CN115087715A - 反应性热熔粘合剂组合物及其用途 - Google Patents

反应性热熔粘合剂组合物及其用途 Download PDF

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CN115087715A
CN115087715A CN202080096278.7A CN202080096278A CN115087715A CN 115087715 A CN115087715 A CN 115087715A CN 202080096278 A CN202080096278 A CN 202080096278A CN 115087715 A CN115087715 A CN 115087715A
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adhesive composition
hot melt
reactive hot
melt adhesive
component
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朱宏业
车爱馥
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Henkel AG and Co KGaA
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Abstract

本发明提供一种反应性热熔粘合剂组合物及其用途。所述反应性热熔粘合剂组合物包含至少一种NCO封端的聚氨酯预聚物，所述NCO封端的聚氨酯预聚物包含以下组分的反应产物：a)至少一种多异氰酸酯，b)至少一种选自以下的多元醇：聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合，和c)任选存在的至少一种不同于组分b)的多元醇，其中NCO/OH比率大于1，优选为约1.5至约2.5，所述NCO/OH比率为组分a)的NCO基团与组分b)和c)的总OH基团的摩尔比。

Description

反应性热熔粘合剂组合物及其用途
技术领域
本发明涉及反应性热熔粘合剂组合物及其用途。具体地，本发明提供具有优异的耐洗涤性，特别是对抗菌衣物清洁剂具有优异的耐受性的粘合剂。此外，所述粘合剂在固化时具有特别短的开放时间和良好的柔软性。
背景技术
反应性热熔粘合剂已经广泛用于将织物与织物粘合，尤其是用于服装或特别是内衣制造领域，以代替缝合和热封带，这简化了工艺，节约了成本，减少了交付时间，并且获得了在市场上更有竞争力的产品。
例如H.F.Hüber和H.Müller在"Shaping Reactive Hotmelts Using LMWCopolyesters",Adhesives Age,November 1987,32至35页中描述了基于异氰酸酯封端的(也称为“NCO-封端的”)聚氨酯预聚物的反应性热熔粘合剂。
然而，现有的反应性热熔粘合剂不能经受频繁的洗涤，尤其是当使用抗菌衣物清洁剂时。因此，本领域需要克服该缺点的反应性热熔粘合剂。
发明内容
本文公开了包含至少一种NCO封端的聚氨酯预聚物的反应性热熔粘合剂组合物，所述NCO封端的聚氨酯预聚物包含以下组分的反应产物：
a)至少一种多异氰酸酯，
b)至少一种多元醇，其选自聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合，和
c)任选存在的至少一种不同于组分b)的多元醇，
其中NCO/OH比率大于1，优选为约1.5至约2.5，该NCO/OH比率为组分a)的NCO基团与组分b)和c)的总OH基团的摩尔比。
本文还公开了根据本发明的反应性热熔粘合剂组合物的固化产物。
本文还公开了根据本发明的反应性热熔粘合剂组合物用于粘合两个基材，尤其是衣服或内衣中的两个基材的用途，其中所述两个基材中的至少一个是织物。
在下面更详细地阐述本主题的其他特征和方面。
具体实施方式
本领域普通技术人员应当理解，本讨论仅是对示例性实施方案的描述，而不旨在限制本发明的更广泛方面。
在一个方面，本发明总体上涉及包含至少一种NCO封端的聚氨酯预聚物的反应性热熔粘合剂组合物，所述NCO封端的聚氨酯预聚物包含以下组分的反应产物，基本上由以下组分的反应产物组成或由以下组分的反应产物组成：
a)至少一种多异氰酸酯，
b)至少一种多元醇，其选自聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合，和
c)任选存在的至少一种不同于组分b)的多元醇，
其中NCO/OH比率大于1，优选为约1.5至约2.5，该NCO/OH比率为组分a)的NCO基团与组分b)和c)的总OH基团的摩尔比。
本文所用的与数值相关的“约”是指数值±该值的10％，优选数值±该值的5％。例如，“约20重量％”因此涉及20±2重量％，优选20±1重量％。
本文所用的“室温”是指约20℃至约25℃，优选约25℃的温度。
根据本发明，聚氨酯预聚物具有大于1的NCO/OH比率，该NCO/OH比率是通过组分a)的NCO基团的摩尔量除以组分b)和c)的OH基团的总摩尔量而计算的。
通过使多异氰酸酯a)与多元醇b)和c)(如果存在)反应获得聚氨酯预聚物。通过将NCO/OH比率设定为大于1，聚氨酯预聚物含有游离异氰酸酯基团并被异氰酸酯基团封端。作为前往交联聚氨酯的中间体，异氰酸酯封端的聚氨酯预聚物与基材表面或环境水分反应以扩展主链并因此形成聚氨酯聚合物。通过水分从大气或基材扩散到粘合剂中并随后反应，聚氨酯预聚物在大气条件下固化。因此，聚氨酯热熔粘合剂组合物是反应性的且可湿固化的。固化的粘合剂产物是主要通过脲基团和氨基甲酸酯基团结合的交联材料。
在一个实施方案中，聚氨酯预聚物具有约1.5至约2.5的NCO/OH比率。在NCO/OH比率落在上述范围内的情况下，聚氨酯预聚物在暴露于水分时充分交联，并且具有所需的粘度，该粘度易于喷涂，但不拉丝或不渗透织物。
在一个实施方案中，基于聚氨酯预聚物的总重量，根据本发明的聚氨酯预聚物具有约1重量％至约5重量％、优选约1.2重量％至约4重量％的NCO含量。在NCO含量落在上述范围内的情况下，聚氨酯预聚物在暴露于水分时充分交联，并且具有所需的粘度，该粘度易于喷涂，但不拉丝或不渗透织物。
根据本发明，聚氨酯预聚物通过组分a)至少一种多异氰酸酯与组分b)至少一种选自聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合的多元醇，任选地还与组分c)至少一种不同于组分b)的多元醇反应而制备。
如本文所用，术语“多异氰酸酯”应理解为每分子优选具有2至4个异氰酸酯基团。优选地，所述多异氰酸酯是二异氰酸酯，包括脂肪族、脂环族或芳族二异氰酸酯。
在一个实施方案中，芳族二异氰酸酯选自2,2'-亚甲基二苯基二异氰酸酯(MDI)、4,4'-亚甲基二苯基二异氰酸酯、2,4'-亚甲基二苯基二异氰酸酯、2,4-甲苯二异氰酸酯(TDI)、2,6-甲苯二异氰酸酯、1,3-亚苯基二异氰酸酯(PDI)、1,4-亚苯基二异氰酸酯、1,4-亚萘基二异氰酸酯(NDI)、1,5-亚萘基二异氰酸酯、四甲基亚二甲苯基二异氰酸酯(TMXDI)、4,4'-二苄基二异氰酸酯、亚二甲苯基二异氰酸酯(XDI)，以及它们的组合。
在一个实施方案中，脂肪族异氰酸酯选自丁烷-1,4-二异氰酸酯、1,6-六亚甲基二异氰酸酯(HMDI)、1,6-二异氰酸基-2,2,4-三甲基己烷、1,12-二异氰酸基-十二烷，以及它们的组合。
在一个实施方案中，脂环族异氰酸酯选自异佛尔酮二异氰酸酯(IPDI)、4,4-二环己基甲烷二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、1-甲基-2,4-二异氰酸基-环己烷，以及它们的组合。
优选地，多异氰酸酯选自2,2'-亚甲基二苯基二异氰酸酯、4,4'-亚甲基二苯基二异氰酸酯、2,4'-亚甲基二苯基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或它们的组合。更优选地，MDI用作多异氰酸酯。
在根据本发明的反应性热熔粘合剂组合物中，基于聚氨酯预聚物的总重量，组分a)至少一种多异氰酸酯的量为约10重量％至约40重量％、优选约15重量％至约35重量％。
根据本发明，组分b)是至少一种选自聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合的多元醇。这些特定的多元醇赋予固化产物优异的耐化学性和优异的耐水解性。
在一个实施方案中，每种组分b)和c)的官能度为2。换言之，每种多元醇b)和c)独立地为二醇。官能度是指每分子多元醇的羟基的平均数。
组分b)优选具有至少一个端羟基，更优选具有两个端羟基，这促进聚氨酯预聚物的形成。
在一个实施方案中，聚四氢呋喃、聚丁二烯多元醇和氢化聚丁二烯多元醇各自具有约1,000至约5,000g/mol，优选约1,000至约3,500g/mol的数均分子量(Mn)。落在上述范围内的Mn使这些特定的聚醚多元醇与配制品中的其它组分相容，并调节粘合剂组合物的粘合强度和开放时间。
在本说明书中，数均分子量(Mn)可以通过凝胶渗透色谱法(GPC)根据DIN 55672，特别是DIN 55672-1用THE作为洗脱剂来测定。
如本文所用，术语“聚四氢呋喃”可与聚(四亚甲基醚)二醇(PTMEG)互换，并且由式HO-(-CH2)4O-)n-H表示。聚四氢呋喃具有优异的耐化学性和优异的耐水解性，并且赋予衍生的聚氨酯粘合剂组合物这些性质。
在一些实施方案中，聚四氢呋喃在室温下为白色蜡状固体或液体。其在约25℃至约40℃下熔化成无色或浅黄色。
聚四氢呋喃可以通过四氢呋喃的阳离子开环聚合而制备。聚四氢呋喃可从KoreaPTG Co.,Ltd以例如PTMEG 1000、PTMEG 1800、PTMEG 2000和PTMEG 3000商购获得。
在一个实施方案中，聚丁二烯二醇具有由式HO-(-C-C＝C-C-)n-OH表示的主链。氢化聚丁二烯二醇具有由式HO-(-C-C-C-C-)n-OH表示的主链。聚丁二烯二醇和氢化聚丁二烯二醇可具有一个或多个接枝在它们的主链上用于改变性质的侧基。所述侧基可以是例如C1-C10烷基。聚丁二烯二醇和氢化聚丁二烯二醇具有优异的耐化学性、耐水解性、耐老化性和耐黄变性，并且赋予衍生的聚氨酯粘合剂组合物这些性质。氢化聚丁二烯二醇在这些性质方面更优异，因此是优选的。
在一些实施方案中，聚丁二烯二醇和氢化聚丁二烯二醇在室温下为无色或浅黄色液体。一些聚丁二烯二醇和氢化聚丁二烯二醇不具有玻璃化转变温度(Tg)。如果具有，则它们的玻璃化转变温度(Tg)通常低于0℃，例如为约-30℃至约-50℃、优选为约-30℃至约-45℃。
如本文所提及的，玻璃化转变温度(Tg)是通过差示扫描量热法(DSC)测量的。
聚丁二烯二醇和氢化聚丁二烯二醇是可商购的。例如，它们由Cray ValleyCorporation以产品名称Krasol销售。聚丁二烯二醇的具体实例包括Krasol LBH-P 2000、Krasol LBH 3000和Krasol LBH-P 3000。氢化聚丁二烯二醇的具体实例包括Krasol HLBH-P2000和Krasol HLBH-P3000。
在一个实施方案中，术语“聚碳酸酯多元醇”理解为具有重复单元-O-C(O)O-并且由一个或多个，优选两个羟基封端。聚碳酸酯多元醇，优选聚碳酸酯二醇具有优异的耐候性和耐水解性，并且赋予衍生的聚氨酯粘合剂组合物这些性质。
在一个实施方案中，聚碳酸酯多元醇是无定形的，因此其赋予聚氨酯预聚物良好的可喷涂性并赋予固化产物良好的柔软性。聚碳酸酯多元醇在室温下可以是固体或液体。对于无定形固体，其玻璃化转变温度(Tg)高于室温。无定形液体的玻璃化转变温度(Tg)，如果具有，则低于室温。
聚碳酸酯多元醇可以例如通过脂肪族二醇如丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、二甘醇、三甘醇或它们的混合物与碳酸二芳基酯或碳酸二烷基酯例如碳酸二甲酯反应而制备。
聚碳酸酯二醇是可商购的。例如，它们由Asahi Kasei Corporation以商品名DuranoITM作为系列产品出售。聚碳酸酯二醇的具体实例包括DuranoITMT5652、DuranoITMT5651、DuranoITMT5650J、DuranoITMT5650E、DuranoITMT4672、DuranoITMT4671、DuranoITMT4692、DuranoITMT4691、DuranoITMT6001、DuranoITMT6002、DuranoITMG3452和DuranoITMG3450J。
在根据本发明的反应性热熔粘合剂组合物中，基于聚氨酯预聚物的总重量，组分b)的量为约5重量％至约70重量％、优选约10重量％至约60重量％、更优选约20重量％至约60重量％。
在一个实施方案中，组分c)即至少一种不同于组分b)的多元醇包含在用于制备聚氨酯预聚物的反应物中。对组分c)没有具体限制，并且可在本文中使用通常用于制备聚氨酯的聚醚多元醇或聚酯多元醇，只要其不会不利地影响本发明的热熔粘合剂组合物的所需性质。
在一个实施方案中，组分c)选自聚醚多元醇、聚酯多元醇以及它们的组合。
组分c)可以是结晶的、无定形的或它们的混合物。
在一个实施方案中，组分c)是结晶的并且具有约40至约100℃的熔点。如果组分c)是结晶的并且具有约40至约100℃的熔点，则晶粒的聚集使表面在短时间内干燥，因此粘合剂组合物具有非常短的开放时间，例如约1分钟至不超过约5分钟、优选约1分钟至约2分钟。
在另一个实施方案中，组分c)是无定形的并且具有约-40至约40℃的玻璃化转变温度(Tg)。优选地，组分c)的玻璃化转变温度(Tg)等于或高于组分b)的Tg。
如果组分c)是无定形的并且具有约-40℃至约40℃的玻璃化转变温度(Tg)，尤其是当组分c)的Tg等于或高于组分b)的Tg时，粘合剂组合物具有较高的粘度，这有助于表面在短时间内干燥，因此粘合剂组合物具有非常短的开放时间，例如约1分钟至不超过约5分钟、优选约1分钟至约2分钟。
组分c)是可商购的。例如，组分c)的商业产品包括来自Evonik Corporation的Dnyacoll系列，例如Tg为约-30℃至约-10℃的无定形液体多元醇，例如Dnyacoll 7210、Dnyacoll 7230和Dnyacoll 7231；Tg为约10℃至约50℃的无定形多元醇，例如，Dnyacoll7110、Dnyacoll 7111、Dnyacoll 7130、Dnyacoll 7131、Dnyacoll 7140和Dnyacoll 7150；熔点为约40℃至约100℃的结晶多元醇，例如，Dnyacoll 7320、Dnyacoll 7330、Dnyacoll7340、Dnyacoll 7360、Dnyacoll 7362、Dnyacoll 7363、Dnyacoll 7365、Dnyacoll 7380和Dnyacoll 7381。组分c)的商业产品还包括Stepan Company以Stepanpol系列出售的芳族聚酯多元醇，例如stepanpol PH-56、PHN-56、PDP-70和PN-110。
在根据本发明的反应性热熔粘合剂组合物中，基于聚氨酯预聚物的总重量，组分c)的量为约0重量％至约75重量％、优选约20重量％至约60重量％。
在一个实施方案中，NCO封端的聚氨酯预聚物包含以下组分的反应产物，基本上由以下组分的反应产物组成或由以下组分的反应产物组成：
a)约10重量％至约40重量％、优选约15重量％至约35重量％的至少一种多异氰酸酯，
b)约5重量％至约70重量％、优选约10重量％至约60重量％、更优选约20重量％至约60重量％的至少一种多元醇，所述多元醇选自聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合，和
c)0重量％至约75重量％、优选约20重量％至约60重量％的至少一种不同于组分b)的多元醇，
以上均基于所述聚氨酯预聚物的总重量。
根据本发明的反应性热熔粘合剂组合物在120℃下具有约10000至约30000cps、优选约15000至约20000cps的布氏(Brookfield)粘度，该布氏粘度是根据ASTM 1084-1997通过配备有Thermosel加热单元的布氏粘度计RVDVII使用转轴27以2.5至10rpm测量的。
在一个实施方案中，粘合剂组合物的熔融温度为约100至约140℃。
在本说明书中，如果没有另外说明，熔融温度是指根据ISO 11357，特别是ISO11357-3，通过差示扫描量热仪(DSC)测量的值。具体地，当温度以10℃/分钟的速率从-50℃升高至250℃时观察到的吸热峰的峰顶被视为熔融温度。
洗涤后，尤其是用抗菌衣物清洁剂洗涤后，固化组合物的粘合强度保持率为约75％或更高、优选约80％或更高、更优选约83％或更高。通过将洗涤后的固化产物的粘合强度除以洗涤前的固化产物的粘合强度来计算粘合强度保持率。
根据JIS L1093方法A-1测量固化产物的粘合强度。抗菌衣物清洁剂包含至少一种清洁剂和至少一种抗菌剂。对清洁剂和抗菌剂没有特别的限制，并且通常用于洗衣的那些在本文中是合适的。例如，清洁剂的可商购实例包括可购自P&G Corporation的Head&Shoulder。抗菌剂的可商购实例包括以商品名
Figure BDA0003790326610000081
和
Figure BDA0003790326610000082
销售的产品。
在一些实施方案中，根据本发明的反应性热熔粘合剂具有非常短的开放时间，例如约1分钟至不超过约5分钟、优选约1分钟至约2分钟。“开放时间”是指从施用粘合剂时到可开始安装时的最小所需时间。
在一些实施方案中，根据本发明的反应性热熔粘合剂组合物可耐受高温下的洗涤，例如在约60℃或更高、约70℃或更高、约80℃或更高和约90℃或更高的温度下，例如在约92℃下的洗涤。
在一些实施方案中，根据本发明的固化组合物具有柔软触感，这使其适用于衣服，尤其适用于内衣。
虽然粘合剂组合物可以如上所述直接使用，但是如果需要，本发明的粘合剂组合物也可以用与组合物相容的常规添加剂配制。这样的添加剂包括消泡剂、增塑剂、相容的增粘剂、固化催化剂、离解催化剂、填料、流变改性剂、抗氧化剂、颜料、粘合促进剂、稳定剂、阻燃剂等。与根据本发明的组合物相容的常规添加剂可简单地通过将潜在添加剂与组合物组合并确定它们是否相容来确定。如果添加剂在产品中是均匀的，则它是相容的。
通常，根据本发明的反应性热熔粘合剂组合物可用于粘合两个基材，特别是在衣服或内衣中的两个基材，其中两个基材中的至少一个是织物。另一个基材可以是织物或泡沫。具体地，根据本发明的反应性热熔粘合剂组合物可用于将衣服中的，尤其是内衣中的织物与织物粘合，或织物与泡沫粘合。
将根据本发明的反应性热熔粘合剂加热至熔融，并将熔融的粘合剂施加到待粘合的基材中的一个或两个上。
最终固化可以使用各种条件进行。特别地，通过空气中水分的作用实现固化，其中相对湿度不小于10％、优选不小于25％、更优选不小于50％。
组合物通常在不存在水分的情况下以其固体形式分配和储存。当组合物准备使用时，在施用前将固体加热并熔化。因此，本发明既包括固体形式的反应性热熔粘合剂组合物，因为其通常是待储存和分配的，也包括就在其施用之前，将其熔融之后，液体形式的反应性热熔粘合剂组合物。
实施例
以下实施例说明了本发明并且不旨在限制本发明。
原料
组分a)：
MDI：4'4-亚甲基二苯基二异氰酸酯，可商购自Convestro。
组分b)：
PTMEG 2000：聚四氢呋喃，Mn：2000g/mol，Tg：-76℃,熔点：32℃，可商购自PTGCo.,Ltd。
HLBH-P 2000：氢化聚丁二烯二醇，Mn：2100g/mol，液体，Tg:-30℃，可商购自CrayValley Corporation。
Duranol T 5652：聚碳酸酯二醇，无定形，液体，Tg：-54℃，可商购自Asahi KaseiCorporation。
组分c)：
Dynacoll 7130：聚酯多元醇，无定形，固体，Tg：30℃，可购自EvonikCorporation。
Dynacoll 7210：聚酯多元醇，无定形，液体，Tg：-15℃，可购自EvonikCorporation。
Dynacoll 7231：聚酯多元醇，无定形，液体，Tg：-30℃，可购自EvonikCorporation。
Dynacoll 7360：聚酯多元醇，结晶，熔点：55℃，可购自Evonik Corporation。
PES 9007：液体聚酯多元醇，无定形，液体，Tg：-20℃，可购自XuchuanCorporation。
PN-110：聚酯多元醇，无定形，Tg：25℃，可购自Stepan Company。
预聚物的制备
根据表1中列出的配方制备预聚物。预聚物的所有组分的总重量为100重量份。
将所有多元醇添加到三颈圆底烧瓶中以熔融并且在真空下混合直到均匀，并且在130℃下脱水2小时。然后在100℃下将MDI加入到混合物中，在110℃真空搅拌下进行聚合，直到1.5小时后反应完成。通过硝化分析剩余的NCO含量以确定反应的完成。
测试方法和评价：
粘合强度保持率
在90至120℃下通过凹印辊(X-TH13，可购自东莞的Xinxin Corporation)将如上制备的每种预聚物以20μm的厚度涂覆到10m*0.5m的聚酯织物(可购自Xiaoshan RongliCorporation)上，然后与另一10m*0.5m的聚酯织物层压以得到层压样品。将层压样品在23℃和50％相对湿度下固化3-7天。根据JIS L1093方法A-1测量固化的层压样品的粘合强度。每个粘合强度测量3次，平均值记录为N1。然后将固化的层压样品浸入Head&Shoulder(清洁剂，可购自P&G Corporation)和
Figure BDA0003790326610000101
(抗菌剂)的水性混合物中72小时。以与N1相同的方式测量洗涤后的粘合强度并记录为N2。
粘合强度保持率＝N2/N1*100％
开放时间
在100至140℃下通过凹印辊(X-TH13，可购自东莞的Xinxin Corporation)用如上制备的每种预聚物以20μm的厚度涂布10cm*1cm纸。每30秒通过手指压力将纸条(1.5cm*5.0cm)附着到涂布的纸上。开放时间定义为直到观察到纸条的纤维撕裂的时间。
柔软性
用5名志愿者的手触摸上面获得的用于测量粘合强度N1的固化的层压样品。如果所有5名志愿者都具有柔软的手感，则认为固化的层压样品具有良好的柔软性。
表1
Figure BDA0003790326610000111
如表1中的结果所示，实施例1-7中制备的粘合剂组合物具有78％或更高的高粘合强度保持率，不超过5分钟的短开放时间和良好的柔软性。在实施例1-6中，组分b)的含量大于10重量％，粘合强度保持率理想地更高(83％或更高)，并且开放时间更短(不超过2分钟)。
实施例1和3中的粘合强度在洗涤后增加。假定这种现象的原因可能在于水润湿时固化的粘合剂分子的重排。
在对比例1中制备的粘合剂组合物不包含组分b)，其粘合强度保持率仅为45.45％，其开放时间长达15分钟。
在不脱离本发明的精神和范围的情况下，本领域的普通技术人员可以实施本发明的这些和其它修改和变化。此外，应当理解，各个实施方案的方面可以整体互换或在反应物中互换。此外，本领域的普通技术人员将理解，前面的描述仅是示例性的，并不旨在限制在所附权利要求中如此进一步描述的本发明。

Claims (12)

1.反应性热熔粘合剂组合物，其包含至少一种NCO封端的聚氨酯预聚物，所述NCO封端的聚氨酯预聚物包含以下组分的反应产物：
a)至少一种多异氰酸酯，
b)至少一种选自以下的多元醇：聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合，和
c)任选存在的至少一种不同于组分b)的多元醇，
其中NCO/OH比率为大于1，优选为约1.5至约2.5，所述NCO/OH比率为组分a)的NCO基团与组分b)和c)的总OH基团的摩尔比。
2.根据权利要求1所述的反应性热熔粘合剂组合物，其中基于所述聚氨酯预聚物的总重量，NCO含量为约1重量％至约5重量％、优选约1.2重量％至约4重量％。
3.根据权利要求1或2所述的反应性热熔粘合剂组合物，其中所述至少一种多异氰酸酯是二异氰酸酯，优选选自以下的二异氰酸酯：2,2'-亚甲基二苯基二异氰酸酯、4,4'-亚甲基二苯基二异氰酸酯、2,4'-亚甲基二苯基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或它们的组合。
4.根据前述权利要求中任一项所述的反应性热熔粘合剂组合物，其中所述聚四氢呋喃、聚丁二烯多元醇和氢化聚丁二烯多元醇各自具有约1,000至约5,000g/mol、优选约1,000至约3,500g/mol的数均分子量(Mn)。
5.根据前述权利要求中任一项所述的反应性热熔粘合剂组合物，其中所述聚碳酸酯多元醇是无定形的。
6.根据前述权利要求中任一项所述的反应性热熔粘合剂组合物，其中所述组分c)选自聚醚多元醇、聚酯多元醇以及它们的组合。
7.根据前述权利要求中任一项所述的反应性热熔粘合剂组合物，其中所述组分c)是结晶的并且具有约40℃至约100℃的熔点；或者所述组分c)是无定形的并且具有约-40℃至约40℃的玻璃化转变温度(Tg)。
8.根据前述权利要求中任一项所述的反应性热熔粘合剂组合物，其中所述NCO封端的聚氨酯预聚物包含以下组分的反应产物：
a)约10重量％至约40重量％、优选约15重量％至约35重量％的至少一种多异氰酸酯，
b)约5重量％至约70重量％、优选约10重量％至约60重量％、更优选约20重量％至约60重量％的至少一种选自以下的多元醇：聚四氢呋喃、聚丁二烯多元醇、氢化聚丁二烯多元醇、聚碳酸酯多元醇以及它们的组合，和
c)0重量％至约75重量％、优选约20重量％至约60重量％的至少一种不同于组分b)的多元醇，
以上均基于所述聚氨酯预聚物的总重量。
9.根据前述权利要求中任一项所述的反应性热熔粘合剂组合物，其中所述粘合剂组合物的熔融温度为约100℃至约140℃。
10.根据权利要求1至9中任一项所述的反应性热熔粘合剂组合物的固化产物。
11.根据权利要求10所述的固化产物，所述固化产物在洗涤后，尤其是在用抗菌衣物清洁剂洗涤后，具有大于约75％、优选大于约80％、更优选大于约83％的粘合强度保持率，其中所述粘合强度保持率是通过将洗涤后的所述固化产物的粘合强度除以洗涤前的所述固化产物的粘合强度来计算的。
12.根据权利要求1至9中任一项所述的反应性热熔粘合剂组合物用于粘合两个基材，尤其是在衣服或内衣中的两个基材的用途，其中所述两个基材中的至少一个是织物。
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