CN100355850C - 作为非织造产品粘合剂用的醋酸乙烯酯/乙烯和氯乙烯聚合物共混物 - Google Patents

作为非织造产品粘合剂用的醋酸乙烯酯/乙烯和氯乙烯聚合物共混物 Download PDF

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CN100355850C
CN100355850C CNB200510103724XA CN200510103724A CN100355850C CN 100355850 C CN100355850 C CN 100355850C CN B200510103724X A CNB200510103724X A CN B200510103724XA CN 200510103724 A CN200510103724 A CN 200510103724A CN 100355850 C CN100355850 C CN 100355850C
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J·R·博兰
C·W·佩里
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Abstract

本发明涉及粘合剂的改进,该粘合剂特别适用于制备非织造产品,并涉及非织造产品。改进的粘合剂含有氯乙烯(VCl)聚合物乳液与可自交联的醋酸乙烯酯-乙烯-N-羟甲基丙烯酰胺(VAE-NMA)聚合物乳液的共混物。可将该VCl聚合物乳液与VAE-NMA聚合物乳液的共混物施加到纤维素及纤维素/合成非织造基材上,并在无酸催化剂的条件下固化,以便提供具有优异湿强度性能的自支撑网。

Description

作为非织造产品粘合剂用的醋酸乙烯酯/乙烯和氯乙烯聚合物共混物
发明背景
由具有湿强度特性的纤维素或纤维素/合成纤维构成的非织造产品一般是通过用能够交联的乳液聚合物浸渍这些纤维而制造的。交联产生赋予非织造产品耐水性的聚合物。通过使诸如醋酸乙烯酯、乙烯、氯乙烯和丙烯酸烷基酯的多种单体与一种功能单体如N-羟甲基丙烯酰胺(NMA)共聚形成许多自交联聚合物,所述功能单体为自身以及为纤维素表面提供有用的自交联能力,以便形成自支撑网。
作为现有技术的代表,引用以下参考文献:
《空气产品技术通报(Air Products Technical Bulletin)》“非织造产品用AIRFLEX_105乳液”公开了水基醋酸乙烯酯-乙烯-NMA聚合物乳液及其在制造非织造产品中的用途。为了促进经NMA基的固化,采用各种二羧酸,例如草酸、柠檬酸以及无机酸盐例如硫酸氢钠和氯化铵。
《空气产品技术通报》151-9317,“非织造品用的AIRFLEX_108超低甲醛乳液”公开了用于制造非织造产品的醋酸乙烯酯-乙烯乳液。这些树脂是自交联的而且提供优良的湿强度性能。推荐加入酸催化剂以便在加热阶段加速和促进粘合剂的固化。
《空气产品技术通报》标题为“非织造品和纺织品用的AIRFLEX_乙烯-氯乙烯(EVCL)乳液”公开了作为非织造品用途粘合剂的乙烯-氯乙烯聚合物乳液。通过与外部交联剂例如三聚氰胺或脲醛树脂产生交联,使湿拉伸性能得到强化。
GB 1088296公开了氯乙烯共聚物,据报道它们以胶乳形式用作非织造品的粘合剂,赋予非织造织物特别优良的回弹性。这些共聚物含有65%-94.8重量%的至少一种α,β-烯属不饱和单羧酸的低级烷基酯,5-34.8重量%的氯乙烯,0.1-5重量%的α,β-烯属不饱和羧酸的N-羟烷基酰胺,基于这些单体的总重量计。
US3380851公开了用由醋酸乙烯酯、乙烯以及约0.5-10%(基于醋酸乙烯酯计)内在丙烯酰胺的共聚物粘合的非织造织物。NMA是被采用的自交联单体。按照基于干重计以20-100%的量将这种粘合剂施加到纤维上。然后,建议添加无机酸催化剂,这是由于促进共聚物固化的机理。
US3787232公开了由偏二卤乙烯单体与羧酸单体和N-羟烷基酰胺单体的乳液聚合制备而形成的卤乙烯和偏二卤乙烯聚合物,其用于涂布纤维。低pH值胶乳聚合物据称可低温固化。
US4449978公开了用乳液粘合剂粘合的非织造产品,该乳液粘合剂含有醋酸乙烯酯、乙烯和50/50摩尔的NMA/丙烯酰胺混合物,其提供低残留游离甲醛含量且拉伸性能优良的非织造产品。通过添加酸催化剂完成粘合剂固化以取得NMA的交联。
US4590102公开了通过浸渍基于醋酸乙烯酯、乙烯和NMA的乳液粘合剂或基于氯乙烯、乙烯和NMA共聚物的乳液而生产非织造产品。采用pka为约1到2的低温固化剂促进固化。低温固化剂的实例包括有机二羧酸,例如草酸和马来酸。
US5244695公开了用于生产过滤器的涂料组合物,其含有10-90%的全水解聚乙烯醇,和0-90%,优选30-70%的聚合物水乳液,该水乳液由醋酸乙烯酯-NMA聚合物水乳液或乙烯-氯乙烯聚合物水乳液组成。两种聚合物水乳液可按照15∶85到85∶15的量组合使用。这种饱和的非织造品可用于空气、油、燃料和真空过滤介质中。优选将酸催化剂添加到该配制物中,以帮助树脂交联。
US3752733和US3758429公开了适合于形成非织造产品的乙烯-氯乙烯共聚物。’733专利公开了加入0.1-10%丙烯酰胺,而’429专利公开了加入NMA以生产可交联的共聚物。为了增强非织造产品的耐洗涤和耐干洗性能,通过与氨基塑料反应缩合并固化这些共聚物。
US5872155公开了由芯、外层和非必要的中间层构成的胶乳形式的氯乙烯共聚物的制备。讨论了经种子微悬浮聚合的氯乙烯共聚物的另外制造过程。据报道,这些乳液聚合物可用于涂料和增塑塑料溶胶用途中。
发明内容
本发明涉及特别适用于制备非织造产品的粘合剂的改进,并涉及这些非织造产品。这些改进的粘合剂含有乳液聚合的氯乙烯(VCl)聚合物如乙烯-氯乙烯(EVCl)与乳液聚合的可自交联醋酸乙烯酯-乙烯-N-羟甲基丙烯酰胺聚合物(常常称作NMA反应活性VAE聚合物乳液或VAE-NMA聚合物乳液)的共混物。可将VCl聚合物乳液与VAE-NMA聚合物乳液的共混物施加到纤维素及纤维素/合成非织造基材上,并在没有酸催化剂存在下固化以提供自支撑网,该网具有优异的湿强度性能。传统上,在施加到纤维的非织造网上之前,由非织造品生产商将VAE-NMA聚合物乳液与酸催化剂混合,以便促进固化和交联。酸催化的乳液的贮藏寿命有限。令人吃惊的是,在本发明中发现,VC l聚合物乳液和VAE-NMA聚合物乳液的共混物不要求酸催化剂来获得增强的湿强度。
使用VCl聚合物乳液和VAE-NMA聚合物乳液的共混物能获得显著优势,它们包括:
使共混物的非织造用品获得出色耐水性,并可能获得NMA交联的全部益处而无需后添加酸催化剂的能力;
消除与处理酸催化剂有关的安全顾虑的能力;
生产拉伸强度与用含酸催化剂的VAE-NMA聚合物乳液粘合在一起的非织造产品的拉伸强度相同的非织造产品的能力;和
生产具有良好贮藏寿命稳定性的VCl/VAE-NMA聚合物乳液共混物,从而制造“涂布机即用型”乳液的能力。
氯乙烯聚合物包括氯乙烯均聚物和含氯乙烯及至少一种能够与氯乙烯共聚的其它单体的聚合物,并形成稳定的胶乳乳液。这类单体可包括乙烯、单羧酸和多羧酸的乙烯酯,例如醋酸乙烯酯、丙酸乙烯酯或苯甲酸乙烯酯;不饱和单及多羧酸,例如丙烯酸、甲基丙烯酸、马来酸、富马酸和衣康酸,以及它们的脂族、环脂族或芳香族酯,它们的酰胺或它们的亚硝酸根化合物;烷基卤、卤乙烯或偏二卤乙烯;烷基乙烯基醚;及烯烃,例如聚丙烯。
具体实施方式
水基VAE-NMA聚合物乳液的众所周知的,并能用常规乳液聚合技术形成。VAE-NMA聚合物乳液通常含有50-94重量%,优选64-79重量%的醋酸乙烯酯,5-40重量%,优选20-30重量%的乙烯,和0.5-10重量%,优选1-6%的NMA,均基于聚合物的总重量计。这些乳液可按照US3380851中的教导制备,其经引用并入本申请。可按照US4449978的教导配制低甲醛、自交联的醋酸乙烯酯-乙烯-NMA聚合物,该专利经引用并入本申请。在美国专利’978中,由于生产非织造产品用的低甲醛可交联聚合物的机理,使用NMA与丙烯酰胺的50/50混合物。
用于制造非织造和纺织产品的乙烯-氯乙烯(EVCl)聚合物水乳液是众所周知的,而且可市购。通过氯乙烯和乙烯与丙烯酰胺或衍生物例如N-羟甲基丙烯酰胺的乳液聚合形成这些聚合物乳液。EVCl聚合物典型地具有0-50℃的Tg,而且含有约55-95重量%,优选60-90重量%的氯乙烯,约5-35重量%,优选10-30重量%的乙烯,和0.1-10重量%,优选1.5-5重量%的丙烯酰胺和/或N-羟甲基丙烯酰胺,其均基于聚合物总重量计。可乳液聚合到聚合物中的其它单体通常是少量的。它们非限定地包括C1至C15烷基乙烯基酯;丙烯酸C1至C15烷基酯或甲基丙烯酸C1至C15烷基酯,例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、和(甲基)丙烯酸2-乙基己基酯;(甲基)丙烯酸C1至C6羟烷基酯,例如(甲基)丙烯酸羟乙酯和(甲基)丙烯酸羟丙酯;马来酸C1至C15烷基酯;富马酸C1至C15烷基酯;丙烯酸;甲基丙烯酸;α,β-不饱和C4-C10链烯二酸如马采酸、富马酸和衣康酸的单和二酯;C1至C18链烷醇;N-羟甲基酰胺、N-羟甲基酰胺的C1至C4链烷酸醚;氨基甲酸烯丙基酯,例如丙烯腈、甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺、N-羟甲基氨基甲酸烯丙基酯;N-羟甲基丙烯酰胺的C1-C4烷基醚或C1-C4链烷酸酯,乙烯基磺酸钠;和丙磺酸2-丙烯酰胺基-2-甲基酯。这些单体能够以少量加入,例如0到约10重量%。在另一个实施方案中,EVCl聚合物含有70至85重量%的氯乙烯,13至26重量%的乙烯,和2至4重量%的丙烯酰胺和/或N-羟甲基丙烯酰胺,基于聚合物的总重量。
在制造EVCl聚合物的聚合方法中,将含基本上全部稳定化体系和全部氯乙烯单体的一部分,优选至少5%的水乳液反应混合物装入反应器。此反应器用乙烯加压,用量为提供聚合物5-35重量%乙烯含量,然后反应混合物经添加自由基发生源而引发。添加氯乙烯和共聚单体使聚合反应继续直到聚合速率基本结束。一般在这一点处终止聚合反应,并将未反应的组分从乳液中除去。在美国专利3752733和美国专利3758429中提供了所述EVCl聚合物乳液的生产方法,经引用将其并入本申请。
可经乳液聚合法生产氯乙烯均聚物以及氯乙烯的其它共聚物,该乳液聚合法的方式与上文生产EVCl共聚物所详述的相似。典型地,单体在间歇法中是预先装料的,或者在连续法中是分阶段加入的。使用自由基引发该聚合反应,并且典型地用表面活性剂控制生成的胶态分散体的粒度。可在《聚合物科学与工程大全(Encyclopedia ofPolymer Science and Engineering)》第二版第17卷,“氯乙烯聚合物聚合”主题下找到氯乙烯乳液聚合的更全面解释。在《聚合物材料大全(Polymeric Materials Encyclopedia)》第11卷,“氯乙烯共聚物”,第8566-8572页描述了氯乙烯的共聚反应。
本发明共聚物组合物中氯乙烯的含量可从15%至100%变化。
适于生产非织造产品的粘合剂体系的共混物能容易地通过使用含水液体共混物制备领域公知的大多数类型的装备和混合容器获得。每100重量份的总聚合物(干基)中,共混物含有约2至70重量份的VCl聚合物,低干10重量份的第三聚合物,和剩余量的VAE-NMA聚合物。优选,共混物由50至80重量份的VAE-NMA聚合物乳液和5至50重量份的VCl聚合物乳液组成。可将其它聚合物以少于10重量%即0至10重量%的量加入到共混物中;优选这些聚合物不与NMA反应。其它聚合物的实例包括聚(醋酸乙烯酯)和基于(甲基)丙烯酸低级烷基酯的丙烯酸系聚合物。优选,共混物基本上由EVCl乳液和VAE-NMA乳液组成,并且它们不包括NMA反应活性聚合物,例如聚(乙烯醇)和含羧基的聚合物。
通常,将预选量的VAE-NMA聚合物乳液加入到共混容器中并搅拌。然后,将预选量的VCl聚合物乳液加入到共混容器中并混合适当的时间,以形成均匀的混合物。然后可将这种共混物浸渍在例如纤维的非织造网中,并干燥除去水。典型地,共混物以占基材重量至少3%,最多约50%,通常占基材重量(干基)10至30%的量引入。在干燥步骤期间进行固化,该步骤包括加热到一般65至180℃的温度,以便从非织造产品中除去水。
制造共混物所用的代表性乳液的物理性能如下:
性能范围 测定的性能90%VAE-NMA聚合物10%VCl聚合物 测定的性能75%VAE-NMA聚合物25%VCl聚合物
固体 40-60% 48% 48%
PH 5-8 5.7 5.9
粘度 50-800cps 86 148
代表性聚合物乳液共混物通常具有以下基于乳液固体的成分百分数:
VAE-NMA聚合物干固体的% VCl聚合物干固体的% 其它聚合物干固体的%
范围 30-98% 2-70% 0-10%
优选范围 50-95% 5-50% 0-10%
最优选范围 65-80% 20-35% 0-10%
提供以下实施例以举例说明本发明的各种实施方案,但无意以此限定本发明的范围。
通用工序
除非另外注释,用于对比例的酸催化剂是硫酸氢钠。代表性的VAE-NMA聚合物乳液可从Air Products Polymers,L.P.市购,商标为AIRFLEX_105、AIRFLEX108和AIRFLEX192。可从Air ProductsPolymers,L.P.得到EVCl聚合物乳液,商标为AIRFLEX 4500、AIRFLEX4514和AIRFLEX 4530。
把这些乳液以20%的固体喷雾施加到纤维素/合成材料基材的双侧,该基材具有60克/平方米的基重。所加乳液以基于干基材重量20%的干聚合物为目标。所喷出的乳液在320_(160℃)的透气烘箱中固化3分钟。按照ASTM方法D5035-95测定所得非织造网的干和湿断裂拉伸强度。
实施例1
用不同比例yAE-NMA/EyCl聚合物乳液粘结的网的湿拉伸强度比较
制备一系列共混物,以便确定非织造基材的湿拉伸强度,这些基材被喷雾施加了VAE-NMA/EVCl聚合物乳液的各种共混物,其以100%的VAE-NMA聚合物乳液对100%的EVCl聚合物乳液开始。这种VAE-NMA干燥聚合物组成由75%的醋酸乙烯酯、21%的乙烯、2%的N-羟甲基丙烯酰胺和2%的丙烯酰胺组成。EVCl干燥聚合物组成由84%的氯乙烯、14%的乙烯和2%的丙烯酰胺组成。未向本实施例所列的任何乳液中添加酸催化剂。表1列出了这些结果。
表1
                                  用VAE-NMA/EVCl乳液粘结的网的湿拉伸强度%干燥乳液
粘合剂   100%VAE-NMA   75%VAE-NMA25% EVCl   50%VAE-NMA50% EyCl   25%VAE-NMA75%EVCl  10%VAE-NMA90%EVCl  100%EVCl
湿拉伸强度g/5cm(无催化剂)   1495   1797   1675   1442  1270  887
表1的结果说明,与单独的未催化VAE-NMA聚合物乳液相比,在25%和50% EVCl水平时,共混物提供优异的湿强度性能。共混物中EVCl为75%及更高水平所显示的湿强度性能小于或等于未催化VAE-NMA聚合物乳液的。当与100%VAE-NMA乳液聚合物比较时,25%至50%EVCl与VAE-NMA的共混物取得优异的湿强度。这一特征令人吃惊,乃是由于使用100%EVCl乳液聚合物的非织造产品的湿强度明显小于仅用VAE-NMA乳液聚合物的。可以预期,当共混物中EVCl的水平增加时,非织造产品的湿强度降低。
实施例2
用VAE-NMA/EVCl聚合物乳液粘结并用酸催化剂固化的网的湿拉伸强度比较
根据实施例1制备一系列非织造产品,不同的是,一些VAE聚合物用酸催化剂固化,而一些只依靠使用EVCl聚合物作为催化剂或湿强度促进剂。采用的VAE和EyCl聚合物组成是实施例1所报道的那些。表2列出了结果。
表2
                     用VAE-NMA/EVCl聚合物乳液粘结的网的湿拉伸强度%干燥乳液
粘合剂     100%VAE-NMA     95%VAE-NMA5%EVCl     90%VAE-NMA10%EVCl     80%VAE-NMA20%EVCl     75%VAE-NMA25%EVCl
湿拉伸强度g/5cm(加催化剂)     1871     1908     1677     1722     1763
湿拉伸强度g/5cm(不加催化剂) 1585 1711 1867 1859 1884
表2的结果说明,与未催化的VAE-NMA聚合物相比,用酸催化的VAE-NMA聚合物粘结的非织造网的湿强度性能更优。这和预期的一样,而且表现出VAE-NMA聚合物中NMA交联功能的作用。令人吃惊的是,在不添加酸催化剂条件下,用EVCl含量为10%至25%的EVCl/VAE-NMA共混物粘结的非织造网的湿强度与酸催化的对照VAE-NMA粘结非织造产品的相等。VAE-NMA和EVCl聚合物乳液的非催化共混物的湿强度性能明显优于非催化VAE-NMA聚合物乳液的。这些结果说明的另一个令人吃惊的特征是,当催化促进NMA交联时,与非酸催化的共混物相比,这些共混物未得到更优的湿强度。相反,催化的共混物表现得与非催化的共混物不一样。
实施例3
EVCl共聚物主链中氯乙烯单体的作用
表3显示了用VAE-NMA/EVCl共混聚合物乳液粘结的非织造基材的非织造物湿拉伸性能,其中EVCl聚合物按照EVCl共聚物主链中氯乙烯单体的量而变化。基于75份VAE-NMA和25份EVCl形成共混物,以干固体为基础计。VAE-NMA组成是实施例1中详述的那些。表3中列出了EVCl干聚合物组成。
表3
粘合剂   100%VAE-NMA无催化剂     100%VAE-NMA有催化剂   VAE-NMA与EVCl的共混物 VAE-NMA与EVCl的共混物 VAE-NMA与EVCl的共混物
EVCl的含量   84%氯乙烯14%乙烯2%丙烯酰胺 75%氯乙烯22%乙烯3%丙烯酰胺 71%氯乙烯26%乙烯3%丙烯酰胺
湿拉伸强度g/5cm   1417     1621   1708 1673 1524
结果显示,随着聚合物中氯乙烯含量的降低,有25份EVCl的非织造网的湿强度降低。但是所有共混物均得到优于非催化VAE-NMA浸渍的非织造物的湿强度性能。
实施例4
聚合物主链中含NMA的EVCl聚合物
本实施例说明用VAE-NMA/EVCl聚合物共混物粘结的非织造网的湿强度性能,共混物中EVCl共聚物在聚合物主链上还含有NMA。乳液以75%VAE-NMA和25%EVCl的干固体比共混。没有向VAE-NMA/EVCl聚合物共混物中加酸催化剂。表4显示了这些结果,其中包括表3的结果。
表4
                       用VAE-NMA和EVCl聚合物乳液共混物粘结的网的湿拉伸强度性能改变EVCl类型
  粘合剂   100%VAE-NMA无催化剂   100%VAE-NMA有催化剂 VAE-NMA与EVCl的共混物 VAE-NMA与EVCl的共混物 VAE-NMA与EVCl的共混物 VAE-NMA与EVCl-NMA聚合物的共混物
  EVCl含量 84%氯乙烯14%乙烯2%丙烯酰胺 75%氯乙烯22%乙烯3%丙烯酰胺 71%氯乙烯26%乙烯3%丙烯酰胺 83wt%氯乙烯14wt%乙烯3wt%NMA
  湿拉伸强度g/5cm   1417   1621 1708 1673 1524 1775
表4说明,与丙烯酰胺相反,通过在EVCl聚合物中添加NMA,非织造基材的湿强度性能取得一定的增加。但是,差异是轻微的。
实施例5
VAE-NMA聚合物乳液中乙烯浓度的影响
按照实施例4的工序制备非织造网,不同的是,改变了乙烯含量,结果列于表5
表5
                 用VAE-NMA聚合物乳液和VAE-NMA/EVCl聚合物乳液共混物粘结的网的湿拉伸强度
  粘合剂   100% VAE-NMA   75%VAE-NMA25%EVCl   100%VAE-NMA   75%VAE-NMA25%EVCl
  VAE-NMA的含量   65wt%醋酸乙烯酯31wt%乙烯2wt%NMA2wt%丙烯酰胺   65wt%醋酸乙烯酯31wt%乙烯2wt%NMA2wt%丙烯酰胺   74wt%醋酸乙烯酯21wt%乙烯5wt% NMA   74wt%醋酸乙烯酯21wt%乙烯5wt% NMA
  EVCl的含量   84wt%氯乙烯14wt%乙烯2wt%丙烯酰胺   84wt%氯乙烯14wt%乙烯2wt%丙烯酰胺
  湿拉伸强度g/5cm(有催化剂)   1483   1485   1995   2004
  湿拉伸强度g/5cm(无催化剂)   1456   1617   1717   2059
表5显示与实施例2类似的结果,即,用非催化共混物比非催化VAE-NMA聚合物乳液获得更优的湿强度结果。但是,出乎预料的是,催化共混物与催化VAE-NMA聚合物乳液相比,也得到类似的优异湿强度结果。
实施例6
EVCl对VAE非织造粘合剂粘度的影响
本实施例的目的是确定当与VAE聚合物乳液共混时,EVCl聚合物乳液的粘度影响,以及这些共混物是否显示出不利的粘度增加,致使它们由于贮藏寿命不足而不可接受。VAE-NMA/EVCl共混物的所希望结果之一是稳定的贮藏寿命粘度。当使某些酸催化剂与VAE-NMA聚合物乳液共混时,并不总是可能有这种稳定性。当使用某些酸催化剂时,聚合物乳液的pH值全面降低到,使得可能发生VAE-NMA聚合物的早期交联的水平,导致聚合物乳液粘度显著上升。聚合物乳液粘度的升高能使聚合物乳液由于施用局限性而不可用。
以下表6说明,与不含酸催化剂的25% EVCl/75%VAE-NMA(干%)聚合物乳液相比,在向VAE-NMA聚合物乳液中加入1%(基于干乳液的干重)硫酸氢钠酸催化剂后,观察到的热老化粘度升高。VAE和EVCl的干聚合物组成是实施例1所详述的那些。在对流烘箱中于120_(49℃)进行2个星期的热老化。用Brookfield LV粘度计,采用速度60rpm的#3转子,测定聚合物乳液的粘度。在聚合物乳液从烘箱中取出并使其冷却到室温后,测定粘度。
表6
                             热老化的粘度稳定性
  粘合剂   VAE-NMA聚合物乳液,无催化剂   VAE-NMA,使用NaHSO4催化剂   VAE-NMA/EVCl共混物(无催化剂)
  起始(粘度,厘泊)   75   82   148
  1周(粘度,厘泊)   64   600   180
  2周(粘度,厘泊)   74   800   160
表6显示,对照的VAE-NMA酸催化聚合物乳液在1个星期中粘度显著增加,并继续上升,而无酸催化剂的VAE-NMA/EVCl共混物的粘度基本未增加。

Claims (15)

1.一种非织造产品,其含有纤维的非织造网,向该网施加非酸催化的粘合剂以形成粘合剂浸渍的网,该非酸催化的粘合剂含有第一聚合物和第二聚合物的乳液共混物,该第一聚合物含有乳液聚合的醋酸乙烯酯、乙烯和N-羟甲基丙烯酰胺单元,而该第二聚合物含有乳液聚合的氯乙烯、乙烯和N-羟甲基丙烯酰胺或丙烯酰胺或N-羟甲基丙烯酰胺和丙烯酰胺单元,其中充分干燥该粘合剂浸渍的网,以便将纤维粘结在一起并形成自支撑网,其中基于100份全部聚合物的干重,共混物含有2至70份的第二聚合物,少于10份的第三聚合物,且剩余的份数由第一聚合物组成。
2.权利要求1的非织造产品,其中第一聚合物基于该聚合物总重量计含有50至94wt%的醋酸乙烯酯、5至40wt%的乙烯和0.5至10wt%的N-羟甲基丙烯酰胺,而第二聚合物基于该聚合物总重量计含有55至95wt%的氯乙烯、5至35wt%的乙烯、和0.1至10wt%的N-羟甲基丙烯酰胺或丙烯酰胺或N-羟甲基丙烯酰胺与丙烯酰胺两者。
3.权利要求2的非织造产品,其中第二聚合物基于该聚合物总重量计含有70至85wt%的氯乙烯、13至26wt%的乙烯、和2至4wt%的N-羟甲基丙烯酰胺或丙烯酰胺或N-羟甲基丙烯酰胺及丙烯酰胺两者。
4.权利要求2的非织造产品,其中第一聚合物基于该聚合物总重量计含有64至79wt%的醋酸乙烯酯、20至30wt%的乙烯、和1至6wt%的N-羟甲基丙烯酰胺。
5.权利要求3的非织造产品,其中第一聚合物基于该聚合物总重量计含有64至79wt%的醋酸乙烯酯、20至30wt%的乙烯、和1至6wt%的N-羟甲基丙烯酰胺。
6.权利要求2的非织造产品,其中每100重量份共混物中,共混物含有50至80重量份的第一聚合物和5至50重量份的第二聚合物。
7.权利要求2的非织造产品,其中粘合剂以基于干基3%至50重量%的添加量施加到非织造网上。
8.权利要求2的非织造产品,其中粘合剂以基于干基约10%至30重量%的添加量施加。
9.权利要求2的非织造产品,其中共混物基本上由第一聚合物和第二聚合物组成。
10.权利要求9的非织造产品,其中共混物不包括N-羟甲基丙烯酰胺反应活性聚合物。
11.权利要求2的非织造产品,其中纤维的非织造网含有纤维素或合成聚合物纤维或纤维素与合成聚合物纤维两者的组合。
12.权利要求2的非织造产品,其中纤维非织造网含有天然聚合物纤维。
13.一种非织造产品,其含有纤维的非织造网,向该网施加非酸催化的粘合剂以形成粘合剂浸渍的网,该非酸催化的粘合剂含有第一聚合物和第二聚合物的乳液共混物,该第一聚合物含有乳液聚合的醋酸乙烯酯、乙烯和N-羟甲基丙烯酰胺单元,而该第二聚合物只含有乳液聚合的氯乙烯单元,或含有乳液聚合的氯乙烯和另一种单体的单元,其中充分干燥该粘合剂浸渍的网,以便将纤维粘结在一起并形成自支撑网,其中基于100份全部聚合物的干重,共混物含有2至70份的第二聚合物,少于10份的第三聚合物,且剩余的份数由第一聚合物组成。
14.权利要求13的非织造产品,其中第一聚合物基于该聚合物总重量计含有50至94wt%的醋酸乙烯酯、5至40wt%的乙烯和0.5至10wt%的N-羟甲基丙烯酰胺,而第二聚合物基于该聚合物总重量计含有55至95wt%的氯乙烯和45至5wt%的选自羧酸的乙烯酯、不饱和单羧酸、不饱和多羧酸、烷基乙烯基醚和烯烃的单体。
15.权利要求13的非织造产品,其中每100重量份共混物中,共混物含有50至80重量份的第一聚合物和5至50重量份的第二聚合物。
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7247586B2 (en) * 2004-09-07 2007-07-24 Air Products Polymers, L.P. Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products
US8152929B1 (en) * 2009-05-01 2012-04-10 Perring David A Non-abrasive cleaning products
US20120028527A1 (en) * 2010-07-30 2012-02-02 Wacker Chemical Corporation Ultra Low Formaldehyde Binders for Nonwoven Substrates
WO2013072713A1 (en) * 2011-11-16 2013-05-23 Celanese Emulsions Gmbh Low formaldehyde binder and finishing compositions for nonwoven substrates, fabrics and textiles
US9340908B2 (en) 2011-12-07 2016-05-17 Wacker Chemical Corporation Low formaldehyde and high wet strength vinyl acetate ethylene copolymer and vinyl acetate polymer dispersions
US20130149928A1 (en) 2011-12-07 2013-06-13 Wacker Chemical Corporation Low formaldehyde and high wet strength polymer binder
EP3448669B1 (en) * 2016-04-28 2019-08-28 Wacker Chemie AG Polyvinyl alcohol-stabilized vinyl acetate/ethylene-copolymer dispersions as adhesives for creped webs

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5244695A (en) * 1992-03-17 1993-09-14 Air Products And Chemicals, Inc. Aqueous binder saturants used in a process for making nonwoven filters
CN1487040A (zh) * 2002-06-17 2004-04-07 �����Ʒ�ۺ��﹫˾ 用于非纤维素型基材的氯乙烯/乙酸乙烯酯/乙烯/自交联聚合物

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3380842A (en) 1963-09-20 1968-04-30 Georgia Pacific Corp Decorative composition and a process for its use
US3380851A (en) 1965-03-31 1968-04-30 Air Reduction Nonwoven fabric with vinyl acetateethylene-n-methylol acrylamide interpolymer as binder
US3752733A (en) 1969-10-29 1973-08-14 Monsanto Co Bonded nonwoven fibrous product
US3682871A (en) 1970-06-10 1972-08-08 Goodrich Co B F Low temperature curing vinylidene-halide-unsaturated monocarboxylic acid-n-alkylol amide polymers
US3758429A (en) 1971-11-26 1973-09-11 Monsanto Co Ethylene vinyl chloride n methhylol acrylamide
US3843580A (en) 1972-05-22 1974-10-22 Monsanto Co Ethylene/vinyl chloride/n-methylolacrylamide/n-(alkoxymethyl)acrylamide latices
JPS603087B2 (ja) 1976-06-17 1985-01-25 住友化学工業株式会社 水性分散液の製造方法
US4449978A (en) 1981-08-31 1984-05-22 Air Products And Chemicals, Inc. Nonwoven products having low residual free formaldehyde content
US4537831A (en) 1984-02-22 1985-08-27 Air Products And Chemicals, Inc. Crosslinking of chlorine-containing polymers
US4590102A (en) 1985-01-07 1986-05-20 Air Products And Chemicals, Inc. Low temperature curing of nonwoven products bonded with N-methylolacrylamide-containing copolymers
US4745025A (en) 1986-02-19 1988-05-17 Air Products And Chemicals, Inc. Nonwoven products bonded with binder emulsions of vinyl acetate/ethylene copolymers having improved solvent resistance
US4774283A (en) 1987-03-02 1988-09-27 Air Products And Chemicals, Inc. Nonwoven binders of vinyl acetate/ethylene/self-crosslinking monomers/acrylamide copolymers having improved blocking resistance
US5109063A (en) 1990-12-10 1992-04-28 Air Products And Chemicals, Inc Vinyl acetate/ethylene/NMA copolymer emulsion for nonwoven binder applications
DE4124560A1 (de) 1991-07-24 1993-01-28 Wacker Chemie Gmbh Beschichtungsmittel zur herstellung von wasserdichten, dampfdurchlaessigen und flammverzoegernden beschichtungen
US7247586B2 (en) * 2004-09-07 2007-07-24 Air Products Polymers, L.P. Vinyl acetate/ethylene and vinyl chloride polymer blends as binders for nonwoven products

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5244695A (en) * 1992-03-17 1993-09-14 Air Products And Chemicals, Inc. Aqueous binder saturants used in a process for making nonwoven filters
CN1487040A (zh) * 2002-06-17 2004-04-07 �����Ʒ�ۺ��﹫˾ 用于非纤维素型基材的氯乙烯/乙酸乙烯酯/乙烯/自交联聚合物

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