CN113831575A - 双尾长链阴离子表面活性剂在水性聚氨酯分散体中的用途 - Google Patents
双尾长链阴离子表面活性剂在水性聚氨酯分散体中的用途 Download PDFInfo
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- CN113831575A CN113831575A CN202110701875.4A CN202110701875A CN113831575A CN 113831575 A CN113831575 A CN 113831575A CN 202110701875 A CN202110701875 A CN 202110701875A CN 113831575 A CN113831575 A CN 113831575A
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Abstract
本发明公开了双尾长链阴离子表面活性剂在水性聚合物分散体中作为添加剂用于制备多孔聚合物涂层、优选用于制备多孔聚氨酯涂层的用途。
Description
本发明属于塑料涂层和人造革(imitation leathers)领域。
本发明更具体地涉及使用双尾长链阴离子表面活性剂作为添加剂生产多孔聚合物涂层,尤其是多孔聚氨酯涂层。
涂覆有塑料的织物,例如人造革,通常由织物载体组成,在该织物载体上层压多孔聚合物层,该多孔聚合物层进而涂覆有顶层或面漆(topcoat)。
在此上下文中,多孔聚合物层优选具有在微米范围内的孔并且是空气能透过的并且因此是透气的,即对水蒸气可渗透,但是防水的。多孔聚合物层通常包含多孔聚氨酯。为了环境友好地生产PU基人造革,最近开发了一种基于水性聚氨酯分散体(称为PUD)的方法。这些通常由分散在水中的聚氨酯微粒组成;固含量通常在30-60重量%范围内。为了生产多孔聚氨酯层,这些PUD被机械发泡,涂覆在载体上(层厚度通常在300-2000μm之间),然后在升高的温度下干燥。在此干燥步骤中,PUD体系中存在的水蒸发,这导致聚氨酯颗粒膜的形成。为了进一步提高膜的机械强度,还可以在生产过程期间向PUD体系中添加亲水性(多)异氰酸酯或碳二亚胺,在干燥步骤期间,这些可以与聚氨酯颗粒表面上存在的游离OH基反应,从而导致聚氨酯膜的额外交联。
如此制备的PUD涂层的机械和触觉特性在很大程度上取决于多孔聚氨酯膜的孔结构。此外,多孔聚氨酯膜的孔结构影响材料的渗透性和透气性。在这里可以利用非常精细、均质分布的孔实现特别好的特性。在上述生产过程中影响孔结构的常用方法是在机械发泡之前或期间将泡沫稳定剂添加到PUD体系中。合适的稳定剂的第一个作用是在发泡操作期间可以将足够量的空气打入PUD体系中。其次,泡沫稳定剂对产生的气泡的形态有直接影响。气泡的稳定性在很大程度上受稳定剂类型的影响。这在发泡的PUD涂层的干燥期间尤其重要,因为其可以此方式防止干燥缺陷,诸如孔粗化或干燥裂纹。
过去在上述PUD方法中已经使用了各种泡沫稳定剂。例如,文献US 2015/0284902A1或US 2006 0079635 A1描述了基于硬脂酸铵的泡沫稳定剂的用途。然而,使用相应的基于硬脂酸铵的稳定剂伴随着许多缺点。这里的一个显著缺点是硬脂酸铵在成品人造革中具有非常高的迁移能力。这样的作用是表面活性剂分子随着时间的推移在人造革表面聚集,导致皮革表面变白。此外,这种表面活性剂迁移会导致在人造革的表面上令人感觉不舒服的油腻膜,尤其是当相应的材料与水接触时。
硬脂酸铵的另一个缺点是其与硬水接触时形成不溶性石灰皂。在基于硬脂酸铵生产的人造革与硬水接触的情况下,人造革表面处因此产生白霜,这尤其在深色皮革的情况下是不希望的。
基于硬脂酸铵的泡沫稳定剂的又一个缺点是它们确实允许水性聚氨酯分散体的有效发泡,但是通常会导致相当粗糙和不规则的泡沫结构。这会对成品人造革的光学和触觉性能产生不利影响。
硬脂酸铵的又一个缺点是所生产的PUD泡沫通常具有不足的稳定性,这会导致其加工过程中的缺陷,尤其是在升高的温度下干燥PUD泡沫时。这样做的结果是,例如,相应的泡沫必须相对温和且缓慢地干燥,这进而又导致人造革生产中更长的加工时间。
作为基于硬脂酸铵的泡沫稳定剂的替代品,多元醇酯和多元醇醚过去被认为是用于水性聚氨酯分散体的有效泡沫添加剂。结构描述于例如文献EP 3487945 A1和WO2019042696A1中。与硬脂酸铵相比,多元醇酯和多元醇醚的主要优点是它们在成品人造革中仅轻微迁移(如果有的话),因此不会导致不希望的表面变色。此外,多元醇酯和多元醇醚对硬水不敏感。
另外,多元醇酯和多元醇醚优于基于硬脂酸铵的泡沫稳定剂的另一个优点是它们通常导致明显更细和更均质的泡沫结构,这对用这些物质生产的人造革材料的性能具有有利影响。多元醇酯和多元醇醚通常还导致更稳定的PUD泡沫,这进而在人造革生产中带来与工艺相关的优势。
尽管有这些优点,但多元醇酯和多元醇醚也并非完全没有潜在的缺点。这里一个潜在的缺点是,在某些情况下,PUD体系中存在的其他助表面活性剂的存在可能会削弱这些化合物类别的泡沫稳定效果。然而,特别是在水性聚氨酯分散体的生产中,助表面活性剂的使用并不罕见。助表面活性剂在这种情况下用于改善聚氨酯预聚物在水中的分散,并且通常保留在最终产品中。在含有多元醇酯或多元醇醚作为泡沫添加剂的水性聚氨酯分散体的机械发泡期间,在某些情况下,相应助表面活性剂会对体系的发泡特性产生不利影响。因此,在某些情况下,通常只有很少的空气(如果有的话)可以打入体系;这对所得泡沫结构是有害的。助表面活性剂还对所生产泡沫的稳定性产生不利影响,这会导致发泡的PUD体系的加工期间的泡沫老化,进而导致所生产的泡沫涂层的故障和缺陷。
一个进一步的潜在的缺点是含有多元醇酯或多元醇醚作为泡沫添加剂的PUD体系通常需要非常高的剪切能来进行有效发泡。在某些情况下,这进而又会带来限制和与工艺相关的缺点。
因此,本发明解决的问题是提供用于生产基于PUD的泡沫体系和泡沫涂层的添加剂,其能够使PUD体系有效发泡并且不具有在现有技术中详述的缺点。已经令人惊讶地发现,双尾长链阴离子表面活性剂能够解决所述问题。
因此,本发明提供了双尾长链阴离子表面活性剂作为水性聚合物分散体、优选水性聚氨酯分散体中的添加剂、优选作为泡沫添加剂,用于制备多孔聚合物涂层、优选用于制备多孔聚氨酯涂层的用途。
本发明使用双尾长链阴离子表面活性剂在此令人惊讶地具有多种优点。
一个优点是双尾长链阴离子表面活性剂能够特别有效地使水性PUD体系发泡。如此产生的泡沫在此以具有特别均质的孔分布的特别细的孔结构而值得注意,这进而对基于这些泡沫生产的多孔聚合物涂层的机械和触觉性能具有非常有利的影响。此外,以这种方式可以改善涂层的渗透性或透气性。
进一步的优点是双尾长链阴离子表面活性剂即使在相对低的剪切速率下也能够使PUD体系有效发泡,这导致在人造革生产期间更少的限制和更广泛的可加工性。
又一个优点是双尾长链阴离子表面活性剂能够生产特别稳定的泡沫。这首先对它们的可加工性具有有利影响。其次,提高的泡沫稳定性的优点在于,在相应泡沫的干燥期间,可以避免干燥缺陷,诸如孔粗化或干燥裂纹。此外,改进的泡沫稳定性能够使泡沫更快地干燥,从环境的角度来看,和从经济的角度来看,这提供了加工优势。
又一个优点是双尾长链阴离子表面活性剂的功效几乎不会被PUD体系中存在的助表面活性剂(如果有的话)削弱。因此,根据本发明的表面活性剂配制物,即使在含有助表面活性剂的PUD体系的情况下,也能够使体系有效发泡,并形成同时极其稳定的精细且均质的泡沫。
又一个优点是根据本发明的双尾长链阴离子表面活性剂在成品人造革中几乎没有任何迁移能力(如果有的话),因此不会导致不希望的表面变色或风化。此外,根据本发明的表面活性剂对硬水几乎不敏感(如果有的话)。
贯穿本发明的表述“双尾长链阴离子表面活性剂”涵盖具有阴离子亲水性头部基团和两个相同或不同的长链疏水烃基的表面活性剂。在本文中“长链”的意思是疏水烃基由至少12个碳原子、优选至少14个碳原子、更优选至少16个碳原子组成。
贯穿本发明的术语“助表面活性剂”包括可与根据本发明的双尾长链阴离子表面活性剂一起存在于聚合物分散体中的另外的表面活性剂。这些尤其包括在聚合物分散体的生产期间使用的表面活性剂。例如,聚氨酯分散体通常通过合成PU预聚物来生产,该PU预聚物在第二步中分散在水中,然后与扩链剂反应。为了改善预聚物在水中的分散,这里可以使用助表面活性剂。在本发明的上下文中,助表面活性剂优选为阴离子助表面活性剂。
在下文中通过示例进一步描述本发明,但无意将本发明限制于这些说明性实施方案。在下面指定范围、通式或化合物类别的情况下,这些旨在不仅包括明确提及的化合物的相应范围或组,而且还包括可通过去除单个值(范围)或化合物获得的化合物的所有子范围和子组。当在本说明书的上下文中引用文献时,其全部内容,特别是关于形成引用该文献的上下文的主题的全部内容,旨在形成本发明的公开内容的一部分。除非另有说明,否则百分比均为重量百分比。在下文给出通过测量测定的参数的情况下,除非另有说明,测量是在25℃的温度和101 325Pa的压力下进行的。在本发明中使用化学(经验)公式的情况下,指定的指数不仅可以是绝对数,还可以是平均值。对于聚合化合物,指数优选代表平均值。本发明中给出的结构式和经验式代表可能通过重复单元的不同排列而产生的所有异构体。
在本发明的上下文中,优选由阴离子头部基团和长链疏水基团组成的那些双尾长链阴离子表面活性剂。这里的疏水基团可以独立地是具有12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子的相同或不同的一价脂族或芳族、饱和或不饱和的烃基。这里的阴离子头部基团优选基于有机羧酸盐或阴离子硫或磷化合物。更优选地,所述阴离子头部基团具有选自羧酸根、磷酸根、膦酸根、次膦酸根、硫酸根和磺酸根的结构单元。
在本发明的上下文中,特别优选符合通式(I)的双尾长链阴离子表面活性剂
其中R1基团独立地是具有12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子的相同或不同的一价饱和或不饱和的、脂族或芳族烃基,并且其中An-是带有n个负电荷的表面活性剂的阴离子头部基团,其中n=1-3,更优选1-2,甚至更优选1,其中cat.m+是带有m个正电荷的阳离子反离子,其中m=1-10,优选1-5,更优选1-2,甚至更优选1。
R1基团在此可通过多种连接基序(linkage motifs)连接至阴离子头部基团,经由例如但不限于酯、酰胺、醚、碳酸酯或硅酮键。此外,R1基团可以经由聚氧化烯桥,优选经由聚氧化乙烯和聚氧化丙烯桥连接到阴离子头部基团上。在这方面特别优选聚氧化烯,优选聚氧化乙烯和聚氧化丙烯桥,具有不超过10个、优选不超过7个、更优选不超过5个、甚至更优选不超过3个烷氧基单元。在这种情况下,相应的聚氧化烯,优选聚氧化乙烯和聚氧化丙烯桥应该被认为是阴离子头部基团的一部分。在本发明的上下文中,所提及的连接和桥连基序的组合同样是优选的。
在本发明的上下文中,优选地,阴离子头部基团An-具有有机羧酸盐或阴离子硫或磷化合物的结构特征。更优选地,此处的阴离子头部基团具有选自羧酸根、磷酸根、膦酸根、次膦酸根、硫酸根和磺酸根的结构单元。
优选的R1基团衍生自具有至少12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子的长链醇、羧酸或烷基胺,以及这些物质的混合物。
如果R1基团衍生自长链醇,则这些优选是月桂醇(1-十二烷醇)、肉豆蔻醇(1-十四烷醇)、鲸蜡醇(1-十六烷醇)、珠光酯基醇(margaryl alcohol)(1-十七烷醇)、硬脂醇(1-十八烷醇)、花生醇(1-二十烷醇)、山萮醇(1-二十二烷醇)、木蜡醇(1-二十四烷醇)、蜡醇(1-二十六烷醇)、蒙旦醇(montanyl alcohol)(1-二十八烷醇)、蜂花醇(1-三十烷醇)、棕榈油醇(顺-9-十六碳烯-1-醇)、油醇(顺-9-十八碳烯-1-醇)和/或反油醇(反-9-十八碳烯-1-醇),以及这些物质的混合物,特别优选棕榈油醇和硬脂醇以及这两种物质的混合物。根据本发明,这里优选纯醇及其具有链长分布或含有不同链长的脂肪酸的混合物的工业品级。
如果R1基团衍生自长链羧酸,则这些优选选自月桂酸(十二烷酸)、肉豆蔻酸(十四烷酸)、棕榈酸(十六烷酸)、硬脂酸(十八烷酸)、花生酸(二十烷酸)、山萮酸(二十二烷酸)、木蜡酸(二十四烷酸)、棕榈油酸((Z)-9-十六碳烯酸)、油酸((Z)-9-十六碳烯酸)、反油酸((E)-9-十八碳烯酸)、顺式异油酸((Z)-11-十八碳烯酸)、亚油酸((9Z,12Z)-9,12-十八碳二烯酸)、α-亚麻酸((9Z,12Z,15Z)-9,12,15-十八碳三烯酸)、γ-亚麻酸((6Z,9Z,12Z)-6,9,12-十八碳三烯酸)、二高-γ-亚麻酸((8Z,11Z,14Z)-8,11,14-二十碳三烯酸)、花生四烯酸((5Z,8Z,11Z,14Z)-5,8,11,14-二十碳四烯酸)、芥酸((Z)-13-二十二碳烯酸)、神经酸((Z)-15-二十四碳烯酸)、蓖麻油酸、羟基硬脂酸和/或十一碳烯酸,以及它们的混合物,例如菜籽油酸、大豆脂肪酸、向日葵脂肪酸、花生脂肪酸和妥尔油脂肪酸。非常特别优选棕榈酸和硬脂酸,尤其是这些物质的混合物。根据本发明,这里优选纯羧酸及其具有链长分布或含有不同链长脂肪酸混合物的工业品级。
如果R1基团衍生自长链胺,这些尤其是月桂胺(1-十二烷基胺)、肉豆蔻胺(1-十四烷基胺)、鲸蜡胺(1-十六烷基胺)、珠光酯基胺(1-十七烷基胺)、硬脂基胺(1-十八烷基胺)、花生胺(1-二十烷胺)、山萮胺(1-二十二烷胺)、木蜡胺(1-二十四烷胺)、蜡胺(1-二十六烷胺)、蒙旦胺(1-二十八烷基胺)、蜂蜡胺(1-三十烷基胺)、棕榈油胺(顺-9-十六碳烯胺)、油胺(顺-9-十八碳烯胺)和/或反油胺(反-9-十八碳烯胺)和混合物,特别优选棕榈油胺和硬脂基胺以及这两种物质的混合物。根据本发明,这里优选纯胺及其具有链长分布或含有不同链长脂肪酸混合物的工业品级。
上述长链醇、胺和羧酸的来源可以是植物或动物脂肪、油或蜡。例如,可以使用:猪油、牛脂、鹅油、鸭油、鸡油、马油、鲸油、鱼油、棕榈油、橄榄油、鳄梨油、籽仁油、椰子油、棕榈仁油、可可脂、棉籽油、南瓜籽油、玉米仁油、向日葵油、小麦胚芽油、葡萄籽油、芝麻油、亚麻籽油、大豆油、花生油、羽扇豆油、菜籽油、芥末油、蓖麻油、麻疯果油、核桃油、荷荷巴油、卵磷脂(例如基于大豆、菜籽或向日葵)、骨油、牛脚油、琉璃苣油、羊毛脂、鸸鹋油、鹿脂、土拨鼠油、貂油、红花油、大麻油、南瓜油、月见草油、妥尔油,以及巴西棕榈蜡、蜂蜡、小烛树蜡、小冠椰子蜡、甘蔗蜡、藤蔓(retamo)蜡、棕榈蜡、酒椰蜡、西班牙草蜡(esparto wax)、苜蓿蜡、竹蜡、大麻蜡、花旗松蜡、软木蜡、剑麻蜡、亚麻蜡、棉蜡、达玛蜡、茶蜡、咖啡蜡、米蜡、夹竹桃蜡和/或羊毛蜡。
在本发明的上下文中,进一步优选符合通式(II)的那些双尾长链阴离子表面活性剂
R2-An-n/m cat.m+ 式(II)
其中R2是支链烃基,其进而由两个相同或不同的一价脂族或芳族、饱和或不饱和的烃基组成,每个烃基具有12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子,且其中An-和cat.m+以及R2基团与亲水性头部基团的连接如上所述。
在本发明的上下文中,R2基团优选衍生自支化伯醇和/或仲醇。此处特别优选格尔伯特醇,即通过格尔伯特缩合形成的支链醇,以及通过Bashkirov法由石蜡氧化形成的支化仲醇。在这方面还优选上述醇的烷氧基化物,优选乙氧基化物和丙氧基化物,优选具有不超过10个、优选不超过7个、更优选不超过5个、甚至更优选不超过3个烷氧基单元。
在这方面,当双尾长链阴离子表面活性剂符合通式(III)或(IV)时是特别优选的:
其中R3基团独立地是具有12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子的相同或不同的一价脂族或芳族、饱和或不饱和的烃基,并且An-和cat.m+如上所述。
在本发明的上下文中,特别优选选自二烷基磺基琥珀酸酯(dialkylsulfosuccinates)、二烷基磷酸酯(dialkyl phosphates)、二烷基磺基琥珀酰胺酸酯(dialkyl sulfosuccinamates)和三官能或更高官能度的羧酸的二烷基酯的那些双尾长链阴离子表面活性剂。在这方面特别优选二棕榈磺基琥珀酸酯二硬脂基磺基琥珀酸酯硬脂基棕榈磺基琥珀酸酯二棕榈磷酸酯、二硬脂基磷酸酯、硬脂基棕榈磷酸酯、二棕榈磺基琥珀酰胺酸酯、二硬脂基磺基琥珀酰胺酸酯、硬脂基棕榈磺基琥珀酰胺酸酯、三官能或更高官能度的羧酸的二棕榈酯、三官能或更高官能度的羧酸的二硬脂基酯、三官能或更高官能度的羧酸的硬脂基棕榈酯,以及这些物质的混合物。在本发明的上下文中,进一步优选选自磺基琥珀酸的单烷基酯、磷酸、硫酸和二元或更高级多元羧酸与长链支链醇的单酯的那些双尾长链阴离子表面活性剂,如上所述。
基于支链长链醇并且在本发明上下文中优选的长链二烷基磺基琥珀酸酯或单烷基磺基琥珀酸酯可合成获得,例如通过使马来酸酐与相应的醇反应,如上所述,然后用亚硫酸氢钠磺化。
在本发明的上下文中优选的二烷基磺基琥珀酰胺酸酯可合成获得,例如通过使马来酸酐与长链胺反应,如上所述,然后用亚硫酸氢钠磺化。
在本发明的上下文中优选的长链二烷基磷酸酯和支链长链醇的单磷酸盐可例如通过使磷酸酐(P4O10)与如上所述相应的醇反应,然后中和形成的偏磷酸酯获得。
在本发明的上下文中优选的三官能或更高官能度的羧酸的二烷基酯和双官能或更高官能度的羧酸与支链长链醇的单酯可合成获得,例如通过使相应的羧酸酸与如上所述相应的醇缩合,然后中和形成的偏酯。
在本发明的上下文中优选的支链长链醇的单硫酸酯可例如通过使三氧化硫与如上所述相应的醇反应,然后中和形成的偏硫酸酯而获得。
本发明整个范围内的术语“中和”也包括部分中和。对于中和,包括部分中和,可以使用常规碱。这些包括水溶性金属氢氧化物,例如氢氧化钡、氢氧化锶、氢氧化钙,优选在水溶液中解离成游离金属和氢氧根离子的碱金属氢氧化物,尤其是NaOH和KOH。这些还包括与水反应形成氢氧根离子的脱水碱,例如氧化钡、氧化锶、氧化钙、氧化锂、氧化银和氨。除了上述这些碱之外,可用作碱的固体物质还有那些同样在溶解于水中时产生碱性反应而没有HO-(在固体化合物中)的物质;这些的实例包括胺,例如单-、二-和三烷基胺,其也可以是官能化的烷基,例如在酰胺胺、单-、二-和三烷醇胺或单-、二-和三氨基烷基胺的情况下,例如,弱酸的盐,如碳酸钾、碳酸钠、磷酸三钠等。此外,也可以使用更高官能度的胺如乙二胺、二亚乙基三胺或三亚乙基四胺用于中和。
在本发明的上下文中,进一步优选地,在式(I)-(IV)中,阳离子cat.m+是金属阳离子,更优选锂、钠、钾、钙、锶、钡或银阳离子,非常特别优选钠或钾阳离子。更优选地,当阳离子是质子化的胺化合物的铵阳离子时,特别优选基于氨的铵离子,胺例如单-、二-和三烷基胺,其中烷基也可以被官能化为例如酰胺胺、单-、二-和三烷醇胺或单-、二-和三氨基烷基胺,以及更高官能度的胺,例如乙二胺、二亚乙基三胺或三亚乙基四胺。
如上所述,可以通过中和高级多元酸的偏酯,例如长链偏磷酸酯,获得本发明上下文中的双尾长链阴离子表面活性剂。由于在本发明的上下文中,术语“中和”也涵盖部分中和,因此在这种情况下阳离子K也可以是与头部基团键合的氢原子或解离的水合氢离子。
如已经描述的,本发明设想了使用如上所述的长链双尾阴离子表面活性剂作为水性聚合物分散体、优选水性聚氨酯分散体中的添加剂的用途。这里的聚合物分散体优选地选自水性聚苯乙烯分散体、聚丁二烯分散体、聚(甲基)丙烯酸酯分散体、聚乙烯酯分散体和/或聚氨酯分散体。这些分散体的固含量优选在20-70重量%的范围内,更优选在25-65重量%的范围内。根据本发明,特别优选在水性聚氨酯分散体中使用长链双尾阴离子表面活性剂作为添加剂。这里特别优选的是基于聚酯多元醇、聚酯酰胺多元醇、聚碳酸酯多元醇、聚缩醛多元醇和/或聚醚多元醇的聚氨酯分散体。
在本发明的上下文中,优选的是,基于水性聚合物分散体的总重量,所述双尾长链阴离子表面活性剂的浓度在0.1-20重量%、更优选在0.2-15重量%范围内,特别优选在0.5-10重量%范围内。
优选在水性聚合物分散体中使用双尾长链阴离子表面活性剂作为发泡助剂或泡沫稳定剂用于使分散体发泡,例如作为发泡添加剂。此外,它们还可用作干燥助剂、流平添加剂、润湿剂和流变添加剂,这同样对应于本发明的优选实施方案。
除了本发明的双尾长链阴离子表面活性剂外,所述水性聚合物分散体还可包含其他添加剂/配制物组分,例如有色颜料、填料、消光剂、稳定剂诸如水解或UV稳定剂、抗氧化剂、吸收剂、交联剂、流平添加剂、增稠剂和其他助表面活性剂。
所述双尾长链阴离子表面活性剂可以以纯的形式或在合适溶剂中的共混形式加入到水分散体中。在这一点上,优选的溶剂选自水、丙二醇、二丙二醇、聚丙二醇、丁基二甘醇、丁基三甘醇、乙二醇、二甘醇、聚乙二醇、基于EO、PO、BO和/或SO的聚亚烷基二醇、基于EO、PO、BO和/或SO的醇烷氧基化物,以及这些物质的混合物,非常特别优选水性稀释液或共混物。所述双尾长链阴离子表面活性剂的共混物或稀释物包括至少5重量%,更优选至少10重量%,甚至更优选至少15重量%的双尾长链阴离子表面活性剂。
在根据本发明的双尾长链阴离子表面活性剂的水稀释物或共混物的情况下,向共混物中加入助水溶化合物以改善配制物特性(粘度、均质性等)可能是有利的。这里的助水溶化合物是由亲水部分和疏水部分组成的水溶性有机化合物,但分子量太低而不能具有表面活性剂特性。它们导致水性配制物中有机物质,尤其是疏水性有机物质的溶解度或溶解度特性的改进。术语“助水溶化合物”是本领域技术人员已知的。本发明上下文中优选的“助水溶化合物”是甲苯磺酸碱金属盐和铵盐、二甲苯磺酸碱金属盐和铵盐、萘磺酸碱金属盐和铵盐、异丙基苯磺酸碱金属盐和铵盐,以及苯酚烷氧基化物,尤其是苯酚乙氧基化物,它们具有至多6个烷氧基化物单元。
所述双尾长链阴离子表面活性剂不以纯形式使用,而是与其他助表面活性剂组合用作水性聚合物分散体、优选水性聚氨酯分散体中的添加剂也可能是有利的。例如,这些可用于改善体系相容性,或者在预先配制的表面活性剂混合物的情况下,用于改善配制特性。在这方面,根据本发明优选的助表面活性剂是例如游离脂肪醇、脂肪酸酰胺、环氧乙烷-环氧丙烷嵌段共聚物、甜菜碱,例如酰胺丙基甜菜碱、氧化胺、季铵表面活性剂、两性乙酸盐、脂肪酸的铵盐和/或碱金属盐、烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基苯磺酸盐、烷基磷酸盐、烷基磺基琥珀酸酯、烷基磺基琥珀酰胺酸酯、烷基肌氨酸盐,以及这些物质的混合物,非常特别优选游离脂肪醇,优选具有12至40个、更优选具有14-30个、甚至更优选具有16-24个碳原子,以及具有12-40个、更优选具有14-30个、甚至更优选具有16-24个碳原子的烷基硫酸盐,以及这些的混合物物质。此外,助表面活性剂可以包含基于有机硅的表面活性剂,例如三硅氧烷表面活性剂或聚醚硅氧烷。在脂肪酸的铵盐和/或碱金属盐的情况下,优选地它们含有低于25重量%的硬脂酸盐,特别是不含硬脂酸盐。
在根据本发明的双尾长链阴离子表面活性剂与如上所述的其他助表面活性剂的组合的情况下,特别优选地,基于根据本发明的双尾长链阴离子表面活性剂和助表面活性剂的组合,这些组合包括在1重量%至60重量%之间,优选在2重量%至50重量%之间,更优选在3重量%至40重量%之间,甚至更优选在5重量%至30重量%之间的助表面活性剂。
因为,如上所述,本发明使用双尾长链阴离子表面活性剂导致由水性聚合物分散体制备的多孔聚合物涂层的明显改进,所以本发明同样提供包含至少一种根据本发明的双尾长链阴离子表面活性剂的水性聚合物分散体,如上面详细描述。
本发明还进一步提供了由水性聚合物分散体制备的多孔聚合物层,该多孔聚合物层通过如上文详细描述的双尾长链阴离子表面活性剂的本发明的用途而获得。
优选地,根据本发明的多孔聚合物涂层可以通过包括以下步骤的方法制备:
a)提供一种混合物,该混合物包含至少一种水性聚合物分散体、至少一种根据本发明的双尾长链阴离子表面活性剂和任选存在的其他添加剂,
b)使所述混合物发泡,以得到泡沫,
c)任选地添加至少一种增稠剂以调节湿泡沫的粘度,
d)将发泡的聚合物分散体的涂层施加到合适的载体,
e)干燥/固化涂层。
所述多孔聚合物涂层具有优选地在微米范围内的孔,更优选平均孔尺寸小于350μm,进一步优选小于200μm,特别优选小于150μm,最优选小于100μm。平均孔尺寸可以优选地通过显微镜,优选地通过电子显微镜来测定。为此,通过具有足够放大倍数的显微镜观察多孔聚合物涂层的横截面并确定至少25个孔的尺寸。然后以所观察的孔或孔尺寸的算术平均值得出平均孔尺寸。
考虑到优选的配置,特别是考虑到优选可用于该方法的双尾长链阴离子表面活性剂和聚合物分散体,参考前述描述以及前述优选实施方案,尤其是如权利要求中详述的。
清楚的是,根据本发明的上述方法的方法步骤在时间上不受任何固定顺序的限制。例如,方法步骤c)可以在早期阶段与方法步骤a)同时执行。
本发明的一个优选实施方案是,在方法步骤b)中,水性聚合物分散体通过施加高剪切力而发泡。发泡可以在本领域技术人员熟悉的剪切单元的辅助下进行,例如Dispermat、溶解器、Hansa混合器或Oakes混合器。
此外,优选的是,在方法步骤c)结束时产生的湿泡沫具有至少5Pa·s、优选至少10Pa·s、更优选至少15Pa·s并且甚至更优选至少20Pa·s,但不超过500Pa·s、优选不超过300Pa·s、更优选不超过200Pa·s,甚至更优选不超过100Pa·s的粘度。泡沫的粘度可以在这里优选地借助于配备有LV-4转子的Brookfield粘度计(LVTD型)来测定。用于测定湿泡沫粘度的相应测试方法是本领域技术人员已知的。
在本发明的优选实施方案中,在方法步骤b)中,泡沫具有最高水平的均质性和孔细度。如果需要,本领域技术人员能够使用他们的经验,以惯用方式通过肉眼的简单直接目视检查或利用视觉辅助设备例如放大镜、显微镜来验证这一点。“孔细度”是指孔尺寸。平均孔尺寸越小,泡沫孔越细。如果需要,可以使用例如光学显微镜或扫描电子显微镜来测定孔细度(cell fineness)。“均质”是指孔尺寸分布。均质泡沫具有非常窄的孔尺寸分布,使得所有孔的尺寸大致相同。这也可以用光学显微镜或扫描电子显微镜来量化。
如上所述,可以向体系中添加额外的增稠剂以调节湿泡沫粘度。
优选地,可有利地用于本发明上下文中的增稠剂在此选自缔结型增稠剂类别。这里的缔结型增稠剂是通过在聚合物分散体中存在的颗粒表面处的缔结而产生增稠效果的物质。该术语是本领域技术人员已知的。优选的缔结型增稠剂在此选自聚氨酯增稠剂、疏水改性的聚丙烯酸酯增稠剂、疏水改性的聚醚增稠剂和疏水改性的纤维素醚。非常特别优选聚氨酯增稠剂。此外,在本发明的上下文中优选的是,基于分散体的总组成,增稠剂的浓度在0.01-10重量%的范围内,更优选在0.05-5重量%的范围内,最优选在0.1-3重量%的范围内。
在本发明的上下文中,另外优选的是,在方法步骤d)中,产生层厚度为10-10 000μm、优选50-5000μm、更优选75-3000μm、甚至更优选100-2500μm的发泡的聚合物分散体的涂层。发泡的聚合物分散体的涂层可以通过本领域技术人员熟悉的方法制备,例如刮涂。此处可以使用直接或间接涂覆方法(称为转移涂覆)。
在本发明的上下文中,还优选地,在方法步骤e)中,在升高的温度下进行发泡的和涂覆的聚合物分散体的干燥。根据本发明,此处优选干燥温度为至少50℃,优选60℃,更优选至少70℃。此外,可以在不同温度下分多个阶段干燥发泡的和涂覆的聚合物分散体,以避免干燥缺陷的发生。相应干燥技术在工业中广泛使用并且为本领域技术人员已知。
如已经描述的,方法步骤c)-e)可以在本领域技术人员已知的广泛实践的方法的帮助下进行。例如,在“Coated and laminated Textiles”(Walter Fung,CR-Press,2002)中给出了这些概述。
在本发明的上下文中,特别优选包含所述双尾长链阴离子表面活性剂并且具有小于350μm、优选小于200μm、特别优选小于150μm、最优选小于100μm的平均孔尺寸的那些多孔聚合物涂层。平均孔尺寸可以优选地通过显微镜检查,优选地通过电子显微镜检查来测定。为此,通过具有足够放大倍数的显微镜观察多孔聚合物涂层的横截面并确定至少25个孔的尺寸。为了获得该评估方法的足够统计数据,所选显微镜的放大倍数应优选为使得在观察场中存在至少10×10个孔。然后以所观察的孔或孔尺寸的算术平均值的形式计算出平均孔尺寸。这种借助显微镜检查测定孔尺寸是本领域技术人员熟悉的。
根据本发明的包含至少一种根据本发明的双尾长链阴离子表面活性剂和任选存在的其他添加剂的多孔聚合物层(或聚合物涂层)可以用于例如纺织工业(例如用于人造革材料),用于建筑行业、电子行业、体育行业或汽车行业。例如,基于根据本发明的多孔聚合物涂层,可以生产日常用品,例如鞋、鞋垫、包、手提箱、小箱子、衣服、汽车部件,优选座套,门部件、仪表板部件、方向盘和/或把手的覆盖物,以及换挡杆罩(gearshift gaiters),室内布置物品(fitout articles)诸如桌垫、靠垫或座具,电子装置中的间隙填充物、医疗应用中的缓冲和阻尼材料,或粘合胶带。
实施例
物质:
十二烷基苯磺酸钠(LAS;CAS:25155-30-0)来自Sigma Aldrich。这是用于生产水性聚氨酯分散体的标准助表面活性剂。
ECO颜料黑:来自Cromogenia的水性颜料分散体(黑色)。
粘度测量:
所有粘度测量均使用配备有LV-4转子的Brookfield粘度LVTD在12rpm的恒定转速下进行。对于粘度测量,将样品转移到100ml广口瓶中,将测量转子浸入其中。一直等待显示恒定粘度计测量值。
测定酸值的方法:
测定酸值的合适方法特别是根据DGF C-V 2、DIN EN ISO 2114、Ph.Eur 2.5.1、ISO 3682和ASTM D 974的那些方法。
实施例1:硬脂基磷酸酯的合成:
在搅拌和引入N2的同时将硬脂醇(≥95%,178.7g,0.661mol)加热至70℃,然后分小份加入P4O10(21.31g,0.0751mol),使反应混合物的温度不会升至80℃以上。在P4O10添加结束后,将反应混合物在80℃下搅拌3小时,同时引入N2,直到酸值恒定。倒出并冷却后,得到酸值为127mg KOH/g的无色固体。
实施例2:硬脂基柠檬酸酯的合成:
在搅拌和引入N2的同时将硬脂醇(≥95%,275.2g,1.02mol,2.1当量)加热至70℃,然后加入柠檬酸(无水,93.10g,0.485mol,1.0当量)。将反应混合物加热至140℃并在150毫巴的压力下引入N2搅拌3小时,直至达到62mg KOH/g的酸值。在120℃的温度下通过压滤机(1μm)在2巴下过滤混合物。冷却后,得到酸值为57mg KOH/g的无色固体。
实施例3:对比例:
除了根据本发明的表面活性剂,还使用了基于聚甘油-3硬脂酸酯的对比表面活性剂,其通过使103.3g聚甘油-OHN=1124mg KOH/g,Mw=240g/mol与155.0工业级硬脂酸反应制备。
实施例4:表面活性剂的共混:
根据表1中详述的组成,将来自实施例1和2的本发明的表面活性剂和来自实施例3的基于聚甘油的对比表面活性剂共混,然后在80℃下均质化。共混后用KOH将本发明的表面活性剂配制物1和2中和至pH=7。对比表面活性剂3在共混后已经具有7的pH值,没有被中和。
表1:下文使用的表面活性剂共混物的组成:
实施例5:发泡测试:
为了测试根据本发明的添加剂组合的功效,进行了一系列发泡实验。为此,在第一步中,使用了来自Covestro的DLU聚氨酯分散体。所用的泡沫稳定剂是本发明的表面活性剂配制物1和2(见表1)以及作为对比的两种表面活性剂Stokal STA(硬脂酸铵)和Stokal SR(磺基琥珀酰胺酸钠)的组合。表2给出了各个实验的组成的概述。
所有发泡实验均手动进行。为此,首先将聚氨酯分散体和表面活性剂置于500ml塑料杯中,并用配备有分散盘(直径=6cm)的溶解器以1000rpm均质化3分钟。为了使混合物发泡,然后将剪切速率增加到2000rpm,确保分散盘始终浸入分散体中至足以形成适当的涡流的程度。在此速度下,混合物发泡至约425ml的体积。然后将混合物在1000rpm下再剪切15分钟。在该步骤中,分散盘充分浸入混合物中,以至于不再有空气进入体系,但整个体积仍在运动。
表2:泡沫配制物的概述:
在所有情况下,在该发泡操作结束时获得精细均质的泡沫。值得注意的是,用本发明的表面活性剂1和2制备的泡沫#1和#2具有更高的粘度(见表2)。借助于配备有施用器框架的涂膜器(来自TQC的AB3220)将泡沫涂覆到硅化聚酯膜上(膜厚度=800μm),然后在60℃下干燥5分钟,并在120℃下再干燥5分钟。
与这样获得的样品#3相比,干燥的本发明样品#1和#2具有更均质的宏观外观和更柔软的感觉。此外,在电子显微镜检查研究中,可以确定更细的孔结构。
实施例6:迁移测试:
为了评估根据本发明的表面活性剂的表面迁移,通过以下方法制备人造革材料。首先,将面漆施加到硅化的聚酯膜(层厚100μm)。然后将其在100℃下干燥3分钟。随后,将泡沫层涂覆到干燥的面漆层(层厚800μm)上并在60℃下干燥5分钟和在120℃下干燥5分钟。在最后一步中,将水性粘合剂层(层厚100μm)涂覆到干燥的泡沫层上,然后将织物载体层压到仍然湿润的粘合剂层上。完成的层压材料再次在120℃下干燥5分钟,然后与聚酯膜分离。
用来自Mathis AG的Labcoater LTE-S执行所有涂覆和干燥操作。面漆和粘合剂层在此根据表3中所列的组成来配制;所使用的泡沫层是表2中所列的泡沫配制物,其通过实施例5中所述的方法发泡。
为了评估表面活性剂的迁移,将制备后的人造革样品放入100℃的水中30分钟,然后在室温下干燥过夜。在这种处理之后,由Stokal STA/SR表面活性剂制备的对比样品(泡沫配制物#3,表2)在人造革表面上具有明显可见的白点,而在用根据本发明的表面活性剂制备的样品(泡沫配制物#1和#2,表2)的情况下没有观察到这种表面变色。
表3:用于制备人造革材料的面漆和粘合剂配制物:
实施例7:助表面活性剂相容性:
为了评估助表面活性剂的相容性,使用YS:3000PUD体系进行了进一步的发泡测试。其含有1-3重量%的阴离子助表面活性剂十二烷基苯磺酸钠(CAS:25155-30-0)。这些实验中使用的表面活性剂是表1中列出的表面活性剂配制物1-3。表4给出了泡沫配制物组成的概述。
表4:泡沫配制物概述:
在这些配制物的基础上,通过实施例5中描述的方法制备泡沫涂料。这里值得注意的是,用非本发明的表面活性剂3制备的样品#6具有更粗糙和更不均质的泡沫结构。泡沫涂层干燥后,还可以观察到泡沫结构中的明显裂缝,这表明泡沫稳定性不足。相比之下,用本发明的表面活性剂制备的样品#4和#5再次显示出极细孔和均质的泡沫结构。它们也没有干燥裂缝。
此外,还进行了一系列发泡实验,其中实际上不含助表面活性剂的DLU体系有意添加了十二烷基苯磺酸钠,这是一种常见的用于稳定PUD的助表面活性剂,如上所述。在这些实验中,使用了表1中列出的表面活性剂配制物1-3。表5概述了泡沫配制物的组成。
表5:泡沫配制物概述:
在这里,泡沫涂料也是通过实施例5中描述的方法制备的。这里再次值得注意的是,用非本发明的表面活性剂3制备的样品#9具有干燥裂纹和更粗糙的孔结构,而两个本发明的样品#7和#8再次显示出精细且均质的孔结构并且没有缺陷。此处几乎没有观察到与类似的无助表面活性剂的样品#1和#2(见实施例5)的区别。因此,这些实验证明了根据本发明的表面活性剂在助表面活性剂相容性方面的明显改进。
Claims (17)
1.双尾长链阴离子表面活性剂在水性聚合物分散体、优选水性聚氨酯分散体中作为添加剂、优选作为泡沫添加剂的用途。
2.根据权利要求1所述的用途,其特征在于,所述双尾长链阴离子表面活性剂具有阴离子亲水性头部基团和两个相同或不同的长链疏水烃基。
4.根据权利要求1至3中至少一项所述的用途,其特征在于,R1基团衍生自具有至少12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子的长链醇、羧酸或烷基胺。
5.根据权利要求1至4中至少一项所述的用途,其特征在于,R1基团衍生自月桂醇(1-十二烷醇)、肉豆蔻醇(1-十四烷醇)、鲸蜡醇(1-十六烷醇)、珠光酯基醇(1-十七烷醇)、硬脂醇(1-十八烷醇)、花生醇(1-二十烷醇)、山萮醇(1-二十二烷醇)、木蜡醇(1-二十四烷醇)、蜡醇(1-二十六烷醇)、蒙旦醇(1-二十八烷醇)、蜂花醇(1-三十烷醇)、棕榈油醇(顺-9-十六碳烯-1-醇)、油醇(顺-9-十八碳烯-1-醇)和/或反油醇(反-9-十八碳烯-1-醇),以及这些物质的混合物,特别优选鲸蜡醇和/或硬脂醇以及这两种物质的混合物,和/或衍生自月桂酸(十二烷酸)、肉豆蔻酸(十四烷酸)、棕榈酸(十六烷酸)、硬脂酸(十八烷酸)、花生酸(二十烷酸)、山萮酸(二十二烷酸)、木蜡酸(二十四烷酸)、棕榈油酸((Z)-9-十六碳烯酸)、油酸((Z)-9-十六碳烯酸)、反油酸((E)-9-十八碳烯酸)、顺式异油酸((Z)-11-十八碳烯酸)、亚油酸((9Z,12Z)-9,12-十八碳二烯酸)、α-亚麻酸((9Z,12Z,15Z)-9,12,15-十八碳三烯酸)、γ-亚麻酸((6Z,9Z,12Z)-6,9,12-十八碳三烯酸)、二高-γ-亚麻酸((8Z,11Z,14Z)-8,11,14-二十碳三烯酸)、花生四烯酸((5Z,8Z,11Z,14Z)-5,8,11,14-二十碳四烯酸)、芥酸((Z)-13-二十二碳烯酸)、神经酸((Z)-15-二十四碳烯酸)、蓖麻油酸、羟基硬脂酸和/或十一碳烯酸,以及它们的混合物,例如菜籽油酸、大豆脂肪酸、向日葵脂肪酸、花生脂肪酸和/或妥尔油脂肪酸,特别优选棕榈酸和/或硬脂酸,以及这些物质的混合物,和/或衍生自月桂胺(1-十二烷基胺)、肉豆蔻胺(1-十四烷基胺)、鲸蜡胺(1-十六烷基胺)、珠光酯基胺(1-十七烷基胺)、硬脂基胺(1-十八烷基胺)、花生胺(1-二十烷胺)、山萮胺(1-二十二烷胺)、木蜡胺(1-二十四烷胺)、蜡胺(1-二十六烷胺)、蒙旦胺(1-二十八烷基胺)、蜂蜡胺(1-三十烷基胺)、棕榈油胺(顺-9-十六碳烯胺)、油胺(顺-9-十八碳烯胺)和/或反油胺(反-9-十八碳烯胺),以及这些物质的混合物,特别优选鲸蜡胺和/或硬脂基胺以及这两种物质的混合物。
6.根据权利要求1或2所述的用途,其特征在于,所述双尾长链阴离子表面活性剂符合通式(II):
R2-An-n/m cat.m+ 式(II)
其中R2是支链烃基,其进而由两个相同或不同的一价脂族或芳族、饱和或不饱和的烃基组成,每个烃基具有12至40个碳原子、优选14至30个碳原子、更优选具有16至24个碳原子,且其中An-是带有n个负电荷的表面活性剂的阴离子头部基团,其中n=1-3,更优选1-2,甚至更优选1,其中cat.m+是带有m个正电荷的阳离子反离子,其中m=1-10,优选1-5,更优选1-2,甚至更优选1。
8.根据权利要求1-7中至少一项所述的用途,其特征在于,所述阴离子头部基团An-基于有机羧酸盐或阴离子硫或磷化合物,其中在这方面的头部基团优选地具有选自羧酸根、磷酸根、膦酸根、次膦酸根、硫酸根和磺酸根的结构单元。
9.根据权利要求1-8中至少一项所述的用途,其特征在于,所述双尾长链阴离子表面活性剂选自二烷基磺基琥珀酸酯,特别优选二棕榈磺基琥珀酸酯、二硬脂基磺基琥珀酸酯和/或硬脂基棕榈磺基琥珀酸酯,选自二烷基磺基琥珀酰胺酸酯,特别优选二棕榈磺基琥珀酰胺酸酯、二硬脂基磺基琥珀酰胺酸酯和/或硬脂基棕榈磺基琥珀酰胺酸酯,选自二烷基磷酸酯,特别优选二棕榈磷酸酯、二硬脂基磷酸酯和/或硬脂基棕榈磷酸酯,选自三官能或更高官能度的羧酸的二烷基酯,特别优选三官能或更高官能度的羧酸的二硬脂基酯和三官能或更高官能度的羧酸的硬脂基棕榈酯,选自磷酸、硫酸和二元或更高级多元羧酸与长链支链醇的单酯,选自基于长链支链醇的单烷基磺基琥珀酸酯,以及这些物质的混合物。
10.根据权利要求1-9中至少一项所述的用途,其特征在于,所述阳离子cat.m+是金属阳离子,更优选锂、钠、钾、钙、锶、钡或银阳离子,非常特别优选钠或钾阳离子,和/或质子化的胺化合物的铵阳离子,优选基于氨的铵离子,胺例如单-、二-和三烷基胺,其中烷基也可以被官能化为例如酰胺胺、单-、二-和三烷醇胺或单-、二-和三氨基烷基胺,以及更高官能度的胺,例如乙二胺、二亚乙基三胺或三亚乙基四胺,和/或水合氢离子,或者在未解离的酸的情况下,是与头部基团键合的氢原子。
11.根据权利要求1-10中至少一项所述的用途,其特征在于,所述双尾长链阴离子表面活性剂与至少一种另外的助表面活性剂组合用作水性聚合物分散体、优选水性聚氨酯分散体中的添加剂,其中所述助表面活性剂优选地包含脂肪醇、脂肪酸酰胺、环氧乙烷-环氧丙烷嵌段共聚物、甜菜碱,例如酰胺丙基甜菜碱、氧化胺、季铵表面活性剂、两性乙酸盐、脂肪酸的铵盐和/或碱金属盐、烷基硫酸盐、烷基醚硫酸盐、烷基磺酸盐、烷基苯磺酸盐、烷基磷酸盐、烷基磺基琥珀酸酯、烷基磺基琥珀酰胺酸酯、烷基肌氨酸盐或基于有机硅的助表面活性剂,以及这些物质的混合物,非常特别优选游离脂肪醇,优选具有12-40个碳原子、更优选具有14-30个碳原子、甚至更优选具有16-24个碳原子,以及具有12-40个碳原子、更优选具有14-30个碳原子、甚至更优选具有16-24个碳原子的烷基硫酸盐,以及这些物质的混合物。
12.根据权利要求1至11中任一项所述的用途,其特征在于,所述水性聚合物分散体选自水性聚苯乙烯分散体、聚丁二烯分散体、聚(甲基)丙烯酸酯分散体、聚乙烯酯分散体和聚氨酯分散体,尤其是聚氨酯分散体,其中基于总分散体,这些分散体的固含量优选在20-70重量%的范围内,更优选在25-65重量%的范围内。
13.根据权利要求1-12中至少一项所述的用途,其特征在于,基于所述水性聚合物分散体的总重量,所述双尾长链阴离子表面活性剂的浓度在0.1-20重量%的范围内,更优选在0.2-15重量%的范围内,特别优选在0.5-10重量%的范围内。
14.水性聚合物分散体、优选水性聚氨酯分散体,其含有双尾长链阴离子表面活性剂,优选如权利要求1至13中所述,其中基于总分散体,该分散体的固含量优选在20-70重量%的范围内,更优选地在25-65重量%的范围内,并且其中基于所述水性聚合物分散体的总重量,所述双尾长链阴离子表面活性剂的浓度在0.2-20重量%的范围内,更优选在0.4-15重量%的范围内,特别优选在0.5-10重量%的范围内。
15.使用双尾长链阴离子表面活性剂作为水性聚合物分散体、优选水性聚氨酯分散体中的添加剂,制备多孔聚合物涂层、优选多孔聚氨酯涂层的方法,优选如权利要求1至13中所述,该方法包括以下步骤:
a)提供一种混合物,该混合物包含至少一种水性聚合物分散体、至少一种根据本发明的双尾长链阴离子表面活性剂,以及任选存在的其他添加剂,
b)使所述混合物发泡,以得到泡沫,
c)任选地添加至少一种增稠剂以调节湿泡沫的粘度,
d)将发泡的聚合物分散体、优选聚氨酯分散体的涂层施加到合适的载体,
e)干燥所述涂层。
16.多孔聚合物涂层、优选多孔聚氨酯涂层,其可通过在这种聚合物涂层的制备中使用双尾长链阴离子表面活性剂作为水性聚合物分散体、优选水性聚氨酯分散体中的添加剂而获得,优选可通过根据权利要求15所述的方法而获得。
17.包含根据权利要求16所述的多孔聚合物涂层的日常用品,优选鞋、鞋垫、包、手提箱、小箱子、衣服、汽车部件,优选座套,门部件、仪表板部件、方向盘和/或把手的覆盖物,以及换挡杆罩,室内布置物品诸如桌垫、靠垫或座具,电子装置中的间隙填充物、医疗应用中的缓冲和阻尼材料,或粘合胶带。
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BR102021012200A2 (pt) | 2022-01-11 |
KR20210158804A (ko) | 2021-12-31 |
EP3929352A1 (de) | 2021-12-29 |
MX2021007304A (es) | 2022-08-02 |
JP2022008231A (ja) | 2022-01-13 |
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