CN102015281A - 具有热激活的聚氨酯脲组合物的层压织物构造 - Google Patents
具有热激活的聚氨酯脲组合物的层压织物构造 Download PDFInfo
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Abstract
包括了包含多个层的制品。该多层制品可以包括与聚氨酯脲组合物，例如膜或水性分散体，相结合的织物或泡沫。
Description
相关申请的交叉引用
本申请是2006年2月10日提交的美国申请第11/351,967号的部分延续，后者是2005年12月13日提交的美国申请第11/300,229号的部分延续，后者是2005年10月19日提交的美国申请第11/253,927号的部分延续，后者是2005年2月11日提交的美国申请第11/056,067号的部分延续，所有这些都通过引用结合进来。
发明背景
发明领域
本发明涉及包括多层构造(multiple layer construction)的制品。所述层包括与聚氨酯脲组合物相结合的织物和/或聚氨酯泡沫。
相关技术概述
聚氨酯类(包括聚氨酯脲)能够用作多种基体(包括纺织织物)的粘合剂。典型地，这种聚氨酯是完全形成的非活性聚合物或活性的异氰酸酯封端的预聚物。这种活性聚氨酯粘合剂通常需要延长的固化时间以发展足够的结合强度，其能够是制造工艺中的缺点。此外，该聚氨酯的异氰酸酯基团已知是对水分敏感的，这限制了包含这种聚氨酯的产品的储存稳定性并降低了其贮藏寿命。
典型地，这种聚合物，当完全形成时，溶解在溶剂中(溶剂携带的(solvent borne))、分散在水中(水携带的)、或处理为热塑性固体材料(热熔性的)。值得一提地，溶剂基粘合剂面临着目标在于降低挥发性有机化合物(VOC)和有害空气污染物(HAP)排放的始终紧绷的健康和环境法规。因此，未来可能需要传统溶剂基产品的替代物。
热熔性粘合剂尽管是环境安全的且易于以膜形式施加，但通常在经过重复拉伸循环时具有高永久变形(high set)和差的恢复性。因此，需要克服热熔性粘合剂的性能缺陷的粘合剂。适宜地，与常规热塑性聚氨酯和热熔性粘合剂相比，这种粘合剂也将为织物提供其他优点，例如挠性、形状保持性和透气性。
发明内容
一些实施方案提供包括至少两个层和聚氨酯脲组合物(apolyurethaneurea composition)的多层制品。该聚氨酯脲组合物可以在基体上形成所述层之一，例如作为聚氨酯脲组合物。该聚氨酯脲组合物可以是任意适合的形式，例如膜或分散体。该聚氨酯脲组合物可以置于所述层的邻近或所述层之间，也可以为该制品提供粘合性、可模塑性、形状保持性和挠性。
一些实施方案提供经过压制、层压和/或模制的、包括多个层(多层)的制品。该制品包括至少两个层，其中一个层是以膜或分散体形式的聚氨酯脲组合物。
另一种实施方案提供包括至少一个织物层和至少一种选自由膜、分散体及其组合构成的组的聚氨酯脲组合物的制品。
发明详述
此处所用的术语“多孔的”是指如下基体：所述基体包括空隙或孔，所述空隙或孔在所述基体的表面中、或在所述基体的厚度内的任何位点处、或通过所述基体的厚度、或朝向本发明的制品可以与其接触的任何材料。
此处所用的术语“压制”或“压制的”表示经过热和/或压力处理以提供基本平坦结构的制品。
此处所用的术语“泡沫”表示可以用于织物构造中的任何适合的泡沫，例如聚氨酯泡沫。
此处所用的术语“分散体”表示其中分散相由细碎颗粒组成且连续相能够为液体、固体或气体的系统。
此处所用的术语“聚氨酯水性分散体”表示如下组合物：其包含已经分散在含水介质，例如水(包括去离子水)，中的至少聚氨酯或聚氨酯脲聚合物或预聚物(例如此处所述的聚氨酯预聚物)，任选地包含溶剂。
除非另外指示，此处所用的术语“溶剂”表示非水介质，其中该非水介质包括有机溶剂，包括挥发性有机溶剂(例如丙酮)和挥发性有些差的有机溶剂(例如MEK或NMP)。
此处所用的术语“无溶剂的”或“无溶剂的系统”表示如下组合物或分散体：其中所述组合物或分散的组分的大部分尚未溶解或分散在溶剂中。
此处所用的术语“制品”表示如下制品：其包括分散体制品或成形制品和基体(例如纺织织物)，其可以具有或可以不具有至少一种弹性性质，所述性质部分是由于此处所述的分散体制品或成形制品的应用。该制品可以为任意适合的构造，例如一维、二维和/或三维的。
此处所用的术语“织物”是指针织、织造或非织造材料。该针织织物可以是平针织物、圆筒形针织物、经编织物、狭幅弹性织物和花边。该织造织物可以具有任何构造，例如棉缎、斜纹、平纹组织、牛津组织、席纹组织和狭幅弹性织物。该非织造材料可以是熔吹的、纺粘的、湿法成网的、梳理的纤维基短纤维网幅等。
此处所用的术语“基体”表示本发明的制品可以与其接触的任意材料。基体能够是基本一维的，如其是纤维；是两维的，如其是平坦片材，或是三维的制品或非平坦片材。平坦片材例如可以包括纺织织物、纸、植绒制品和网幅。三维制品例如可以包括皮革和泡沫。其他基体可以包括木材、纸、塑料、金属和复合材料，例如混凝土、沥青、健身房地板和塑料碎片。
此处所用的术语“硬纱线”表示基本无弹性的纱线。
此处所用的术语“模制的”制品是指通过响应于热和/或压力的施加而改变制品或成形制品的形状的结果。
此处所用的术语“源自”表示在由另一对象形成的物质。例如，膜可以源自能够干燥的分散体。
此处所用的术语“模量”表示以每单位线密度或面积的力表示的在物体上的应力比。
在一些实施方案中是包括以膜或分散体形式存在的至少一层聚氨酯脲组合物的多层制品。这些制品具有至少两个层，所述层包括至少一种聚氨酯脲组合物。该聚氨酯脲组合物可以形成该层之一，例如作为在基体上的聚氨酯脲组合物。该聚氨酯脲组合物可以是任意适合的形式，例如膜或分散体。该聚氨酯脲组合物可以位于所述层的临近或之间，而且也可以为该制品提供拉伸和恢复、提高的弹性模量、粘合性、可模制性、形状保持性和挠性性质。这些制品可以成形为织物和/或服装。
可以将多种不同的聚氨酯脲组合物与一些实施方案的膜和分散体一起使用。例如，所述一些实施方案的膜可以由溶液、水性分散体或基本无溶剂的水性分散体浇铸而成。很多这种溶液或分散体是现有技术中已知的。例如，依照本发明的一些实施方案，可以使用聚氨酯脲溶液(例如来自商业斯潘德克斯弹性纤维生产线的纺丝溶液)来浇铸膜。下面描述可与本发明一起使用的水性分散体和由其浇铸的膜的特别实例。
在其中该制品包括包括三个或更多个层且其中一层是膜的多层制品的实施方案中，该膜可以是两个织物层之间、两个泡沫层之间、织物层和泡沫层之间、或临近与织物层临近的泡沫层的中间层。这些织物/泡沫/膜排列的组合也是考虑了的。例如，该制品可以按顺序包括织物层、泡沫层、膜层、泡沫层和织物层。该制品包括两个单独的织物层、两个单独的泡沫层、和膜层。在任意这些实施方案中，可以用聚氨酯脲分散体替代该聚氨酯脲膜。因此，该制品可以包括一个或多个聚氨酯脲膜和一个或多个聚氨酯脲分散体层。
在另一实施方案中，可以将单层织物或泡沫折叠以形成该多层制品的两个或更多个层，聚氨酯脲膜或分散体作为中间层。在该实施方案中，然后也可以将该制品模制或压制成所需形状，例如用于塑身服装。在折叠点处设置带的情况下，该带可以提供另外的拉伸恢复能力，例如在边缘(hem)处或用于塑身服装，以提供另外的支撑。这也可用于服装例如贴身胸罩中，其中该膜/带设置可以提供提高的壁强度或刚性，且可以防止该服装在边缘处翻转。
在包括两个或更多个层的实施方案中，该聚氨酯脲组合物可以形成外层。在外表面上包括该聚氨酯脲组合物形成很多有利功能。例如，该聚氨酯脲组合物可以提供提高摩擦力的锚或区域以减少包括该聚氨酯脲组合物的制品和外部基体之间的相对运动。在该制品是包括接触皮肤(其中穿用者的皮肤是该基体)的表面的内衣时这是特别有用的。可替代地，该基体可以是与本发明制品的聚氨酯脲组合物接触的外衣。在该基体是穿用者的外衣且该制品被穿作内衣的情况下，该制品防止或降低该外衣的相对运动。此外，外衣(例如服饰)可以包括聚氨酯脲组合物以保持内衣的相对位置(例如滑动)
在织物、泡沫和该聚氨酯脲组合物的层已经选定后，它们随后可以通过压制或模制粘合以形成平坦或成型的制品。如果需要，一些实施方案的用于制备该压制的和模制的制品的方法包括压力和热的使用。例如，可以在约150℃～约200℃或约180℃～约190℃(包括约185℃)加热充分时间以获得模制的制品。适合的加热时间包括但不局限于约30秒～约360秒，包括约45秒～约120秒。可以通过任何已知的方法(包括但不局限于微波、红外、传导、超声、随时间加压(即夹持(clamping))及其组合)实现结合。
由于对包括聚氨酯脲膜或分散体的制品施加了热和压力，而且假定膜和织物本身是多孔材料，我们认识到该膜或分散体可以部分或完全浸渍该制品的织物或泡沫。例如，该聚氨酯脲组合物可以形成与周围的层部分分开的层，或者可以完全转移到周围的一个或多个层中以形成没有可区分开的单独聚氨酯脲组合物层的整体式制品。
本发明的多层制品的一种应用是塑身服装，例如胸罩(尤其是在罩杯或两翼中)和男性内衣。这些制品能够提供舒适、塑身和支撑的合意特征，同时仍提供舒适、透气性、空气渗透性、水分/蒸气传输、芯吸性及其组合。在本发明的一些实施方案的制品中，所述层可以采取预设的形状，且可以相对于彼此以预设的取向设置在模制或成形制品(例如胸罩构造的罩杯)的设计中。这些织物的层可以单独使用或与缝纫到、粘合到或以其它方式施加到该织物上的其他材料组合使用。
在一些实施方案中，有用于构造具有由该织物提供的整体式成型能力的塑身服装的系统。该构造系统可以用于多种不同的服装构造中，例如运动服、运动衣、男性或女性贴身内衣(例如胸罩、内衣、短衬裤、塑性服装、袜子)和针织品(例如女用裤袜)、现成的服装(例如粗斜纹布牛仔裤)、女背心、定制衬衫、和男用短衬裤及其它。这种构造可以用于任何可成型的身体区域。尽管包括了该织物构造的很多优点，但进一步认识到其实用性并不限制于服装，而发现可和任何可成型或可成形的介质一起使用，包括用于家具的软垫，其也会经过与该可成形区域接触的织物的运动和可能的滑动。
为了添加另外的支撑和其他特征，可以将该聚氨酯脲组合物添加到该制品的不同区域。例如，在使用膜时，其或者可以延伸通过该制品的全部区域或者到达选定部分以提供不同优点。例如，胸罩可以包括在罩杯部分中的一些实施方案的分层织物。在胸罩罩杯中，能够有用的是将一部分膜用在该罩杯的下部中用于支撑，在该罩杯的中心部分中用于显得端庄(modesty)，在侧面部分中用于塑形，或在特定区域中用于修饰或装饰。
降低多层织物中的膜含量以满足织物的需求也可以提高该织物的透气性。如实施例中所示，源自此处所述的水性分散体的该聚氨酯脲组合物比源自聚氨酯脲溶液的那些提供更大的透气性。由该水性分散体浇铸的膜与可在市场上获得的可获自Bemis的热塑性聚氨酯(TPU)膜相比在透气性方面表现更好。也可以通过改变该膜以使其多孔或成为多孔的(即“潜在的”透气性)或通过为该膜穿孔而提高透气性。
由一些实施方案的水性分散体浇铸的膜的另一优点是关于该膜的手感或触感。与硅橡胶或可在市场上获得的TPU膜相比，其提供了更柔软的手感，同时保持了所需的摩擦性以减少移动，这是用于皮肤接触应用的另一优点。而且，更小的弯曲模量提供了更好的悬垂性和织物手感。
尤其与在可在市场上获得的热塑性聚氨酯脲组合物相比，在用于服装中时，该聚氨酯脲组合物提供了另外的优点。这些优点包括形状保持性、塑形能力、粘着性、保持基体摩擦、湿度管理和蒸气渗透性。
取决于所需功能(可能是视觉审美)，可以将该聚氨酯脲组合物添加到其他构造中。可以将该聚氨酯脲膜或分散体添加到制品、织物或服装中，以模制成一种设计，以粘合装饰物(例如装饰织物和亮片)，以标签或标识的形式，及其组合。
取决于在以来自此处描述的水性分散体的膜或分散体形式施加时该聚氨酯脲组合物的所需效果，该膜中该聚合物的数均分子量可以在约40000～约150000范围变化，包括约100000～约150000和约120000～约140000。
在一些实施方案中，该聚氨酯脲组合物可以用作用于粘合两个或更多个织物或泡沫的层或将织物层粘合到泡沫上的粘合剂。一种适用于实现此的方法是通过任何适合方法将分散体施加到层上。一些实施方案的用于施加该分散体的方法包括喷雾、开压边浇口(kissing)、印刷、刷涂、浸渍、填充、分布、计量加入、涂抹及其组合。在此之后可以施加热和/或压力。
在本发明的一些实施方案的多层制品中可以包括其他粘合剂。粘合剂的实例包括热固性或热塑性粘合剂、压敏粘合剂、热熔粘合剂及其组合。该粘合剂可以用于粘合不同层且可以施加到织物、泡沫或聚氨酯脲膜或分散体的任意上。而且，该聚氨酯脲水性分散体也可以用作粘合剂，以粘合一些实施方案中所述的任意织物、泡沫或聚氨酯脲膜的多于一层。
如上所述，有多种可用于本发明的制品的织物构造。此外，在任意这些实施方案中，该聚氨酯组合物可以是膜或分散体。此外，该聚氨酯脲组合物可以提供构造性质、挠性、粘合性或其任意组合。层排列的顺序可以是(1)织物层、泡沫层、聚氨酯脲组合物层；(2)织物层、泡沫层、聚氨酯脲组合物层、泡沫层、织物层；(3)织物层、聚氨酯脲组合物层、织物层；(4)泡沫层、聚氨酯脲层、泡沫层；(5)泡沫层、聚氨酯脲组合物层；(6)织物层、聚氨酯脲层；或这些的任意组合，可以将其结合以在该织物构造中获得更多层。可以包括粘合剂以粘合任意所述层，包括其中该聚氨酯脲组合物是粘合剂。
可以将多种不同的纤维和纱线和一些实施方案的织物一起使用。这些包括棉花、羊毛、丙烯酸类、聚酰胺(尼龙)、聚酯、斯潘德克斯弹性纤维、再生纤维素、橡胶(天然或合成的)、竹子、丝、大豆或其组合。
适用于本发明的一些实施方案中的聚氨酯水性分散体是由特定氨基甲酸乙酯预聚物提供的，下面对其详细描述。
氨基甲酸乙酯预聚物或封端的多元醇通常能够概念化为在将该预聚物分散在水中并链扩增之前，多元醇、聚异氰酸酯、和一旦中和能够形成盐的化合物的反应产物。这种预聚物通常能够在一个或多个步骤中制备，用或不用溶剂。取决于该预聚物是溶解在将保留在该分散体中的较小挥发性的溶剂(例如MEK或NMP)中，还是溶解在能够随后除去的挥发性溶剂(例如丙酮)中，或者分散在没有任何溶剂的水中，能够将该分散方法在实际中分类为溶剂方法、丙酮方法或预聚物混合方法。该预聚物混合方法具有环境和经济优点，因此也可用作用于制备本发明中的水性分散体的基本方法。
在该预聚物混合方法中，重要的是该预聚物的粘度充分低，足够在不用溶剂稀释的情况下转移和分散在水中。在一种实施方案中，本发明涉及源自这种预聚物的聚氨酯分散体，其满足这种粘度需要且在该预聚物中或在该分散体中不具有任何有机溶剂。依照本发明，该预聚物是多元醇(a)、二异氰酸酯(b)和二醇化合物(c)的反应产物。然而，也考虑了包括有机溶剂的预聚物。
本发明能够提供稳定的聚氨酯水性分散体，能够对其处理并直接用作用于通过常规技术涂覆、结合和层压到基体上的粘合材料(即不需要任何另外的粘合材料)。落入本发明的范围内的聚氨酯水性分散体可以使用或不使用挥发性有机材料；在制备中具有可接受的固化时间；且在最终制品中和在实际应用中具有良好的粘合强度、耐热性和拉伸/恢复性质。
本发明还能够提供可以是或可以不是能够涂覆在脱模纸上的成型制品，由此能够将本发明的水性分散体用于粘合和层压到包括纺织织物的基体上。通过在基体和粘合剂膜上施加热和/或压力小于1分钟(例如约15秒～约60秒)的停留时间能够激发该粘合。由此结合的制品具有良好的拉伸/恢复性质，并预期在正常磨损和洗涤循环中是耐久的。
依照本发明，适用作用于制备氨基甲酸乙酯预聚物的原料的多元醇组分是数均分子量为约600～约3500的聚醚二元醇、聚碳酸酯二元醇和聚酯二元醇。
能够使用的聚醚多元醇的实例包括具有两个或更多个羟基的那些二元醇，来自氧化乙烯、氧化丙烯、氧杂环丁烷、四氢呋喃和3-甲基四氢呋喃的开环聚合和/或共聚，或来自在各分子中具有少于12个碳原子的多元醇(优选二醇或二醇混合物，例如乙二醇、1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、新戊二醇、3-甲基-1，5-戊二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，10-癸二醇和1，12-十二烷二醇)的缩聚。优选直链的双官能聚醚多元醇，在本发明中特别优选分子量为约1700～约2100的聚(四亚甲基醚)二醇，例如官能度为2的
1800(Invista)。
能够使用的聚酯多元醇的实例包括具有两个或更多个羟基且由脂肪族多羧酸和低分子量的(每个分子中不多于12个碳原子)多元醇或其混合物缩聚制备的那些酯二元醇。适合的多羧酸的实例是丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二羧酸和十二烷二羧酸。适用于制备该聚酯多元醇的多元醇的实例是乙二醇、1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、新戊二醇、3-甲基-1，5-戊二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，10-癸二醇和1，12-十二烷二醇。优选具有约5℃～约50℃的熔点的直链双官能聚酯多元醇。
能够使用的聚碳酸酯多元醇的实例包括具有两个或更多个羟基且由光气、氯甲酸酯、二烷基碳酸酯或二烯丙基碳酸酯和低分子量(每个分子中不多于12个碳原子)的脂肪族多元醇或其混合物缩聚制备的那些碳酸酯二元醇。适用于制备该聚碳酸酯多元醇的多元醇的实例为二乙二醇、1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、新戊二醇、3-甲基-1，5-戊二醇、1，7-庚二醇、1，8-辛二醇、1，9-壬二醇、1，10-癸二醇和1，12-十二烷二醇。优选具有约5℃～约50℃的熔点的直链双官能聚碳酸酯多元醇。
适用作用于依照本发明制备氨基甲酸乙酯预聚物的另一原料的聚异氰酸酯组分(b)能够是包含4，4’-亚甲基双(苯基异氰酸酯)和2，4’-亚甲基双(苯基异氰酸酯)的二苯基甲烷二异氰酸酯(MDI)的同分异构体混合物，4，4’-MDI与2，4’-MDI同分异构体的比例在约65∶35～约35∶65范围内，优选在约55∶45～约45∶55范围内，更优选为约50∶50。适合的聚异氰酸酯组分的实例包括
ML(Bayer)、
MI(BASF)和
50O，P’(Dow Chemical)。
适用作用于依照本发明制备氨基甲酸乙酯预聚物的另一原料的二醇化合物(c)包括具有以下的至少一种二醇化合物：(i)两个能够与聚异氰酸酯b)反应的羟基；和(ii)至少一个一旦中和能够生成盐且不能与聚异氰酸酯(b)反应的羧酸基。具有羧酸基的二醇化合物(c)的典型实例包括2，2-二羟甲基丙酸(DMPA)、2，2-二羟甲基丁酸、2，2-二羟甲基戊酸和DMPA引发的己内酯，例如
HC 1060(Solvay)。DMPA是本发明中优选的。
所述预聚物能够通过在一个步骤中将原料(a)、(b)和(c)混合在一起并在约50℃～约100℃的温度下反应足够时间直至所有羟基都基本消耗掉并达到所需的异氰酸酯基的％NCO来制备。可替代地，也能够通过以下在两个步骤中制备该预聚物：首先使原料(a)与过量的(b)反应，然后与组分(c)反应直至达到预聚物最终所需的％NCO。例如，该％NCO可以在约1.3～约6.5范围，例如约1.8～约2.6。重要的是，在反应之前、期间或之后，不将有机溶剂添加到原料中或与其混合。任选地，可以使用催化剂来促进预聚物的形成。
在本发明的实施方案中，该预聚物包含组分(a)、(b)和(c)，将其组合在一起并以以下基于该预聚物总重量的重量百分比范围提供：
约34％～约89％的组分(a)；
约59％～约10％的组分(b)；和
约7.0％～约1.0％的组分(c)。
在本发明的另一实施方案中，该预聚物包括
1800聚醚二元醇作为组分(a)、
ML二异氰酸酯作为组分(b)、和2，2-二羟甲基丙酸(DMPA)作为组分(c)。在这些实施方案中，这些组分例如可以以以下基于该预聚物总重量的重量百分比范围提供：
a)
1800聚醚二元醇；约61％～约80％；
b)
ML二异氰酸酯；约35％～约18％；和
c)2，2-二羟甲基丙酸(DMPA)；约4.0％～约2.0％。
由组分(a)、(b)和(c)制备的该预聚物通过在40℃的落球法测定应当具有小于约6000泊(例如小于约4500泊)的体积粘度(没有任何溶剂存在)。能够用高速分散器将沿聚合物链包含羧酸基的该预聚物分散到包括以下的去离子水介质中：至少一种中和剂(d)，以与酸生成离子盐；至少一种表面活性剂(离子性和/或非离子性分散剂或表面活性剂)；和任选的至少一种二胺链扩增组分(f)。可替代地，在分散到该水介质中之前，能够将该中和剂与该预聚物混合。在分散该预聚物之前、期间或之后能够将至少一种消泡剂和/或防泡剂和优选至少一种流变改性剂添加到该水介质中。
适用于将所述酸基团转变为盐基团的中和剂(d)的实例包括：叔胺(例如三乙胺、N，N-二乙基甲基胺、N-甲基吗啉、N，N-二异丙基乙基胺和三乙醇胺)和碱金属氢氧化物(例如氢氧化锂、氢氧化钠和氢氧化钾)。也可以使用伯和/或仲胺作为用于该酸基团的中和剂。中和度通常为所述酸基团的约60％～约140％，例如约80％～约120％范围内。
适合的二胺链扩增剂(f)的实例包括：1，2-乙二胺、1，4-丁二胺、1，6-己二胺、1，12-十二烷二胺、1，2-丙二胺、2-甲基-1，5-戊二胺、1，2-环己二胺、1，4-环己二胺、4，4’-亚甲基-双(环己胺)、异氟尔酮二胺、2，2-二甲基-1，3-丙二胺、间-四甲基二甲苯二胺和分子量小于500的
(Texaco)。
适合的表面活性剂的实例包括：阴离子、阳离子或非离子分散剂或表面活性剂，例如十二烷基硫酸钠、十二烷基苯磺酸钠、乙氧基化壬基酚和溴化十二烷基吡啶鎓。
适合的防泡或消泡或泡沫控制剂的实例包括：Additive 65和Additive 62(获自Dow Corning的硅酮基添加剂)、
I 300(获自Cognis的矿物油基无硅酮消泡剂)和SurfynolTM DF 110L(获自AirProducts & Chemicals的高分子量炔属二元醇非离子表面活性剂)。
适合的流变改性剂的实例包括疏水改性的乙氧基化氨基甲酸乙酯(HEUR)、疏水改性的可碱膨胀的乳液(HASE)和疏水改性的羟基-乙基纤维素(HMHEC)。
用于异氰酸酯基团的封端剂(e)可以或者是单官能醇或者是单官能胺。所述封端剂可以在形成所述预聚物之前的任何时间、在所述预聚物形成过程中、或者在所述预聚物形成之后(包括在分散该预聚物到水性介质比如去离子水之前和之后)添加。在一些实施方案中，封端剂是任选的，或者可以被排出在外。在其它实施方案中，基于预聚物的重量，所述封端剂可以以大约0.05％-大约10.0％(包括大约0.1％-大约6.0％和大约1.0％-大约4.0％)的量被包括进来。基于最终分散体的重量，所述封端剂可以以大约0.01％-大约6.0％的量存在，包括大约0.05％-大约3％和大约0.1％-大约1.0％。
包括封端剂使得可以控制聚合物在分散体中的重均分子量并对聚合物分子量分布进行控制。封端剂提供这种控制的有效性取决于封端剂的类型和在分散体的制备过程中封端剂加入的时刻。例如，可以在预聚物形成之前、之中或之后加入单官能醇。所述单官能醇封端剂也可以加入到于其中分散所述预聚物的水性介质中，或者在将预聚物分散到水性介质中之后立刻加入。但是，当希望对最终分散体中的聚合物分子量和分子量分布进行控制时，所述单官能醇如果在预聚物分散之前被加入并反应作为所述预聚物的一部分，那么所述单官能醇可以是最有效的。如果所述单官能醇在所述预聚物的分散期间或之后加入到所述水性介质中，那么由于所述竞争性的链扩增反应，它在控制聚合物分子量方面的有效性下降。
能用于本发明的单官能醇的实例包括至少一个选自由如下物质组成的组的成员：具有1-18个碳的脂族和环脂族伯醇和仲醇、酚、取代的酚、分子量小于大约750(包括小于500)的乙氧基化的烷基酚和乙氧基化脂肪醇、羟胺、羟甲基和羟乙基取代的叔胺、羟甲基和羟乙基取代的杂环化合物和其组合，包括糠基醇、四氢糠基醇、N(2-羟乙基)琥珀酰亚胺、4-(2-羟乙基)吗啉、甲醇、乙醇、丁醇、新戊醇、己醇、环己醇、环己烷甲醇、苄基醇、辛醇、十八烷基醇、N，N-二乙基羟基胺、2-(二乙基氨基)乙醇、2-二甲基氨基乙醇和4-哌啶乙醇及其组合。
当采用单官能胺化合物比如单官能二烷基胺作为异氰酸酯基团的封端剂时，它可以在分散体制备过程中的任何时间加入，合意地所述单官能胺封端剂在所述预聚物分散期间或之后加入到水介质中。例如，单官能胺封端剂能够在所述预聚物分散之后即刻加入到水混合物中。
适合的单官能二烷基胺封端剂的实例包括：N，N-二乙基胺、N-乙基-N-丙基胺、N，N-二异丙基胺、N-叔丁基-N-甲基胺、N-叔丁基-N-苯甲基胺、N，N-二环己基胺、N-乙基-N-异丙基胺、N-叔丁基-N-异丙基胺、N-异丙基-N-环己基胺、N-乙基-N-环己基胺、N，N-二乙醇胺和2，2，6，6-四甲基哌啶。该胺封端剂与该预聚物在分散到水中之前的异氰酸酯基的摩尔比通常应当在约0.05～约0.50范围，例如约0.20～约0.40。对于该去封端反应可使用催化剂。
任选地，在分散该预聚物并添加该封端剂之后，可以将至少一种聚合物组分(g)(MW＞约500)添加到该水介质中，其中每摩尔所述聚合物具有至少三个或更多个伯和/或仲氨基。适合的聚合物组分的实例包括：聚氮丙啶、聚(乙烯基胺)、聚(烯丙基胺)和聚(氨基胺)枝状物、和其组合。
可以任选地包括在该水性分散体或预聚物中的其他添加剂包括：抗氧化剂、UV稳定剂、着色剂、颜料、交联剂、相变材料(即可在市场上获自Outlast Technologies，Boulder，Colorado的
)、抗菌剂、矿物(即铜)、微胶囊化的健康添加剂(即真芦荟、维生素E凝胶、真芦荟、海藻、烟碱、咖啡因、香味物或芳香剂)、纳米颗粒(即二氧化硅或碳)、碳酸钙、阻燃剂、抗粘添加剂、抗氯降解添加剂、维生素、药物、香料、电导添加剂、和/或染料助剂(即可在市场上获自E.I.DuPontde Nemours，Wilmington，Delaware的
)。可以添加到该预聚物或水性分散体中的其他添加剂包括增粘剂、抗静电剂、抗成坎剂、抗蠕动剂、荧光增白剂、促凝剂、导电添加剂、发光添加剂、流平剂、冻-融稳定剂、润滑剂、有机和无机填料、防腐剂、织构剂、热变色添加剂、杀虫剂和润湿剂。
可以在分散该预聚物之前、期间或之后，根据方法允许，可以将这种任选的添加剂添加该水性分散体中。任何时候在该水性分散体中都不添加有机溶剂。
落入本发明范围内的聚氨酯水性分散体应当预期具有约10wt％～约50wt％的固含量，例如约30wt％～约45wt％。落入本发明范围内的聚氨酯水性分散体的粘度可以根据加工和施加需求在约10厘泊～约100000厘泊的宽范围内变化。例如，在一种实施方案中，该粘度在约500厘泊～约30000厘泊范围内。可以通过使用适当量(例如基于该水性分散体总重量的约0～约2.0wt％)的增稠剂来改变粘度。
在一些实施方案的膜和分散体的制备中也可以使用有机溶剂。该有机溶剂可以用于通过溶解和稀释而降低该预聚物的粘度，和/或用于帮助具有羧酸基团的二醇化合物(例如2，2-二羟甲基丙酸(DMPA))的固体颗粒的分散以提高分散质量。其也可以用于改进该膜均匀性的目的，例如减少该涂覆工艺中的条纹缺陷和裂缝。
选用于这些目的的溶剂基本或完全对异氰酸酯基团不起反应，在水中稳定，且具有对DMPA、DMPA和三乙基胺形成的盐和该预聚物良好的溶解能力。适合溶剂的实例包括N-甲基吡咯烷酮、N-乙基吡咯烷酮、二丙二醇二甲基醚、丙二醇正丁基醚乙酸酯、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、2-丙酮(丙酮)和2-丁酮(甲基乙基酮或MEK)。
添加到一些实施方案的膜/分散体的溶剂量可以不同。当包括溶剂时，溶剂的适合范围包括小于该分散体重量的50％。也可以使用较小的量，例如少于该分散体重量的20％，少于该分散体重量的10％，少于该分散体重量的5％，少于该分散体重量的3％。
有很多方法在该制备方法的不同阶段将该有机溶剂引入到该分散体中，例如：
1)在完成聚合之后并在转移和分散该预聚物之前，能够将该溶剂添加到该预聚物中并与其混合，该稀释的预聚物在主链中包含羧酸基团并在链端包含异氰酸酯基团，在分散到水中的同时被中和并扩增链。
2)所述溶剂能够和其他成分(例如
1800、DMPA和
MI)一起添加并混合，以在该溶液中形成预聚物，然后将在溶液中的该在主链中包含羧酸基团并在链端包含异氰酸酯基团的预聚物分散在水中并同时将其中和并扩增链。
3)所述溶剂能够与DMPA和三乙基胺(TEA)的中和盐一起添加，并与1800和
MI混合，以制备预聚物，然后所述预聚物被分散。
4)该溶剂能够与TEA混合，然后添加到形成的预聚物中，然后所述预聚物被分散。
5)所述溶剂能够和二元醇一起添加并混合，然后顺序添加DMPA、TEA以及MI到位于溶液中的中和过的预聚物中，然后所述预聚物被分散。
一些实施方案的聚氨酯水性分散体特别适用于粘合成型制品，所述粘合成型制品在施加热和压力相对短的时间时能够用于织物结合、层压和粘合目的。根据所用的结合方法，压力能够例如在约大气压～约60psi范围内，时间能够在小于约1秒～约30分钟的范围内。
这种成型制品可以通过以下制备：将该分散体涂覆在脱模纸上并通过市场上可获得的方法在低于约100℃的温度下干燥除去水，以在所述纸上形成膜。能够将所述形成的膜片材切成所需宽度的带状物，并卷绕成卷，供随后用于形成拉伸制品，例如纺织织物。这种应用的实例包括：无缝合或无缝的服装构造；缝密封和增强；结合到服装上的标签和补缀；和局部拉伸/恢复增强。粘合结合能够在约100℃～约200℃(例如约130℃～约200℃，例如约140℃～约180℃)的温度下在0.1秒～几分钟的时间内(例如小于约1分钟)形成。典型的结合机是Sew Free(可在市场上获自SewSystems，Leicester，England)、Macpi缝边机(可在市场上获自Macpi Group，Brescia，Italy)、Framis热空气焊接机(可在市场上获自Framis Italy，s.p.a，Milano，Italy)。这种结合在暴露于在纺织织物服装中的重复磨损、洗涤和拉伸时预期是坚固和耐用的。
可以将该涂层、分散体或成型制品涂色或着色，在这一点上也可以将其用作设计元素。
此外，能够模制具有层压膜或分散体的制品。例如，在适用于织物中的硬纱线的条件下能够模制织物。而且，模制可以在模制该成型制品或分散体的温度但低于适用于模制该硬纱线的温度进行。
能够使用任何其中对层压体表面施加热的方法进行层压以将该成型制品固定到织物上。热施加的方法包括例如超声、直接加热、间接加热和微波。这种直接层压可以提供的与现有技术中所用的其他方法相比的优点在于该成型制品不仅可以通过机械相互作用而且可以通过化学键合而结合到基体上。例如，如果该基体具有任何活性氢官能团，那么这种基团可以与该分散体或成型制品上的异氰酸酯和羟基基团反应，由此在基体和该分散体或成型制品之间提供化学键。该分散体或成型制品与该基体的这种化学键合能够提供更强得多的结合。这种结合可以发生在固化到基体上的干成型制品中，或发生在在一个步骤中干燥和固化的湿分散体中。没有活性氢的材料包括聚丙烯织物和具有含氟聚合物或硅酮基表面的任何材料。具有活性氢的材料包括例如尼龙、棉花、聚酯、羊毛、丝、纤维素、醋酸酯、金属和丙烯酸酯。此外，用酸、等离子体或其他蚀刻形式处理的制品可以具有用于粘合的活性氢。染料分子也可以具有用于结合的活性氢。
用于施加一些实施方案的聚氨酯脲组合物的方法和装置包括但不局限于：辊涂(包括逆向辊涂)；使用金属工具或刀片(例如将分散体倾注到基体上，然后通过使用金属工具(例如刀片)将其铺展在该基体上而将该分散体浇铸成均匀厚度)；喷雾(例如使用泵喷瓶)；浸渍；涂抹；印刷；冲压；和浸渗该制品。这些方法能够用于将该分散体直接施加到基体上，而不需要另外的粘合材料，而且如果需要另外的/更重的层，则能够重复。能够将分散体施加到由用于涂覆、结合、层压和粘合目的合成、天然或合成/天然混合材料制成的任何针织、制造或非织造的织物上。在该工艺过程中能够用干燥排除分散体中的水(例如通过空气干燥或使用炉子)，从而将沉淀和聚结的聚氨酯层保留在该织物上以形成粘合结合。
任选地可以使用至少一种促凝剂(coagulant)来控制或最小化依照本发明的分散体到织物或其他制品内的渗透。可以使用的促凝剂的实例包括硝酸钙(包括硝酸钙四水合物)、氯化钙、硫酸铝(水合的)、乙酸镁、氯化锌(水合的)和硝酸锌。
能够用于施加分散体的工具的实例是刀片。该刀片能够由金属或任何其他适合的材料制成。该刀片能够具有预设宽度和厚度的间隙。该间隙的厚度范围可以为例如0.2密耳～50密耳，例如5密耳、10密耳、15密耳、25密耳、30密耳或45密耳的厚度。
该膜、溶液和分散体的厚度可以根据应用而变化。在干成型制品的情况下，最终的厚度可以在例如约0.1密耳～约250密耳的范围，例如约0.5密耳～约25密耳，包括约1～约6密耳(1密耳＝千分之一英寸)。
适合的厚度包括约0.5密耳～约12密耳，约0.5密耳～约10密耳，和约1.5密耳～约9密耳。对于水性分散体，其用量可以例如约2.5g/m2～约6.40kg/m2范围，例如约12.7～约635g/m2，包括约25.4～约152.4g/m2。
能够用落入本发明范围内的分散体和成型制品涂覆的平坦片材和带的类型包括但不局限于：纺织织物(textile fabric)，包括织造物(wovens)和针织物(knits)；非织造织物(nonwovens)；皮革(真实的或合成的)；纸；金属；塑料；和稀松布(scrim)。
能够使用落入本发明的范围内的分散体和成型制品制备的最终制品包括但不局限于：服饰，其包括任何类型的服装或布料制品；针织手套；室内装饰；头发附件；床单；地毯和地毯背衬；传送带；医疗应用，例如绷带；个人护理品，包括失禁和女性卫生品；和鞋类。涂覆有分散体或覆盖有膜或带的制品可以用作声抑制制品。
层压到成型制品上的非弹性织物能够具有改进的拉伸和恢复性和改进的模制性质。
包括成型制品、膜、带或聚氨酯水性分散体的制品可以被模制。该制品可以制备有基体和成型制品、膜、带或分散体的多个层。该多层制品也可以被模制。模制和非模制的制品可以具有不同的拉伸和恢复程度。所述模制制品可以包括塑身或身体支撑服装，例如胸罩。
能够使用落入本发明范围内的分散体和成型制品制备的服饰或服装的实例包括但不局限于：内衣、胸罩、妇女或儿童穿短裤、女内衣裤、游泳衣、塑形衣、女背心、袜类、睡衣、围裙、湿式潜水服、鞋带、擦洗布、太空服、制服、帽子、吊袜带、吸汗带、腰带、运动服、外衣、雨衣、冷天夹克、裤子、衬衫衣料、女服、罩衫、男用或女用上衣、毛衣、胸衣、汗衫、衬裤、短袜、高及膝的、女服、罩衫、围裙、宴会短礼服、bisht、长袍、hijab、jilbab、thoub、厚呢短斗篷、斗篷、套装、潜水服、苏格兰打褶短裙、和服、紧身运动套衫、袍子、防护衣、莎丽、莎笼、裙子、鞋罩、古罗马妇女的外套、套装、紧身衣、托加袍、紧身衣、毛巾、制服、面罩、紧身潜水衣、医用压缩服、绷带、衣服衬里、腰带和其中的所有部件。
在Walter等的“Solving common coating flaws in Reverse RollCoating，”AIMCAL Fall Technical Conference(10月26-29日，2003)中描述了用于执行和克服逆向辊涂中共同的问题的方法，其全部公开内容通过引用引入此处。
本发明的另一方面是包括该成型制品和基体的制品，其中该成型制品和该基体相附着以形成层压物，由此该弹性层压物的摩擦系数大于单独该基体的摩擦系数。其实例是具有包括聚氨酯水性分散体的涂层或膜的腰带，其防止该服装从另一服装(例如罩衫或衬衫)上滑动，或者可替代地防止该腰带在该服装穿用者的皮肤上滑动。
成型制品，例如该聚氨酯脲水性分散体的膜，可以具有以下性质：
在拉伸后的永久变形为约0～10％，例如约0～5％，典型地为约0～约3％，
约400～约800％的拉伸率，和
约0.5～约3Mpa的韧度(tenacity)。
由制品和基体制备的层压物可以具有以下性质：
在50次洗涤之后的剥离强度，其中从洗涤前的强度保持至少50％，
至少约0～约0.5cfm的透气率，和
在24小时内至少约0～约300g/m2的水蒸气渗透率。
分析方法
在以下实施例中，使用以下分析方法：
用于粘合结合的剥离强度
修正ASTM D903-93(其全部公开内容通过引用结合进来)来测试膜层压织物。用于测试的样品尺寸为1英寸×6英寸(2.5cm×15cm)。分离速率为2英寸/分钟(5厘米/分钟)。数据报道为每英寸样品宽度的力的磅数(千克/毫米)，如表2和4中所示。
洗涤试验
使用AATCC试验方法150-2001(其全部公开内容通过引用结合进来)来洗涤模制的胸罩罩杯。机器工作周期为(I)标准/棉厚重质地(cottonsturdy)。洗涤温度为(III)41℃。干燥程序为(A)(i)翻滚棉厚重质地66℃30分钟，10分钟冷却时间。
水蒸气传送
使用ASTM E96-00(其全部公开内容通过引用结合进来)来测试制品的水蒸气传送性质。数据报道为24小时时间的克/平方米，如表7中所示。
透气性
使用ASTM D-737(其全部公开内容通过引用结合进来)来测试制品的透气性质。数据报道为立方英尺空气/分钟/平方英尺织物(cfm，立方厘米空气/秒/平方厘米织物(ccs))，如表7中所示。
拉伸率(elongation)、韧度(tenacity)和永久变形(set)
使用动态拉伸试验仪Instron对膜测试拉伸率和韧度性质。样品尺寸为1×3英寸(1.5cm×7.6cm)，沿着长尺寸测量。将样品放置在夹具中，并以200％拉伸率/分钟的应变速率延展，直至达到最大拉伸率。刚好在膜断裂之前测试韧度和拉伸率。类似地，通过以200％/分钟的应变速率将1×3英寸的膜样品(1.5cm×7.6cm)从0～50％拉伸率延展5个循环来测试永久变形％。在第5个循环之后测试永久变形％。
实施例
HP 4000D是数均分子量为400的线性伯羟基封端的聚丙烯醚二醇(可在市场上获自BASF，Brussels，Belgium)；
DMPA是2，2-二羟甲基丙酸。
以下预聚物样品是用包含高含量的2，4’-MDI的MDI同分异构体混合物(例如
MI和
ML)制备的。
实施例1
该预聚物的制备是在氮气气氛的手套箱中进行的。在装备有气压驱动搅拌器、加热罩和热电偶温度测量装置的2000ml
玻璃反应釜中加入约382.5克的
1800二元醇和约12.5克的DMPA。在搅拌下将该混合物加热到约50℃，然后添加约105克的
MI二异氰酸酯。然后在连续搅拌下将该反应混合物加热到约90℃，并在约90℃保持约120分钟，在该时间之后完成反应，因为该混合物的％NCO下降到稳定值，符合具有异氰酸酯端基的该预聚物的计算值(1.914的％NCO目标值)。使用在约40℃操作的Model DV-8Falling BallViscometer(由Duratech Corp.，Waynesboro，VA销售)依照ASTMD1343-69的通用方法测定该预聚物的粘度。用S.Siggia，“QuantitativeOrganic Analysis via Functional Group”，3rd Edition，Wiley & Sons，NewYork，pp.559-561(1963)的方法测定该封端二元醇预聚物以NCO基团重量百分比计的总异氰酸酯部分含量，通过引用将其全部公开内容结合进来。
实施例2
使用依照实施例1中所述的程序和组合物制备的无溶剂预聚物来制备本发明的聚氨酯脲水性分散体。
在2000ml的不锈钢烧杯中添加约700克的去离子水、约15克的十二烷基苯磺酸钠(SDBS)和约10克的三乙基胺(TEA)。然后用冰/水将该混合物冷却到约5℃并用具有转子/定子混合头(Ross，Model100LC)的高剪切实验室混合器以约5000rpm混合约30秒。将以实施例1的方式制备且容纳在金属管状圆柱体内的该粘性预聚物用施加的气压通过软管添加到该水溶液中的混合头的底部。将该预聚物的温度保持在约50℃～约70℃。用水在约5000rpm的连续混合下将该挤出的预聚物物流分散并链扩增。在约50分钟的时期内，将总量约540克的预聚物引入并分散在水中。在添加并分散该预聚物之后，立即在该分散混合物中添加约2克Additive 65(可在市场上获自Dow
MidlandMichigan)和约6克的二乙基胺(DEA)。然后将该反应混合物再混合约30分钟。所得到的无溶剂的水性分散体是乳白色和稳定的。用添加和混合用量为该水性分散体的约2.0wt％的Hauthane HA增稠剂900(可在市场上获自Hauthway，Lynn，Massachusetts)来调节该分散体的粘度。然后将该粘性分散体过滤通过40微米Bendix金属筛网过滤器并储存在室温下用于膜浇铸或层压用途。该分散体具有43％的固含量和约25000厘泊的粘度。由该分散体浇铸的膜是柔软的、发粘的和弹性体的。
实施例3
制备程序与实施例2中相同，只是在混合该预聚物之后不将DEA添加到该分散体中。最初，该分散体呈现为与实施例2没有不同。然而，当该分散体在室温下老化一周或更长时间之后，由该分散体浇铸的膜是易碎的，且不适用于粘合或层压。
实施例4
依照上述ASTM测试方法测试数种多层制品的透气率；该结果示于下表中。
测试结果显示，与可在市场上获得的热塑性聚氨酯膜和由聚氨酯脲溶液浇铸的膜相比，本发明的聚氨酯脲分散体的膜提供了更大的透气率。
尽管已经以示例性的方式描述了本发明，但应当认识到所用的术语意于为表述或描述的性质而非限制性质。此外，尽管已经根据几个示例性实施方案方面描述本发明，但应当认识到本领域技术人员将容易将这些教导应用于本发明的其他可能的变型。
Claims (35)
1.包括多个层的制品，所述制品包括：
a)至少两个层；和
b)至少一个聚氨酯脲膜。
2.权利要求1的制品，其中所述膜是由聚氨酯脲水性分散体浇铸而成的。
3.权利要求2的制品，其中所述分散体是基本无溶剂的。
4.权利要求2的制品，其中所述分散体包含预聚物，所述预聚物包含：
(a)选自聚醚类、聚酯类、聚碳酸酯类及其组合的至少一种多元醇，其中该多元醇具有600～3500的数均分子量；
(b)4，4’-和2，4’-亚甲基双(苯基异氰酸酯)(MDI)同分异构体的混合物，其中4，4’-MDI与2，4’-MDI同分异构体的比例在65∶35～35∶65范围；和
(c)至少一种二醇化合物，所述二醇化合物包含：(i)能够与组分b)的MDI同分异构体的混合物反应的羟基，和(ii)至少一个一旦中和能够生成盐的羧酸基团，其中所述至少一个羧酸基团不能与MDI同分异构体的所述混合物反应。
5.权利要求1的制品，其中该膜在所述至少两个层之间。
6.权利要求1的制品，其中所述至少两个层选自由以下构成的组：(a)两个织物层，(b)两个泡沫层，(c)织物层和泡沫层，及其组合。
7.权利要求1的制品，其中所述至少两个层包括至少两个织物层和至少两个泡沫层。
8.权利要求7的制品，其中该膜在每一侧上都与泡沫层相邻，且每一泡沫层与织物层相邻。
9.权利要求1的制品，其中该制品是模制的。
10.权利要求1的制品，其中该制品是压制的。
11.权利要求1的制品，其中该膜延伸遍及该多层制品的全部区域。
12.权利要求1的制品，其中该膜延伸到该多层制品的一部分区域。
13.权利要求1的制品，其中包括至少两个聚氨酯脲膜。
14.权利要求4的制品，其中所述聚氨酯脲分散体包含具有约40000～约150000的重均分子量的聚合物。
15.权利要求4的制品，其中所述聚氨酯脲分散体包含具有约100000～约150000的重均分子量的聚合物。
16.权利要求4的制品，其中所述聚氨酯脲分散体包含具有约120000～约140000的重均分子量的聚合物。
17.权利要求1的制品，其中所述膜是多孔的。
18.权利要求1的制品，其中所述膜是穿孔的。
19.权利要求1的制品，其为衣服的形式。
20.权利要求6的制品，进一步包括在两个或更多个层之间的粘合剂。
21.权利要求20的制品，其中所述粘合剂是热熔粘合剂、接触粘合剂、热固性物、热塑性物或者聚氨酯脲水性分散体。
22.包括多个层的制品，所述制品包括：
a)至少两个层；和
b)聚氨酯脲水性分散体。
23.权利要求22的制品，其中所述分散体包含预聚物，所述预聚物包含：
(a)选自聚醚类、聚酯类、聚碳酸酯类及其组合的至少一种多元醇，其中该多元醇具有600～3500的数均分子量；
(b)4，4’-和2，4’-亚甲基双(苯基异氰酸酯)(MDI)同分异构体的混合物，其中4，4’-MDI与2，4’-MDI同分异构体的比例在65∶35～35∶65范围；和
(c)至少一种二醇化合物，所述二醇化合物包含：(i)能够与组分b)的MDI同分异构体的所述混合物反应的羟基，和(ii)至少一个一旦中和能够生成盐的羧酸基团，其中所述至少一个羧酸基团不能与MDI同分异构体的所述混合物反应。
24.权利要求23的制品，其中所述分散体基本无溶剂。
25.权利要求22的制品，其中所述分散体是粘合剂。
26.权利要求22的制品，其中所述分散体在层之间。
27.权利要求22的制品，其中所述至少两个层选自由以下构成的组：(a)两个织物层，(b)两个泡沫层，(c)织物层和泡沫层，及其组合。
28.权利要求22的制品，其中将该分散体喷涂在层上。
29.权利要求22的制品，其为衣服的形式。
30.制品，包括：
(a)至少两个层；和
(b)至少一个聚氨酯脲膜；
其中所述膜层压在所述至少两个层之间，且所述制品经过模制。
31.权利要求30的制品，其中所述至少两个层选自由以下构成的组：(a)两个织物层，(b)两个泡沫层，(c)织物层和泡沫层，及其组合。
32.权利要求30的制品，进一步包括聚氨酯脲水性分散体。
33.制品，包括：
(a)至少一个织物层；和
(b)至少一种选自由膜、分散体及其组合构成的组的聚氨酯脲组合物。
34.权利要求33的制品，其中所述制品是衣服，且所述聚氨酯脲组合物降低了衣服和基体之间的相对运动。
35.权利要求34的制品，其中所述基体是皮肤。
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| US11/745,668 US20070264462A1 (en) | 2005-02-11 | 2007-05-08 | Laminated fabric construction with heat activated polyurethaneurea compositions |
| US11/745,668 | 2007-05-08 | ||
| PCT/US2008/059860 WO2008140877A2 (en) | 2007-05-08 | 2008-04-10 | Laminated fabric construction with heat activated polyurethaneurea compositions |
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Family
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| EP (1) | EP2152508A2 (zh) |
| JP (2) | JP2010534573A (zh) |
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| CN (1) | CN102015281A (zh) |
| BR (1) | BRPI0810349A2 (zh) |
| TW (1) | TW200906618A (zh) |
| WO (1) | WO2008140877A2 (zh) |
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2007
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-
2008
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- 2008-04-10 BR BRPI0810349 patent/BRPI0810349A2/pt not_active IP Right Cessation
- 2008-04-10 WO PCT/US2008/059860 patent/WO2008140877A2/en active Application Filing
- 2008-04-10 CN CN2008800237965A patent/CN102015281A/zh active Pending
- 2008-04-10 JP JP2010507501A patent/JP2010534573A/ja active Pending
- 2008-04-10 EP EP08745462A patent/EP2152508A2/en not_active Withdrawn
- 2008-04-21 TW TW97114523A patent/TW200906618A/zh unknown
-
2013
- 2013-11-15 JP JP2013236811A patent/JP2014040109A/ja active Pending
-
2014
- 2014-11-24 US US14/552,060 patent/US20150079339A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4801644A (en) * | 1985-10-04 | 1989-01-31 | Polyvinyl Chemicals Inc. | Coating compositions |
| US5769106A (en) * | 1996-05-15 | 1998-06-23 | Achuff; Jonathan M. | Convertible panel and shelter system |
| US20040058603A1 (en) * | 2002-09-23 | 2004-03-25 | Hayes James F. | Laminated tarp material |
| US20060183849A1 (en) * | 2005-02-11 | 2006-08-17 | Invista North America S.A R.L. | Solvent free aqueous polyurethane dispersions and adhesive films therefrom for stretch fabrics |
| WO2006086715A2 (en) * | 2005-02-11 | 2006-08-17 | Invista Technologies S.A R.L. | Solvent free aqueous polyurethane dispersions and shaped articles therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795693A (zh) * | 2014-06-11 | 2017-05-31 | 英威达技术有限公司 | 包括水性聚氨酯组合物的分散体和膜 |
| TWI763876B (zh) * | 2017-07-04 | 2022-05-11 | 德商科思創德意志股份有限公司 | 含膨脹之ｔｐｕ及塗層之物件 |
| CN112867745A (zh) * | 2018-09-27 | 2021-05-28 | 科思创知识产权两合公司 | 分散体胶粘剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0810349A2 (pt) | 2014-10-14 |
| WO2008140877A2 (en) | 2008-11-20 |
| US20070264462A1 (en) | 2007-11-15 |
| EP2152508A2 (en) | 2010-02-17 |
| WO2008140877A3 (en) | 2010-11-18 |
| US20150079339A1 (en) | 2015-03-19 |
| KR20100017682A (ko) | 2010-02-16 |
| JP2014040109A (ja) | 2014-03-06 |
| TW200906618A (en) | 2009-02-16 |
| JP2010534573A (ja) | 2010-11-11 |
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Application publication date: 20110413 |