CN101287783A - 复合制品和使用异氰酸酯基封端的预聚物作为粘结剂的制备方法 - Google Patents

复合制品和使用异氰酸酯基封端的预聚物作为粘结剂的制备方法 Download PDF

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CN101287783A
CN101287783A CNA200680038271XA CN200680038271A CN101287783A CN 101287783 A CN101287783 A CN 101287783A CN A200680038271X A CNA200680038271X A CN A200680038271XA CN 200680038271 A CN200680038271 A CN 200680038271A CN 101287783 A CN101287783 A CN 101287783A
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general formula
composite product
particulate matter
isocyanate
urethane
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CN101287783B (zh
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P·蓬塞
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Dow Global Technologies LLC
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Abstract

本发明涉及一种复合制品，该复合材料制品通过使颗粒物与聚氨酯粘胶剂粘结或粘合获得，其中聚氨酯粘胶剂源自通过异氰酸酯与基于含有三级氮原子的引发剂的聚醚多元醇反应获得的氨基甲酸乙酯改性异氰酸酯。这些复合材料制品可为，例如休闲垫或瓦片、运动或跑步用跑道、或地板材料或层压材料。

Description

复合制品和使用异氰酸酯基封端的预聚物作为粘结剂的制备方法
技术领域
本发明涉及一种粘结颗粒物质的复合制品；一种加工该复合材料的方法，其中使用选择氨基甲酸乙酯改性异氰酸酯粘合剂为粘结剂；层压产品，其中一层或多层包含该复合产品。
背景技术
广泛熟知，使用聚氨酯粘结剂或粘合剂，通过例如橡胶、人造树脂、木材的有机颗粒或例如沙子或石英的无机颗粒生产复合产品。例如，在德国专利申请DE1955267和英国专利公开GB 1,373,923和GB1,359,761中描述了使用双组份聚氨酯粘结剂以粘结弹性颗粒。在专利申请GB 1,384,619和GB1,294,017中公开了湿固化单组分聚氨酯粘结剂。
通常，通过使含有多羟基化合物的聚异氰酸酯与同时或随后含有颗粒物的化合物混合获得基于已知双组份聚氨酯粘结剂的复合材料。加入的聚异氰酸酯与大气中的水分反应。除了别的以外，大气湿度和颗粒物中残余水分含量决定了这两个反应发生的比例，这使得复合材料的加工过程和最终性质难以进行控制。通过使用单组分聚氨酯粘结剂(其仅通过与大气水分的反应变硬)，在某种程度上改善该不足。或者，通过选择存在于加工过程中的氨基甲酸乙酯催化剂，在一定程度上改善该不足。
通常，单组分粘结剂由包含异氰酸酯基的预聚物组成，该预聚物通过摩尔含量过量的聚异氰酸酯与常规的多羟基化合物进行反应获得。然而，已知的单组分聚氨酯粘结剂具有多个由其化学结构和反应性所决定的不足。基于二苯甲烷-4，4’-二异氰酸酯的预聚物在温度为0℃左右或略微高于0℃时有结晶趋势，因此受限于在低温条件下储存和使用。基于商业化二苯甲烷二异氰酸酯且可能额外含有三异氰酸酯、四异氰酸酯和二异氰酸酯系列的更高官能化聚异氰酸酯的预聚物具有明显降低的结晶趋势，但另一方面，这些预聚物在室温下的粘度太高以致其难于加工，除非随后通过加入稀释剂、溶剂对其粘度进行改性或者提升加工过程的温度。因为存在风险(某些颗粒物可能由于吸收溶剂而膨胀并随后在固化过程中释放出溶剂，因此可能造成例如尺寸不稳定性的问题)，溶剂的存在是不理想的。此外，对挥发性有机物排放引起的环境问题的意识增强，使得有必要避免出现此种挥发性有机物溶剂。
对于聚氨酯粘结剂体系的反应性，使用催化剂以调整该反应性分布(reactivity profile)是非常普遍的。催化剂类型的选择会限制所得复合材料的最终用途。
调整聚氨酯体系反应性分布的另一方法是使用更高固有反应性的起始原料，例如含有三级氮原子的多元醇。在多个出版物包括美国专利公开US 3,317,481和US 4,426,487中公开了含有基于三级氮的多元醇的异氰酸酯基封端的预聚物。专利公开EP 1,268,598建议了异氰酸酯基封端的预聚物的常规制备方法，该异氰酸酯基封端的预聚物适于通过源自交替胺引发剂的多元醇制备柔性聚氨酯泡沫。
发明内容
本发明的目的之一在于改善已知聚氨酯粘结剂的上述不足，并提供制造具有交替聚氨酯粘结剂体系的复合制品，以满足最终用户对具有更简单加工(包括固化时间和湿度灵敏度)、更少的与溶剂或催化剂存在的敏感性相关的限制和提升的机械性能的体系的一个或多个要求。
本发明涉及通过使颗粒物与聚氨酯粘胶剂粘结或粘合所获得的复合制品，其中聚氨酯粘胶剂源自氨基甲酸乙酯改性异氰酸酯(其通过异氰酸酯与源自含有三级氮的引发剂的聚醚多元醇反应获得)。这些复合制品可为，例如休闲垫(recreational mattings)、瓦片(tiles)、运动或跑步用跑道(tracks)、地板材料或层压材料。
在第一方面，本发明是复合材料，该复合材料由基本被基于氨基甲酸乙酯改性异氰酸酯的未发泡聚氨酯粘结剂涂布的颗粒物组成，其特征在于氨基甲酸乙酯改性异氰酸酯是如下的反应产物：
a)化学计量过量的脂肪族或芳香族聚异氰酸酯，或其混合物，与
b)包含聚醚多元醇(b1)的多元醇复合材料，其中该聚醚多元醇具有1000至12000分子量且通过至少一种具有通式(I)或通式(II)的引发剂分子的烷氧基化获得：
HmA-(CH2)n-N(R)-(CH2)p-AHm    通式(I)
其中n和p独立地为2至6的整数，
A在每一处独立地为氧、氮、硫或氢，条件是同时只有一个A为氢，
R为C1至C3烷基，
当A为氢时m等于0，当A为氧时m等于1，当A为氮时m等于2，
H2N-(CH2)t-N-(R)-H           通式(II)
其中t为2至12的整数，
R为C1至C3烷基。
在第二方面，本发明是生产复合材料的方法，其中复合材料包含基本由未发泡聚氨酯粘结剂涂布并粘结在一起的颗粒物，该方法包括：使所述颗粒物与氨基甲酸乙酯改性异氰酸酯组合物紧密接触的第一步和使所得混合物固化以获得复合制品的第二步，其特征在于该氨基甲酸乙酯改性异氰酸酯为如上所述。
在第三方面，本发明是层压制品，该层压制品包含与第二层接触的第一层，其中第一层或第二层的至少一层是本文上述的复合材料。
在第四方面，本发明涉及具有上簇绒毛织物表面(upper tufted piletextile surface)的垫子，其中上簇绒毛织物表面包括丛生于衬底结构中的纱线簇，该衬底结构包括来自弹性胶末的弹性背衬和如本文上述的聚氨酯粘结剂。
据发现，使用这种氨基甲酸乙酯改性异氰酸酯(基于由含氮引发剂制得的多元醇)作为聚氨酯粘结剂的体系，提供了具有提升的固化和更佳的可使用性的更理想的反应性分布，因此方便了如以运动场地面为例的复合材料的制备。固化分布的提升提供了可操作和经济节约的特性，因为在生产过程中进入下一步的等待时间明显缩短。
使用包含该种氨基甲酸乙酯改性异氰酸酯(基于源自含氮引发剂的多元醇)的聚氨酯粘结剂可以减少或甚至去除通常存在以加速聚氨酯粘胶剂的固化的催化剂。这有利于提供具有对水或颗粒物湿度含量灵敏度降低的体系，从而避免容易形成泡沫。由于该降低的水灵敏度，在干燥和制备颗粒物以用于制备复合材料中需要更少的时间。减少或去除固化催化剂存在的能力表明该聚氨酯粘结剂体系如今可用于之前由于这些催化剂物质相关的敏感性而被排除在外的某些最终用途。
本发明复合制品包含基本由非多孔聚氨酯基体或粘结剂涂布并粘结在一起的颗粒物，该非多孔聚氨酯基体或粘结剂源自本文公开的氨基甲酸乙酯改性聚异氰酸酯。通常，复合制品包含以总复合材料重量计50至99，优选60至97，更优选75至95重量％的颗粒物。相应地，未发泡聚氨酯基体占总复合材料重量的1至50，优选3至40，更优选5至25重量％。
这样的复合制品可为致密制品，但在某些情况下，如以作为垫子的层压组分时为例，可为含空隙的半致密制品。当复合制品为半致密制品时，通常，该制品包含50至95重量％的颗粒物、5至95重量％的非多孔聚氨酯粘结剂，且其中复合材料的空隙体积为15至85体积％。
颗粒物可为有机物或无机物质、或其混合物。无机物质的实例为沙子、石英、大理石、其它地面石材、毛玻璃或胶凝材料。基于无机物的复合材料，例如沙子，可应用于铸造工业。有机物质的实例为弹性粒状生胶、重磨泡沫材料或颗粒木质纤维物如以软木、木材、草或草杆为例。用于本发明复合材料的优选颗粒物为包括如源自苯乙烯和丁二烯的弹性橡胶、重磨泡沫材料或软木且任选为可恢复/可循环材料的有机物质。该颗粒物非常适合生产用于表面、吸声材料、休闲品表面的顶层或底层、路面、屋盖顶或地板(例如用于地毯料的垫子、衬垫或瓦片)的复合材料。当由优选种类的颗粒有机物制备复合制品时，有利地，最长维度的平均粒度小于大约20mm，优选小于大约15mm，更优选小于大约10mm。为方便处理和加工，有利地，最长维度的平均粒度至少为1mm，优选至少3mm。
非多孔聚氨酯粘结剂是通过使异氰酸酯与除水以外的异氰酸酯反应性材料反应而获得的双组份聚氨酯粘结剂。或者，非多孔聚氨酯粘结剂是通过在没有其它含羟基物质(包括水)的情况下固化异氰酸酯而获得的单组分粘结剂。在这两种情况下，异氰酸酯皆为通过使摩尔量过量的聚异氰酸酯与包含基于具有三级氮原子引发剂的聚醚多元醇的多元醇组合物反应而获得的氨基甲酸乙酯改性异氰酸酯。通常，氨基甲酸乙酯改性异氰酸酯具有1至23，优选5至18，更优选7至14重量％的平均异氰酸酯含量。
用于制备氨基甲酸乙酯改性异氰酸酯的多元醇组合物可含有一个或多个的附加多元醇，该附加多元醇未由含氮原子引发剂引发。这些多元醇为本技术领域所熟知，且在如High Polymers，Vol.XVI；“Polyurethanes，Chemistry and Technology”，by Saunders and Frisch，Interscience Publishers，New York，Vol.I，pp.32-42，44-54(1962)and Vol.II.pp.5-6，198-199(1964)；Organic Polymer Chemistry by K.J.Saunders，Chapman and Hall，London，pp.323-325(1973)；和Developments inPolyurethanes，Vol.I，J.M.Burst，ed.，Applied Science Publishers，pp.1-76(1978)的这些出版物中进行了描述。适宜的多元醇的例子包括聚酯、聚内酯、聚醚、聚烯烃、聚碳酸酯多元醇以及多种其它多元醇。优选地，附加多元醇为聚醚或聚酯多元醇。必要时，多元醇配方也可含有共聚物多元醇，例如苯乙烯/丙烯腈(SAN)、聚异氰酸酯聚加成反应产物(PIPA)或聚脲多元醇(PHD)。附加多元醇通常具有1.6至8的公称羟基官能度和1000至12,000的分子量。
在制备氨基甲酸乙酯改性异氰酸酯时，组合物中的来自含氮引发剂的多元醇(b1)的量可根据用于给定终端用途的聚氨酯粘结剂体系内所需的内部反应性强度而变化。通常，适宜的组合物中多元醇(b1)占多元醇组合物总重量的5至60，优选5至50，更优选5至40重量％。剩余的多元醇来自非含氮引发剂且多元醇的总重量百分数为100。
用于制备氨基甲酸乙酯改性异氰酸酯的多元醇(b1)通常是具有1000至12000，优选1500至8000，更优选2000至6000道尔顿平均分子量的物质，且通过至少一种具有通式(I)或通式(II)的引发剂分子的烷氧基化获得：
HmA-(CH2)n-N(R)-(CH2)p-AHm    通式(I)
其中n和p独立地为2至6的整数；A在每一处独立地为氧、氮、硫或氢，条件是同时只能一个A为氢；
R为C1至C3烷基；当A为氢时m等于0，当A为氧时m等于1，当A为氮时m等于2，
H2N-(CH2)t-N-(R)-H    通式(II)
其中t为2至12的整数，且
R为C1至C3烷基。
在通式I的优选具体实施方案中，R是甲基。在另一个优选的具体实施方案中，R是甲基且n和p是具有相同数值的整数。在一个更优选的具体实施方案中，n和p为2至4的整数。优选当A不为氢时，A在每一处为氧或氮。在一个更优选的具体实施方案中，一个A为氧、剩余A为氮，且最终多元醇为三元醇。在又一个更优选的具体实施方案中，A在每一处为氮且最终多元醇为四元醇。
通式I的烷基胺为商业上可购得的或可通过本领域已知技术来制备，例如美国专利4,605,772，其公开内容以引用的方式并入本文。例如，甲胺与适宜的环氧烷烃反应以制备其中A为氧的化合物。优选环氧烷烃为环氧乙烷(EO)、环氧丙烷(PO)或环氧丁烷(BO)，当每个A为氧时，给定n为2至4的优选范围。该引发剂化合物的例子为N-甲基二乙醇胺、N-甲基二丙醇胺、N-甲基二丁醇胺和N-甲基乙醇丙醇胺。
甲胺可与任何已知的能与胺反应且含有附加氮的反应性基团反应以制备其中每个A为氮的化合物。例如，2摩尔X(CH2)nNR’R”可与1摩尔甲胺进行反应，其中X为氯、溴或碘；R’和R”为H或烷基；n同上述定义。这些引发剂化合物的例子包括3，3’-二氨基-N-甲基二丙胺，2，2’-二氨基-N-甲基二乙胺，2，3-二氨基-N-甲基-乙基-丙胺。
可使用如JP09,012,516中所描述的方法制备其中一个A为氮且一个A为氧的化合物，其公开内容以引用的方式并入本文。
在通式II的一个具体实施方案中，R是甲基。通式II中t优选为2至10，更优选2至6，最优选2至4的整数。在优选具体实施方案中，R为甲基且m是2至4的整数。可通过本领域已知的标准程序来制备通式II的化合物。通式II的商业上可购得的化合物的例子包括N-甲基-1，2-乙二胺和N-甲基-1，3-丙二胺。
可使用本领域所熟知的程序通过引发剂的烷氧基化来制备多元醇。一般而言，通过阴离子或阳离子反应或使用双金属氰化物(DMC)催化剂下，将环氧烷烃(EO、PO或BO)或这些环氧烷烃的组合加入到引发剂中来制备多元醇。对于某些用途，仅使用了一种环氧烷烃单体；对于其它用途，使用这些环氧乙烷单体的混合物，且在某些情况下，优选顺序加入这些单体，例如PO后加入EO或EO后加入PO。
本发明中，过量聚异氰酸酯与上述包含脂肪族聚异氰酸酯、芳香族聚异氰酸酯或其混合物的多元醇组合物反应。适宜的脂肪族聚异氰酸酯包括六亚甲基二异氰酸酯和异佛尔酮二异氰酸酯。优选芳香族聚异氰酸酯包括甲苯二异氰酸酯、二苯甲烷二异氰酸酯(MDI)及它们的异构体，和聚亚甲基多苯基异氰酸酯(粗MDI)。在优选具体实施方案中，芳香族聚异氰酸酯为异氰酸酯混合物，该异氰酸酯混合物包含占总异氰酸酯重量的至少大约40，优选至少50，更优选至少60重量％的2-环二苯甲烷二异氰酸酯(MDI)异构体。优选MDI包含2，4’-和4，4’-二苯甲烷二异氰酸酯异构体，且二者的摩尔比为10∶90至90∶10，优选20∶80至80∶20，更优选20∶80至70∶30。异氰酸酯混合物的剩余物当不是二苯甲烷二异氰酸酯时，可包含甲苯二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、聚亚甲基多苯基异氰酸酯、二苯甲烷二异氰酸酯的碳二亚胺、allophonate或脲酮亚胺加成物及这些化合物的混合物。优选构成组合物剩余物的异氰酸酯为聚亚甲基多苯基异氰酸酯、二苯甲烷二异氰酸酯的碳二亚胺、allophonate或脲酮亚胺加成物。
通过使异氰酸酯和多元醇在20-100℃下结合，且必要时，在氨基甲酸乙酯发泡催化剂(例如叔胺或锡化合物)存在下，以传统方法制备氨基甲酸乙酯改性异氰酸酯。选择异氰酸酯和多元醇的相对量以达到最终产品所需的游离NCO含量。对本领域技术人员来说，制备预聚物是常规操作；见例如专利公开WO2004074343，其以引用的方式并入本文。
本发明涉及颗粒物的复合材料，该颗粒物被源自所述氨基甲酸乙酯改性异氰酸酯的非泡沫聚氨酯所粘结；和层压材料制品，其中一片或多片的层压薄片可由该复合制品组成。在文献中广泛记载了制备该复合制品和层压材料的方法，其以引用的方式并入本文。这些出版物的示例包括美国专利4,112,176、4,025,579、4,107,100、4,614,686、4,857,368、5,514,722、5,472,743、6,565,918、6,649,696；美国专利申请2002/022086；欧洲专利公开1,312,469；英国专利1,373,923、1,359,761、1,384,619、1,509,108和2,035,336。
简言之，用于制备为基本被未发泡聚氨酯粘结剂包覆并粘结在一起的颗粒物的复合材料的方法包括使所述颗粒物与氨基甲酸乙酯改性异氰酸酯组合物紧密接触的第一步和使所得混合物固化以获得复合制品的第二步。
可通过使用聚氨酯粘结剂涂布颗粒物(通常为重磨硫化橡胶)并将该混合物转移至其将散布且固化的表面上以轻松制得用于表面、吸声材料、休闲品表面的衬底或其它路面或地板的胶粉弹性复合材料。
本发明的氨基甲酸乙酯改性异氰酸酯也可用于从无机颗粒物制备复合材料。例如，在英国专利1,294,017中公开了人造石的加工，其中使用聚氨酯粘结剂把石英砂粘结于人造石上。
在出版物EP-A-1,518,668；EP-A-1,511,894；EP-A-1,511,893和EP-1,549,797中公开了制备垫子的方法，该垫子包括由聚丙烯面料、簇状尼龙面料(tufted nylon)、针织聚酯面料或机织聚酯织布面料(wovenpolyester)组成的织物表面、包含弹性胶末或性能优良的硫化橡胶的弹性背衬层和聚氨酯粘结剂，这些出版物以引用的方式并入本文。总之，该方法包括：混合弹性胶末和粘结剂，沉积该胶末/粘结剂混合物于一层内，放置织物表面部分于该层上以形成垫子组件，在硬化粘结剂时压缩该垫子组件，由此弹性胶末结成一体形成了包含空隙于弹性胶末之间的弹性背衬且该织物表面部分粘结于该弹性背衬。
下列示例用于说明本发明，但不应解释为对本发明进行任何的限定。除非另有说明，所有的“份”和“百分数”为重量单位。VORANOL、ISONATE和VORANATE为Dow Chemical Company的商标。
多元醇1：Dow Chemical Company提供的专有多元醇，具有大约1700的羟基当量，且通过使3，3′-二氨基-N-甲基二丙胺与EO/PO混合物进料以重量比12∶88反应而制得。
多元醇A：甘油EO/PO多元醇，具有大约1700的羟基当量，可从Dow Chemical Company获得的VORANOL 1421。
多元醇B：4000分子量基于环氧丙烷且以环氧乙烷封端的二元醇，可从Dow Chemical Company获得的VORANOL EP1900。
聚异氰酸酯A：碳二亚胺改性MDI，可从Dow Chemical Company获得的ISONATE 143L。
聚异氰酸酯B：50∶50重量比2，4′-和4，4′-MDI混合物，可从DowChemical Company获得的ISONATE OP 50。
聚异氰酸酯C：粗二苯甲烷二异氰酸酯，可从Dow ChemicalCompany获得的VORANATE 229。
实施例1：
制得根据本发明的聚氨酯粘结剂(粘结剂1或2)并与被认为代表了本领域常规状态的粘结剂A和B进行性能比较。通过使聚异氰酸酯与表I中显示的多元醇反应制得氨基甲酸乙酯改性异氰酸酯组合物。所得粘结剂随后与苯乙烯-丁二烯颗粒橡胶在少量残留水存在下和任选地胺催化剂JBFFCAT DMDEE(可购自Huntsman Chemicals)存在下进行混合，把所得混合物铲入保持大约90℃的模子内以制得40mm厚的瓦片。表1中记录了组合物的开放时间(open time)和干燥时间。“开放时间”代表了混合物可被操作的时段；在本领域，开放时间越长通常越有利。“干燥时间”代表在可进行下一步加工操作前混合物必须静止并固化的时段；在本领域，通常期望更短的干燥时间。
粘结剂1和2提供了有吸引力的开放时间，并且提供了比粘结剂A和B更出众的干燥时间；并且值得注意，是在缺少固化催化剂的情况下。
表1
Figure A20068003827100141
对本领域技术人员来说，通过对本发明所公开的说明书或实践的思考，很明显可得出本发明其它的具体实施方案。本发明说明书和所得实施例仅用于示范，而通过权利要求书表示本发明的实际范围和精神。

Claims (10)

1、一种复合制品，其由基本被基于氨基甲酸乙酯改性异氰酸酯的未发泡聚氨酯粘结剂涂布的颗粒物组成，其特征在于，以复合制品总重量计：
a)颗粒物为50至99重量％；和
b)未发泡聚氨酯粘结剂为1至50重量％，且其中氨基甲酸乙酯改性异氰酸酯是如下的反应产物：
i)化学计量过量的脂肪族或芳香族聚异氰酸酯，或其混合物，与
ii)包含聚醚多元醇(b1)的多元醇组合物，其中该聚醚多元醇具有1000至12000的分子量且通过至少一种具有通式(I)或通式(II)的引发剂分子的烷氧基化获得：
HmA-(CH2)n-N(R)-(CH2)p-AHm    通式(I)
其中n和p独立地为2至6的整数，
A在每一处独立地为氧、氮、硫或氢，条件是同时只能一个A为氢，
R为C1至C3烷基，
当A为氢时m等于0，当A为氧时m等于1，当A为氮时m等于2，
H2N-(CH2)t-N-(R)-H           通式(II)
其中t为2至12的整数，且
R为C1至C3烷基。
2、根据权利要求1所述的复合制品，其中颗粒物为有机材料。
3、根据权利要求2所述的复合制品，其中颗粒有机物质包括弹性橡胶、重磨泡沫材料或颗粒木质纤维物质。
4、根据权利要求3所述的复合制品，其中颗粒木质纤维物质包括软木、木材、草或草杆。
5、根据权利要求1所述的复合制品，其中颗粒物为无机材料。
6、根据权利要求5所述的复合制品，其中无机颗粒物质包括沙子、石英、大理石、其它地面石材、毛玻璃或胶凝材料。
7、一种生产复合材料的方法，该复合材料为基本被未发泡聚氨酯粘结剂涂布并粘结在一起的颗粒物，其中所述方法包括：使所述颗粒物与氨基甲酸乙酯改性异氰酸酯组合物紧密接触的第一步和使所得混合物固化以获得复合制品的第二步，其特征在于所述氨基甲酸乙酯改性异氰酸酯为以下的反应产物：
a)化学计量过量的脂肪族或芳香族聚异氰酸酯，或其混合物，与
b)包含聚醚多元醇(b1)的多元醇复合材料，其中该聚醚多元醇具有1000至12000的分子量且通过至少一种具有通式(I)或通式(II)的引发剂分子的烷氧基化获得：
HmA-(CH2)n-N(R)-(CH2)p-AHm    通式(I)
其中n和p独立地为2至6的整数，
A在每一处独立地为氧、氮、硫或氢，条件时同时只能一个A为氢，
R为C1至C3烷基，
当A为氢时m等于0，当A为氧时m等于1，当A为氮时m等于2，
H2N-(CH2)t-N-(R)-H           通式(II)
其中t为2至12的整数，且R为C1至C3烷基。
8、一种层压制品，其包含与第二层接触的第一层，其中第一层或第二层中至少一层是根据权利要求1所述的复合材料。
9、一种具有簇状绒毛织物表面的垫子，其包括丛生于簇绒衬底中的纱线簇和由弹性胶末和粘结剂形成的弹性背衬，该弹性背衬为根据权利要求1所述的复合制品。
10、根据权利要求9所述的垫子，其通过包括如下步骤的方法获得：混合弹性胶末与粘结剂，沉积胶末/粘胶剂混合物于一层，放置织物表面部分于该层上以形成垫子组件，在硬化粘胶剂时压缩该垫子组件，以使弹性胶末固结以形成包含空隙于弹性胶末之间的弹性背衬且该织物表面部分粘结于该弹性背衬。
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