。
P2)在一个实施方案中，所用非织造布在与生产方向垂直的方向上的拉伸强度为5牛顿(N)/5cm-1000N/5cm，优选40N/5cm-1000N/5cm，尤其是100-1000N/5cm(根据DIN EN 12127测量)。
P3)在一个实施方案中，根据DIN EN 29073第3部分测量的所用非织造布在生产方向上的伸长率为10％-800％，优选50％-800％，尤其是250％-800％。
P4)在一个实施方案中，根据DIN EN 29073第3部分测量的所用非织造布在与生产方向相对方向上的伸长率为10％-800％，优选50％-800％，尤其是250％-800％。
在优选的实施方案中，非织造布具有特征P1-P4中至少两个，更优选至少3个特征，尤其是所有特征P1-P4。
所用非织造布包含热塑性聚氨酯。这理解为指所用非织造布包含热塑性聚氨酯，优选包含它作为主要组分。在优选的实施方案中，所用非织造布包含的热塑性聚氨酯的量基于非织造布总重量为60重量％-100重量％，尤其优选超过80重量％，尤其超过95重量％。
除了热塑性聚氨酯，所用非织造布还可包含其它聚合物或助剂如聚丙烯或聚丙烯的共聚物、聚乙烯或聚乙烯的共聚物和/或聚苯乙烯和/或聚苯乙烯的共聚物如苯乙烯/丙烯腈共聚物。
热塑性聚氨酯是当在通常用于加工和使用该材料的温度范围内将它们重复加热且冷却时仍然保持热塑性的聚氨酯。此处热塑性理解为指在通常用于聚氨酯的150℃-300℃的温度范围内聚氨酯由此重复地加热软化冷却固化的聚氨酯性能，并且在软化状态时可以通过流动成成型制品、挤出物或加工部件反复成型以得到半成品或制品。
通过使(a)异氰酸酯与(b)数均分子量优选为500-10000g/mol的异氰酸酯反应性化合物，和如果合适(c)分子量为50-499g/mol的增链剂，如果合适在(d)催化剂和/或(e)助剂存在下进行反应可得到用于非织造布的热塑性聚氨酯。通常已知并且可以商购相应的原材料以及产物即TPU和基于TPU的非织造布。
在优选的实施方案中，根据DIN 53505测量的用于生产非织造布的热塑性聚氨酯的肖氏硬度为50肖氏A-74肖氏D，尤其优选80肖氏A-54肖氏D。
此类热塑性聚氨酯的密度通常为800-1300克/升(g/l)，优选1000-1250g/l。
可以用已知方法制备TPU，例如使用反应挤出机或者带根据一步法或者预聚物法连续地进行，或者根据已知预聚物法分批进行。在这些方法中，参与反应的组分(a)、(b)以及如果合适(c)、(d)和/或(e)可以彼此接连地混合或者同时混合，反应立即开始。
在挤出机方法中，将组分(a)、(b)以及如果合适(c)、(d)和/或(e)单独或者作为混合物引入挤出机中，并且例如在100-280℃，优选140-250℃反应，然后挤出、冷却并且成粒得到的TPU。
在许多应用中非织造布的耐光性是重要的。即使非织造布仅用作基材，有可能表面层的厚度不足以过滤掉所有UV光。因此在此种情况下优选脂族非织造布即基于脂族异氰酸酯的那些非织造布。
通常可以通过所属技术领域已知的熔喷法或者纺粘法从上述热塑性聚氨酯生产包含热塑性聚氨酯的非织造布。熔喷法和纺粘法是技术领域中的已知方法。得到的非织造布通常在其机械性能和一致性上不同。因此纺粘法生产的非织造布在水平和垂直方向上都特别稳定，但具有开孔结构。熔喷法生产的非织造布具有特别紧密的纤维网，因此形成对液体特别好的阻隔性。
也可以通过组合熔喷法和纺粘法制造非织造布。这些非织造布有特别紧密的纤维网以及对液体有非常好的阻隔性，并且具有非常优良的机械性能。优选通过组合熔喷法和纺粘法生产非织造布。
基于聚氨酯泡沫的基材层(ii)
基材层(ii)还可以基于通常已知的聚氨酯泡沫，例如软质或者半硬质泡沫如WO 2006/034 800、EP 1 595 901、DE 10 2004 048 571、EP 0 897 402、WO 2006/089890或WO 2006/097508中描述的那些。
根据DIN 7726，将泡沫定义为在整个材料上分布有孔并且总密度低于骨架物质的密度的材料。优选大部分开孔的泡沫。开孔定义为通过气相与其它孔连接的孔。泡沫的密度优选为50g/l-800g/l，尤其优选150g/l-600g/l，特别是150-500g/l，尤其优选200g/l-400g/l。泡沫的断裂伸长率优选超过100％。
“Kunststoffhandbuch第7卷，聚氨酯”，Carl Hanser Verlag，1993年第3版，第5章和第7章也描述了相应泡沫的制备。
如果聚氨酯泡沫用作基材层(ii)，则优选软质聚氨酯泡沫作为基材层(ii)。
如果聚氨酯泡沫用作基材材料，则基材层的厚度优选为10μm-5mm，尤其优选30μm-1mm，特别是50μm-600μm。EP-A 1 595 901中描述了特别优选的软质聚氨酯泡沫。
相反，也已知大量用于制备微孔PU涂层的其它方法。可以在E.中发现该情形概述。与该现有技术相关的专利实例是DE 24 35 880。
基材材料的制备可以通过刮涂技术或通过喷涂以连续(优选)或者分批方式进行。
本发明还涉及制备复合材料尤其是人造皮革的方法，使用塑性水分散体，优选聚氨酯分散体，优选包含异氰酸酯交联剂的聚氨酯分散体制备顶层(i)，优选通过喷涂、刮涂、辊涂和/或浇注将顶层应用到基于硅橡胶的底层的结构表面上，底层的温度为80-90℃，并且基于热塑性聚氨酯的膜，基于热塑性聚氨酯和/或聚氨酯泡沫的非织造布作为基材层(ii)然后结合到顶层(i)的背离底层的结构表面的顶层(i)的表面上。可以通过喷涂施用将基材层(ii)牢固地结合到顶层(i)上。这种类型的方法例如描述于WO2006/097508中。

Claims (16)

1.一种复合材料，其中该复合材料以牢固结合的形式包含：
(i)基于塑性分散体的顶层和
(ii)选自基于热塑性聚氨酯的膜、基于热塑性聚氨酯和/或聚氨酯泡沫的非织造布的基材层。
2.如权利要求1所述的复合材料，其中顶层的可见表面具有粒状结构。
3.如权利要求1所述的复合材料，其中顶层(i)是包含交联剂的聚氨酯水分散体的反应产物。
4.如权利要求1所述的复合材料，其中顶层(i)的厚度为20μm-100μm。
5.如权利要求1所述的复合材料，其中顶层(i)通过聚氨酯分散体粘结到层(ii)上。
6.如权利要求1所述的复合材料，其中基于热塑性聚氨酯的膜是水蒸气渗透性的。
7.如权利要求1所述的复合材料，其中基于热塑性聚氨酯的膜基于通过双官能引发剂的烷氧基化制备的聚醚二醇，所用的烯化氧是环氧乙烷，并且环氧乙烷基于所用烯化氧总重量的重量比例为至少50重量％。
8.如权利要求1所述的复合材料，其中非织造布基于使用脂族异氰酸酯制备的热塑性聚氨酯。
9.如权利要求1所述的复合材料，其中非织造布由长径比大于300的纤维组成。
10.如权利要求1所述的复合材料，其中非织造布的纤维的直径为100μm-0.1μm。
11.如权利要求1所述的复合材料，其中根据ISO 9073-2测量的非织造布(ii)的厚度为0.01mm-5mm。
12.如权利要求1所述的复合材料，其中根据ISO 9073-1测量的非织造布(ii)每单位面积质量为20g/m2-1000g/m2。
13.如权利要求1所述的复合材料，其中聚氨酯泡沫是软质泡沫。
14.如权利要求1所述的复合材料，其中聚氨酯泡沫的厚度为50μm-600μm。
15.如权利要求1所述的复合材料，其中聚氨酯泡沫的密度为150-500g/l。
16.一种生产复合材料的方法，其中顶层(i)使用塑性水分散体制备，优选通过喷涂、刮涂、辊涂和/或浇注将顶层施用到基于硅橡胶的底层的结构表面上，底层的温度为80-90℃，并且基于热塑性聚氨酯的膜，基于热塑性聚氨酯和/或聚氨酯泡沫的非织造布作为基材层(ii)然后结合到顶层(i)的背离底层的结构表面的表面上。
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