CN111989349B - 无甲醛粘合剂组合物 - Google Patents
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Abstract
一种用于纤维粘合的水性粘合剂组合物,其可在水性介质中在聚乙烯醇存在下通过乙酸乙烯酯和乙烯的自由基引发聚合而获得,特征在于,在水解度为80‑99mol%的聚乙烯醇的存在下共聚以下组分:a)60‑94重量%的乙酸乙烯酯,b)5‑30重量%的乙烯,c)0.4‑5重量%的丙烯酰胺和/或甲基丙烯酰胺,d)0.4‑5重量%的丙烯酸和/或甲基丙烯酸,e)0.2‑2重量%的马来酸酐和/或马来酸,其中,以重量%计的数值在每种情况下均基于共聚单体的总重量,且在每种情况下合计为100重量%。
Description
本发明涉及一种无甲醛的粘合剂组合物及其在制备织物片状结构中的用途。
用于织物片状结构的粘合剂组合物通常包含基于烯键不饱和单体的聚合物作为粘合剂组分,且在大多数情况下以水分散体形式存在。所述聚合物通常包含交联单体的单元,因此可以彼此交联,如果适用的话也可以与纤维交联,从而有助于形成具有更高强度的织物片状结构。因此,可以实现纤维的永久固定并增加所述织物片状结构的机械应力的耐久性。织物片状结构也已知为术语“无纺布”,可以通过例如气流成网、湿法成网或纺丝成网工艺来制备。
迄今为止,在工业实践中,主要是包含N-羟甲基丙烯酰胺单元(NMA)的聚合物被用作粘合剂组分。N-羟甲基丙烯酰胺基团可以与纤维素或淀粉的OH基团反应,从而导致粘合剂聚合物和纤维之间形成共价键。不利的是,在这些聚合物交联的过程中会形成甲醛,其因毒理学原因应避免出现。另外,由于其制造,这样的聚合物在许多情况下都已经包含甲醛作为伴随物质,如在通过使用释放甲醛的引发剂例如甲醛次硫酸钠的聚合反应的制造中。
因此,需要最小化粘合剂组合物中的甲醛含量,并尽可能以有效方式使无甲醛的织物片状结构易于制备。
在EP 0 596 318 B1中,为了在聚合过程中降低聚合物水分散体中的甲醛含量,使用了抗坏血酸替代甲醛次硫酸氢钠作为氧化还原引发剂体系中的还原剂。WO 2013/124417A1描述了一种含NMA的无纺布粘合剂,其中N-羟甲基丙烯酰胺单体单元被丙烯酰胺单体单元部分代替。WO 2017/189350 A1使用了由聚乙烯醇稳定的乙酸乙烯酯-乙烯共聚物,以及N-羟甲基丙烯酰胺和丙烯酰胺共聚单体单元的组合。WO 2013/085764 A1描述了使用聚乙烯醇稳定的基于乙酸乙烯酯-乙烯共聚物分散体的纤维粘合剂,其不包含任何N-羟甲基丙烯酰胺,并且其包含氯化铵以提高所述粘合剂的湿强度。EP 0 609 849 A1描述了一种无纺布粘合剂,其为具有N-丁氧基甲基丙烯酰胺和丙烯酰胺单体单元的乙酸乙烯酯-乙烯共聚物的乳化剂稳定的水分散体。EP 0 184 153B1描述了用阴离子乳化剂稳定的、基于具有丙烯酰胺和二羧酸单体单元的丙烯酸酯共聚物的无甲醛胶乳粘合剂。JP 2008-297523 A描述了基于用聚乙烯醇稳定的乙酸乙烯酯-乙烯共聚物的粘合剂,其还包含衍生自丙烯酰胺和丙烯酸的共聚单体单元。
本发明解决的问题是提供一种用于纤维粘合的水性粘合剂,即使不添加交联催化剂,该粘合剂也可导致纤维复合材料具有高湿强度而不释放甲醛。
本发明涉及一种用于纤维粘合的水性粘合剂组合物,其可通过在水性介质中在聚乙烯醇的存在下通过自由基引发聚合乙酸乙烯酯和乙烯而获得,其特征在于
在水解度为80-99mol%的聚乙烯醇的存在下共聚以下组分:
a)60-94重量%的乙酸乙烯酯,
b)5-30重量%的乙烯,
c)0.4-5重量%的丙烯酰胺和/或甲基丙烯酰胺,
d)0.4-5重量%的丙烯酸和/或甲基丙烯酸,
e)0.2-2重量%的马来酸酐和/或马来酸,
其中,以重量%计的数值在每种情况下均基于共聚单体的总重量,并且在每种情况下合计为100重量%。
优选,基于所述共聚单体的总重量,a)70-85重量%的乙酸乙烯酯进行共聚。
优选,基于所述共聚单体的总重量,b)15-28重量%的乙烯进行共聚。
每种情况下,基于所述共聚单体的总重量,优选将c)0.5-2重量%,特别优选0.7-1.2重量%的丙烯酰胺和/或甲基丙烯酰胺共聚。优选,仅丙烯酰胺作为共聚单体c)进行共聚。
优选,在每种情况下,基于所述共聚单体的总重量,共聚d)0.5-2重量%,特别优选0.7-1.2重量%的丙烯酸和/或甲基丙烯酸。优选,仅丙烯酸作为共聚单体d)进行共聚。
优选,在每种情况下,基于所述共聚单体的总重量,共聚e)0.2-1重量%,特别优选0.4-0.6重量%的马来酸酐和/或马来酸。优选,仅马来酸酐作为共聚单体e)进行共聚。
在另一个优选的实施方案中,所述单体c)和e)可以全部或部分用马来酰胺酸代替。
最优选,共聚单体成分c):共聚单体成分d):共聚单体成分e)的重量比为约1:1:(0.5-1)。
所述聚合物可通过自由基引发聚合获得。所述聚合物可以已知的方式制备,如通过悬浮聚合方法或优选通过在水中的乳液聚合方法。聚合温度通常为20-120℃,且通常在5-100巴的压力下操作。所述聚合的引发可以用通常用于乳液聚合或悬浮聚合的水溶性或单体可溶性引发剂或氧化还原引发剂组合来进行。优选的还原剂是抗坏血酸、异抗坏血酸或其盐或不含甲醛的还原剂,如Brüggolite FF6。优选的氧化剂是过硫酸盐化合物和过氧化物,尤其是过硫酸铵或碱金属过硫酸盐或过氧化氢。优选,不使用释放甲醛的物质如甲醛次硫酸盐作为引发剂。
基于所述共聚单体的总重量,优选在1-10重量%的一种或多种聚乙烯醇的存在下进行所述聚合,在每种情况下,所述一种或多种聚乙烯醇的水解度为80-99mol%,优选为85-90mol%,特别优选87-89mol%。所述聚乙烯醇在4%水溶液中的霍普勒粘度通常为2-40mPas,优选2-15mPas(根据霍普勒在20℃下的方法,DIN 53015)。所提及的聚乙烯醇可商购获得,并且可以通过本领域技术人员已知的方法获得。
任选,基于所述共聚单体的总重量,少量的乳化剂,如0.1至2.0重量%,可额外用于所述聚合中。优选,在聚合过程中不使用乳化剂。所述水分散体的固体含量通常为40-60重量%,优选45-55重量%。所述水分散体的布氏(Brookfield)粘度优选为50-2000mPas,特别优选100-1500mPas(使用布氏粘度计在23℃,20rpm下以分散体的固体含量为49-51重量%的条件测定)。
所述粘合剂组合物还可包含一种或多种添加剂,例如乳化剂,如具有低乙氧基化度(特别是2至5)的脂肪醇乙氧基化物,或磺基琥珀酸二异十三烷基酯或其盐,如钠盐。基于所述聚合物的干重,乳化剂的典型用量为0-1重量%,优选0-0.6重量%。使用这种粘合剂组合物制成的织物片状结构的亲水性可以通过乳化剂来提高。其它添加剂是酸性催化剂,如氯化铵,柠檬酸或硫酸。基于所述聚合物的干重,酸性催化剂的用量通常为0-2重量%,优选0.1-1重量%。如果所述酸性催化剂是布朗斯台德酸,则其用量应使得pH优选为0-4,特别优选2-3。最优选,在所述水性粘合剂组合物中不使用催化剂。
根据本发明在制备织物片状结构中的用途通常通过使纤维与一种或多种根据本发明的水性粘合剂组合物相接触并随后干燥来实现。所述干燥优选在≤160℃,特别优选在120-160℃,最优选在140-160℃的温度下进行。
所述纤维通常基于天然或合成(尤其是有机的)材料。其实例是基于可形成纤维的聚合物例如粘胶纤维,聚酯,聚酰胺,聚丙烯和聚乙烯纤维的合成纤维。天然纤维材料的实例是木材,羊毛,棉,黄麻,亚麻,***,椰子,麻和剑麻纤维,尤其是纤维素纤维。所述纤维可以松散地使用,或者也可以束或机织织物,纱线的形式使用,或者优选以无纺布的形式使用,如羊毛,稀松布或针织物。所述无纺布可任选进行热或机械预压实,例如针刺。
所述纤维可以具有任何长度,优选5-100mm,特别优选7-75mm,最优选10-60mm。所述纤维可具有常规直径,优选直径为0.1μm至1mm,特别优选0.5μm至100μm,最优选1μm至50μm。
为了以本发明的方式制备所述织物片状结构,所述水性粘合剂组合物的用量优选为1-50重量%,特别优选10-30重量%,最优选15-25重量%,在每种情况下都基于所述纤维的总重量。所述纤维的比例,每种情况下都基于所述织物片状结构的总重量,优选为40-99重量%,特别优选60-90重量%,最优选70-80重量%。
为了以根据本发明的方式制备所述织物片状结构,可以在所述压实之前,将所述纤维在大面积上拉伸。其方法是已知的,主要取决于被压实的纤维材料的预期应用。可以通过例如气流成网,湿法成网,直接纺丝或梳理设备来铺置纤维。如果合适的话,在用粘合剂压实之前,也可以通过例如交叉铺网,针刺或喷水压实进行机械压实。随后,可以将所述粘合剂组合物施加到铺置的纤维上,其中可以将所述粘合剂组合物以片状,点状或图案化形式施加。随后,可以通过施加热和任选施加压力来将纤维粘合。
所述水性粘合剂组合物也适用于制备层压板,在这种情况下,将两层纤维层相互粘合,或将一层纤维层粘合至另一基材上。这可以通过铺置纤维层并在铺置之后施加所述粘合剂组合物,并且通过例如气流成网在顶部上铺置另一个纤维层来完成。代替所述两个纤维层,还可以在其上放置另一个基材,如塑料膜。随后,通过施加热量和任选施加压力进行粘合。例如,该方法可使回收的棉质隔热材料与作为表面材料的纤维网持久地叠合在一起。
所述粘合剂组合物还可适用于制造蓬松的无纺布或填料,如用作由纤维材料制备模制品的半成品或用作填料,衬垫,隔热和过滤填料。为此,可将所述粘合剂组合物施加到所述纤维上并优选在模具中通过加热压实。
根据本发明制备的织物片状结构优选是无纺布,特别是薄纸,毡,衬垫或粗网,松散的织造物或针织物。所述织物片状结构可以,例如,被用于汽车领域中,用于诸如桌布之类的家用产品,诸如卫生纸之类的卫生制品,服装业,医学纺织品或土工织物。
下列实施例进一步阐明了本发明:
粘结剂组合物:
为了进行测试,制备了固含量为约55%的乙酸乙烯酯-乙烯共聚物的水分散体。
通过76-78重量%的乙酸乙烯酯,21-22重量%的乙烯以及表1中给出的量的丙烯酰胺(AAM),丙烯酸(AA),马来酸酐(MA),马来酰胺酸(MAA)和N-羟甲基丙烯酰胺(NMA)的乳液聚合进行所述制备。
所述聚合分别在压力反应器中在40-75℃的温度区间和至多85巴的压力下进行。
基于所述共聚单体的总重量,在10重量%的霍普勒粘度为5mPas(4%水溶液)且水解度为88摩尔%的聚乙烯醇(PVOH)的存在下进行所述聚合。
过氧化氢和Brüggolith FF6被用于引发。
表1:
实施例 | AAM(%) | AA(%) | MA(%) | NMA(%) | MAA(%) | 稳定化 |
实施例1 | 1 | 1 | 0.5 | 0 | 0 | PVOH |
比较实施例2 | 0 | 0 | 0 | 0 | 0 | PVOH |
比较实施例3 | 0 | 0 | 0.5 | 0 | 0 | PVOH |
比较实施例4 | 1 | 1 | 0 | 0 | 0 | PVOH |
比较实施例5 | 0 | 0 | 0 | 1 | 0 | PVOH |
比较实施例6 | 0 | 1 | 0 | 0 | 1 | PVOH |
比较实施例7 | 1 | 1 | 0 | 0 | 0 | 乳化剂 |
比较实施例8 | 1 | 1 | 0.5 | 0 | 0 | 乳化剂 |
测定气流成网无纺布的湿强度值:
将用水稀释至固含量为20%的相应(比较)实施例的聚合物分散体均匀喷涂到热法预粘合的气流成网(75g/m2;88%绒毛纸浆和12%PP/PE两组分纤维;厚度为0.85mm)的两侧上,所用气流成网方法是根据无气工艺(Unijet 8001E狭缝喷嘴;5巴),用半自动喷涂组件施加可喷涂液体,然后在实验室中用空气干燥器(Mathis LTF;来自Mathis/CH)在160℃下干燥3分钟(施涂量:20%重量聚合物,基于聚合物和纤维网的总重量)。
对于每个断裂强度测试,在与机器生产方向成横向的方向上制备10个网板条(夹紧长度20厘米;夹紧长度5厘米)。为了测量湿断裂强度,将所述样品条各自在测量前在水中储存1分钟。
以类似于DIN EN 29073(第3部分:无纺布的测试方法,1992)来测定湿断裂强度,在使用软件(版本11.02)的/>1445测试机(100N测量室)(Zwick Roell)上对测试样品进行极限拉伸力测量,夹紧长度为100±1mm,夹紧宽度为15±1mm,变形速率为150mm/min。
测试结果总结在表2中。
表2:
*=没有催化剂/具有1%柠檬酸,-=没有测量
实施例1表明,用本发明的粘合剂组合物即使不添加催化剂也能获得高的湿断裂强度。这也适用于实施例6的实施方案,其中丙烯酰胺和马来酸酐被马来酰胺酸取代。
在含NMA的粘合剂组合物中,如比较实施例5中,仅在酸性催化剂下获得了类似的高的数值,而在没有催化剂的情况下,湿断裂强度不足。
与实施例1中用聚乙烯醇稳定的粘合剂组合物相反,比较实施例7和8的乳化剂稳定的粘合剂组合物仅获得不高的值。
Claims (12)
1.一种用于纤维粘合的水性粘合剂组合物,其可在水性介质中在聚乙烯醇存在下通过乙酸乙烯酯和乙烯的自由基引发聚合而获得,特征在于:
在水解度为80-99mol%的聚乙烯醇的存在下共聚以下组分:
a)60-94重量%的乙酸乙烯酯,
b)5-30重量%的乙烯,
c)0.4-5重量%的丙烯酰胺和/或甲基丙烯酰胺,
d)0.4-5重量%的丙烯酸和/或甲基丙烯酸,
e)0.2-2重量%的马来酸酐和/或马来酸,
其中,以重量%计的数值在每种情况下均基于共聚单体的总重量,且在每种情况下合计为100重量%。
2.如权利要求1所述的水性粘合剂组合物,特征在于,基于所述共聚单体的总重量,将a)70-85重量%的乙酸乙烯酯共聚。
3.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,基于所述共聚单体的总重量,将b)15-28重量%的乙烯共聚。
4.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,基于所述共聚单体的总重量,将c)0.5-2重量%的丙烯酰胺共聚。
5.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,基于所述共聚单体的总重量,将d)0.5-2重量%的丙烯酸共聚。
6.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,基于所述共聚单体的总重量,将e)0.2-1重量%的马来酸酐共聚。
7.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,所述共聚单体成分c):共聚单体成分d):共聚单体成分e)的重量比约为1:1:(0.5-1)。
8.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,所述共聚单体c)和e)全部或部分被马来酰胺酸代替。
9.如权利要求1或2任一所述的水性粘合剂组合物,特征在于,所述组合物在一种或多种水解度为80-99mol%且在4%水溶液中霍普勒粘度为2-15mPas的聚乙烯醇的存在下共聚,所述粘度根据DIN 53015根据在20℃下的方法测定的。
10.如权利要求1-9任一所述的水性粘合剂组合物用于制备织物片状结构的用途。
11.如权利要求10所述的用途,其中,使纤维与所述水性粘合剂组合物相接触,然后干燥。
12.如权利要求10或11任一所述的用途,特征在于,所述水性粘合剂组合物中不存在催化剂。
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