CN111201091A - 用于在涂覆聚合物材料之前对其进行腐蚀的制剂 - Google Patents
用于在涂覆聚合物材料之前对其进行腐蚀的制剂 Download PDFInfo
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Abstract
本发明涉及使用现有技术中已知和所述的技术,基于阳离子Cr(III)的盐和/或络合物的使用,在聚合物的金属化或涂覆之前对聚合物进行蚀刻处理浴的新制剂。本发明的制剂涉及Cr(III)盐和/或络合物,其中Cr(III)配位于至少一个或若干个单、双、三、四、五、六齿或桥联配体,这些配体通过至配体的氧、硫或氮原子或这些原子中的若干原子配位于铬。一旦用上述蚀刻制剂对聚合物片进行蚀刻,在金属化的情况下通过化学和电镀浴或通过油漆或其他有机涂层来施加金属涂层。
Description
技术领域
本发明涉及使用现有技术中已知和所述的技术,基于阳离子Cr(III)的盐和/或络合物的使用,在聚合物的金属化或涂覆之前对聚合物进行蚀刻处理浴。
背景技术
目前,在聚合物团中添加或不添加无机负载和其他添加剂的情况下,预处理浴的技术发展和工业应用、聚合物(主要是ABS及其共混物,诸如ABS聚碳酸酯、聚酰胺、聚丙烯和热固性材料)的处理和蚀刻,基于使用含有氧化态六价铬盐的水浴。浴通常含有浓度为至多400gr/l的硫酸和铬(VI)化合物,主要为铬酸、三氧化铬或或重铬酸盐。
这种表面处理过程或蚀刻是初始关键处理,然后应用具有多个功能层的体系,包括活化、加速、化学镀镍沉积、铜、铜电沉积、镍甚至铬亮面,并进行相应的中间清洗,从而得到表面金属化的塑料。
对于有机涂层或涂漆涂层,在上述蚀刻表面处理的初始关键工艺之后,使用现有技术中当前可用的不同方法中的一种对塑料进行涂覆或涂漆。
只有适当的预处理或蚀刻与一些进一步的理想处理相结合,才能为所需的相应应用提供所有关键的必要要求,并且初始蚀刻处理是整个工艺的必要因素。
已证实,在蚀刻中使用的氧化态铬(VI)盐对人类有毒且具有致癌性,这导致人们关注于替代这些六价铬盐的任何用途,特别是它们在聚合物处理和蚀刻浴中的用途。
对于用其他化学氧化剂来替代含有六价铬盐的浴已经提出了不同的选择方案,主要是在酸性和碱性介质中的Mn(VII)、Mn(VI)盐以及甚至是Mn(III)盐,如专利US8603352B1和US20130186774中所示。
然而,这些基于锰盐的体系在金属化或随后涂覆聚合物片时不会产生相同的粘附结果,并且由于需要除去锰盐的还原产物而需要非常复杂的洗涤。浴随着时间的推移也是不稳定的,并且对于工业应用而言持续时间较短。
另选地,已如专利DE19740431 C1中那样提出了基于过氧化氢的体系,如US6559242 B1中的铁和/或铜的过氧化物和盐,具有过渡金属的氯化物配体的阴离子络合物(US4568571 A),过渡金属在有机溶剂中的有机金属化合物(EP0081129 A1),以及在弱酸性水性介质中不使用络合物情况下的过渡金属的氯化物盐或硝酸盐(US20070099425 A1)。
迄今为止,在任何情况下都没有获得适用于自动化部门所要求的最终粘附性要求的结果,这些结果可以通过基于六价铬盐的处理获得。最近发表了一篇关于这一主题的综述文章:Plating on acrylonitrile-butadiene-styrene(ABS)plastic:A review。《材料科学杂志》,2016,51,3657-3674。因此,现有技术需要一种蚀刻浴,该蚀刻浴在聚合物上的金属化和其他种类的涂覆的粘附效果,浴随时间推移和使用的稳定性,安全特性,对人和环境的无毒性,在这些处理浴环境适宜条件下易于回收、再循环或去除等方面有效,并且没有Cr(VI)。
发明目的
本发明的目的是通过使用在酸性介质中含有盐和/或铬(III)络合物的水溶液来预处理、处理和/或蚀刻聚合物。
本发明基于使用以盐形式加入的阳离子Cr(III),并且化学配位于至少一个或若干个单、双、三、四、五、六齿或桥联配体,这些配体通过氧、硫或氮原子配位于铬。
对有机聚合物进行处理,以便在物理和化学上对其表面进行改性,从而使得可以在聚合物的表面上形成可以通过现有技术中当前描述的技术粘附或可金属化的涂层。
具体实施方式
通过化学浴利用金属或利用有机涂层涂覆聚合物需要事先进行蚀刻处理,以使待涂覆的聚合物的表面具有足够的粘附力以满足最终产品的应用要求。
这种蚀刻处理工艺所使用的聚合物是热塑性塑料,如ABS,ABS与其他聚合物的共混物,诸如聚碳酸酯、聚酰胺、PVC、聚碳酸酯、聚酯、聚缩醛、聚烯烃,热固性材料,诸如环氧树脂、不饱和聚酯树脂、乙烯基酯环氧树脂或弹性体,诸如SBR和EPDM橡胶或市场上可买到的不同类型的热塑性弹性体。聚合物可以含有不同类型的无机负载,诸如石英、碳酸钙、硅灰石、硅酸盐、滑石,以及通过挤出、注塑、在热板上成型或用于制造物体、板或热固性材料或弹性体形式的不同技术对它们进行处理所必需的对应添加剂。
聚合物表面处理或蚀刻工艺是具有一些预先要求的方法,诸如处理或蚀刻浴的特定组成以及这些浴在受控温度和时间下的作用或处理。
蚀刻工艺的先决条件:
初始待处理的基底的表面应不含污染物、油脂、腐蚀性产品和其他材料。因此,在该过程之前,对基础基底进行适当的制备是值得推荐的要求,尽管并不是严格必要的。基底的预先制备在现有技术中是众所周知的。
蚀刻工艺中使用的浴的组成是水性浴:
浴是通过添加盐或铬(III)络合物来制备的,并且基于使用通过配体的氧、硫或氮原子与铬配位的至少一个或若干个单、双、三、四、五、六齿或桥联配体。
除了别的之外,可用于氧化态三价铬的配体是甲酸盐、乙酸盐、丙酸盐、丁酸盐、苯甲酸盐、苯乙酸盐、苯丙酸盐、氰酸盐、苯甲酸烷基盐、丙酮酸盐、乙酰丙酸盐、柠檬酸盐、异柠檬酸盐、乌头酸盐、偏苯三酸盐、甘氨酸盐、缬氨酸盐、亮氨酸盐、苏氨酸盐、赖氨酸盐、色氨酸盐、组氨酸盐、苯基丙氨酸盐、异亮氨酸盐、精氨酸盐、蛋氨酸盐、丙氨酸盐、脯氨酸盐、丝氨酸盐、半胱氨酸盐、天冬酰胺盐、谷氨酰氨酸盐、酪氨酸盐、天冬氨酸盐、聚天冬氨酸盐、谷氨酸盐、半胱氨酸盐、同型半胱氨酸盐、鸟氨酸盐、烟酸盐、草酸盐、丙二酸盐、丁二酸盐、戊二酸盐、己二酸盐、马来酸盐、富马酸盐、邻苯二甲酸盐、间苯二甲酸盐、对苯二甲酸盐、酒石酸盐、衣康酸盐、中康酸盐、柠康酸盐、乙醇酸盐、乳酸盐、扁桃酸盐、水杨酸盐、葡萄糖酸盐、乙二胺四乙酸盐、次氮基三乙酸盐、亚氨基二琥珀酸盐、乙二胺丁二酸氢盐、甲基甘氨酸二醋酸盐、N,N,谷氨酸二乙酸盐、亚环己基二次氮基四乙酸酯、二亚乙基三胺五乙酸盐、氨基乙基乙基乙二醇四乙酸盐、三乙基四氨基六乙酸盐、二氢甲基甘氨酸盐、亚氨基二乙酸盐、草氨酸盐、次氮基三丙酸盐、乙二胺二丙酸盐、硫代二丙酸盐、二硫代二丙酸盐、氨基丙酸盐、氨基戊酸盐、氨基己酸盐、2-氨基苯甲酸盐、3-氨基苯甲酸盐、4-氨基苯甲酸盐、3-环己胺-丙胺、乙二胺、1,3-丙二胺、二甲基氨基丙胺、二乙基氨基丙胺、双(3-氨基丙基)-甲胺、二乙烯三胺、二丙烯三亚胺、三乙烯四胺、四乙烯戊胺、多胺、3-(2-氨基乙基)氨基丙胺、N,N′-双(3-氨基丙基)乙二胺、新戊烷二胺、环己二胺、1,6-己二胺、咪唑、1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、N-(3-氨基丙基)-咪唑、吡唑、烟酰胺、联吡啶、菲咯啉或其共混物。
所使用的配体优选为甲酸盐、乙酸盐、丙酸盐、甘氨酸盐、精氨酸盐、天冬氨酸盐、聚天冬氨酸盐、谷氨酸盐、烟酸盐、草酸盐、丙二酸盐、丁二酸盐、戊二酸盐、己二酸盐、马来酸盐、富马酸盐、邻苯二甲酸盐、水杨酸盐、酒石酸盐、柠檬酸盐、乙醇酸盐、乳酸盐、葡萄糖酸盐、乙二胺四乙酸盐、次氮基三乙酸盐、2-氨基苯甲酸盐。最优选使用的配体为草酸盐、丙二酸盐、丁二酸盐、马来酸盐、富马酸盐、邻苯二甲酸盐、乙醇酸盐、乳酸盐、水杨酸盐、甘氨酸盐、谷氨酸盐或其共混物。
可以将浴中含有的铬(III)络合物以与以制备和分离的带有上述配体的铬(III)络合物的形式添加到浴中,如在科学文献中针对,例如,草酸盐型络合物所指出的:“Complex Ions of Chromium.III.Reactions between Hexaquochromium(III)andOxalate lons”,Randall E.Hamm,Robert E.Davis《美国化学会志》,1953,75,3085-3089页(1953)。
铬(III)络合物也可以通过单独添加铬(III)盐和构成所需络合物的配体而在浴中原位形成,例如在专利US3900689中针对富马酸盐型络合物所指出的。
在原位形成铬(III)络合物的情况下,这些络合物的起始盐可以是无机阴离子或有机阴离子盐,诸如氯化物、溴化物、高氯酸盐、氢氧化物、氧化物、硫酸盐、亚硫酸盐、硫化物、硝酸盐、亚硝酸盐、磷酸盐、二磷酸盐、偏磷酸盐、多磷酸盐、硼酸盐、硅酸盐、甲酸盐、乙酸盐、苯甲酸盐、乳酸盐、甲磺酸盐、乙磺酸盐、丙磺酸盐、丁磺酸盐、羧酸盐、烷基磷酸盐或其混合物。一旦将这些盐加入到水性浴中,就将相应的配体以它们的质子化形式或以碱金属或碱土金属盐的形式或游离形式加入到该浴中以形成络合物。这样,获得蚀刻浴中所需的铬(III)络合物。
最后,还可以通过待使用配体的化学反应或还原形式以及添加到Cr(VI)化合物的浴中来获得蚀刻浴中所需的Cr(III)络合物,Cr(VI)通过形成络合物的配体的直接作用(如果是还原剂)或通过向配体中添加其他还原剂(诸如抗坏血酸、抗坏血酸盐、硫代硫酸盐、亚硫酸盐、硫化物、亚硝酸盐、亚磷酸盐、次磷酸盐、甲醛磺酸盐、连二亚硫酸盐、草酸盐、碱金属或碱土金属的羧酸盐、肼及其衍生物、羟胺或现有技术中已知的任何其他还原剂)被还原成氧化态(III)的络合物。
存在于浴中的Cr(III)络合物的浓度可在2mM和2M之间,并且更优选地在5mM和1M之间,并且甚至更优选地在0.01M和0.4M之间。
所示的Cr(III)络合物用于酸性水性介质中,蚀刻浴中所含有的酸可以是硫酸、氨基硫酸(氨基磺酸)、磷酸、二磷酸、偏磷酸、多磷酸、甲磺酸、乙磺酸、丙磺酸、丁磺酸、链烷磺酸、苯磺酸、甲苯磺酸、异丙苯磺酸、烷基苯磺酸、单烷基磷酸、二烷基磷酸、羟乙磺酸、高氯酸、氯酸、硝酸、三氟甲基磺酸、三氟乙酸、四氟硼酸、六氟磷酸、六氟硅酸、氢氟酸、硼酸或其共混物。优选地,存在于蚀刻浴中的酸可以是硫酸、磷酸、二磷酸、偏磷酸、多磷酸、甲磺酸、乙磺酸、丙磺酸、苯磺酸、甲苯磺酸、异丙苯磺酸、烷基苯磺酸、单烷基磷酸、二烷基磷酸或其共混物,以及更优选存在于浴中的酸可以是硫酸、磷酸或其共混物。
考虑到所含酸的总质量/质量百分比,蚀刻浴中酸的浓度可在10%和98%之间,优选地在40%和95%之间,更优选地在55%和92%之间,其余为Cr(III)络合物和水。酸总量可由两种或更多种酸的混合物组成。
蚀刻浴使用的温度可以在10℃和95℃之间变化,更优选地在15℃和80℃之间,并且甚至更优选地在20℃和75℃之间。为了达到工作温度,处理槽被加热或冷却,直到通过为此目的应用任何适当的技术来保持理想的工作温度。
将要在蚀刻浴中处理的任何形状和大小的聚合物片浸没其中一段之间,该段时间在30秒和1小时之间,优选地在1分钟和45分钟之间,或更优选地在2分钟和30分钟之间。
在本发明所涉及的蚀刻工艺之后,用水、水溶液或具有当前现有技术已知特性的有机液体进行必要的洗涤步骤。
在洗涤之后,以湿法通过具有所需特性的化学浴进行必要的处理以获得金属涂层。
另选地,在洗涤之后,如果将诸如清漆或油漆的聚合物涂层放置在处理过的片上,则可对该片进行干燥或不进行干燥。
实施例
用于以下实施例中的基底为通过注射相应的热塑性聚合物获得的基底:ABS、ABS-聚碳酸酯、聚酰胺6、具有20%硅灰石无机负载的聚酰胺6、聚丙烯或具有20%滑石无机负载的聚丙烯。
通过现有技术已知的方法固化热固性基底;它们是具有40%的玻璃纤维的不饱和聚酯树脂和具有40%玻璃纤维的环氧树脂。
在每种情况下,在蚀刻之前洗涤基底。洗涤通过浸没于水浴、1%十二烷基硫酸钠水溶液的浴以及通过浸没于两个水浴中的两次后续冲洗来完成。这种洗涤的目的是从基底上移除污垢和油脂和/或制备用于蚀刻的表面。根据制备所述片的工艺,可避免这种洗涤。
蚀刻处理用下面示例中给出的相应的浴来进行。
在蚀刻工艺之后,通过浸入水浴中进行另外两次冲洗。
一旦聚合物被蚀刻,通过现有技术中已知的方法沉积了也被称为无电镍的自催化无电镍:
通过在25℃的活化剂浴中浸没2分钟来处理。在水浴中冲洗。在25℃的加速浴中处理2分钟。在水浴中冲洗。在29℃下浸浴8分钟以用于无电镍金属化。通过在水浴中浸没洗涤两次。
类似地,一旦进行蚀刻并且干燥了基底,就用有机碱或油漆的涂层覆盖聚合物。
实施例1:
作为在蚀刻工艺中获得的结果的参考,基于使用具有以下组成的Cr(VI)盐,在浴中进行蚀刻:
蚀刻浴含有380gr/L的铬酸和400gr/L的浓硫酸。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例2:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体为乙酸盐,并且其通过62%的H2O的溶液制备;4%的乙酸铬(III);34%的H2SO4。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例3:
基于Cr(III)盐的蚀刻浴,其中苯甲酸盐为与铬配位的配体,并且其通过40%的H2O的溶液制备;3%的苯甲酸铬(III);57%的甲磺酸。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例4:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体为甘氨酸盐,并且其通过21%的H2O的溶液制备;2.5%的甘氨酸铬(III);65.5%的H2SO4。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例5:
基于Cr(III)盐的蚀刻浴,其中氨基己酸盐为与铬配位的配体,并且其通过21%的H2O的溶液制备;2.2%的CrCl3·6H2O;1.3%的氨基己酸;36.5%的H3PO4(75%的水);39%的H2SO4。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例6:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体为柠檬酸盐,并且其通过17%的H2O的溶液制备;1.2%的Cr(NO3)3.9H2O;2.6%的柠檬酸;39.7%的H3PO4(75%的水);39.5%的H2SO4。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例7:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为三乙烯四胺,并且其通过19%的H2O的溶液制备;0.8%的Cr(NO3)3.9H2O;1.1%的三乙烯四胺;38.4%的H3PO4(75%的水);40.7%的H2SO4。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例8:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体为硫代二丙酸盐,并且其通过18.5%的H2O的溶液制备;0.7%的CrCl3·6H2O;0.9%的硫代二丙酸;38%的H3PO4(75%的水);41.9%的H2SO4;将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例9:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为乙二胺四乙酸(EDTA),并且其通过18%的H2O的溶液制备;0.6%的Cr(NO3)3.9H2O;0.3%的乙二胺四乙酸;39.7%的H3PO4(75%的水);41.4%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例10:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为乙二胺四乙酸(EDTA),并且其通过18.3%的H2O的溶液制备;0.6%的Cr(NO3)3.9H2O;0.5%的乙二胺四乙酸二钠盐;39.2%的H3PO4(75%的水);41.4%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例11:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为乙二胺四乙酸(EDTA),并且其通过18%的H2O的溶液制备;0.6%的Cr(NO3)3.9H2O;0.3%的乙二胺四乙酸;39.7%的H3PO4(75%的水);41.4%的H2SO4。将待蚀刻的片在40℃的温度下放置在浴中3分钟。
实施例12:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为乙二胺四乙酸(EDTA),并且其通过18%的H2O的溶液制备;2%的Cr(NO3)3.9H2O;1%的乙二胺四乙酸;35.5%的甲磺酸(75%的水);43.5%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例13:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为富马酸盐,并且其通过18%的H2O的溶液制备;0.6%的Cr(NO3)3.9H2O;0.3%的富马酸;39.7%的H3PO4(75%的水);41.4%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例14:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体是通过18%的H2O溶液的草酸化合物;0.9%的Cr(NO3)3.9H2O;0.6%的草酸H2C2O4.2H2O;39.7%的H3PO4;40.8%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例15:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体是通过17.7%的H2O溶液的草酸化合物;1.2%的Cr(NO3)3.9H2O;0.6%的草酸H2C2O4.2H2O;39.7%的H3PO4(75%);40.8%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中15分钟。
实施例16:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体为水杨酸盐,并且其通过18%的H2O的溶液制备;0.6%的Cr2O3;0.8%的水杨酸;39.7%的H3PO4(75%的水);40.9%的H2SO4。将待蚀刻的片在25℃的温度下放置在浴中3分钟。
实施例17:
基于Cr(III)盐的蚀刻浴,其中与铬配位的配体为水杨酸盐,并且其通过18%的H2O的溶液制备;0.6%的Cr2O3;0.8%的水杨酸;39.7%的H3PO4(75%的水);40.9%的H2SO4。将待蚀刻的片在60℃的温度下放置在浴中3分钟。
实施例18:
基于Cr(III)盐的蚀刻浴液,其中与铬配位的配体为葡萄糖酸盐,并且其通过18%的H2O的溶液制备;0.6%的Cr2(SO4)3·H2O;2%的葡萄糖酸钠;38%的H3PO4(75%的水);41.4%的H2SO4。
将待蚀刻的片在25℃的温度下放置在浴中3分钟。
金属化片通过交叉切割测试(ISO 2409)进行粘附力测试,这是通常用于测定涂层对聚合物的粘附性的方法之一。将粘附结果从0至5进行评分,其中0为优异的粘附力,并且剥离方法遵循标准DIN 53494。
在片的蚀刻和金属化之后获得的金属层的粘附结果示于下表中:
在浴处理之后,通过在40℃的空气中干燥2小时来制备涂覆有油漆或有机涂层的片,然后用气刷涂覆。所用的油漆为标准类型,称为基于三乙二醇二丙烯酸酯的100%固体和根据制造商的建议施加的UV固化。
进行ISO2409测试的油漆的粘附结果:
浴实施例 | 聚合物 | ISO 2409 |
浴实施例1 | 20%滑石的聚丙烯 | 3 |
浴实施例2 | 20%滑石的聚丙烯 | 3 |
浴实施例3 | 20%滑石的聚丙烯 | 3 |
浴实施例10 | 20%滑石的聚丙烯 | 3 |
浴实施例11 | 20%滑石的聚丙烯 | 3 |
Claims (9)
1.通过基于使用Cr(III)配位络合物的化学工艺对包括热塑性塑料、热固性材料或弹性体的聚合物材料进行酸蚀刻的制剂的用途,其目的在于通过施加化学浴或有机涂层来使它们金属化,蚀刻浴中酸的浓度可为10%至最高98%。
2.根据权利要求1所述的使用聚合物材料的酸蚀刻浴的制剂以对其进行金属化或有机涂覆的用途,其中铬(III)络合物基于使用通过氧、硫或氮原子或通过这些原子中的若干原子与铬配位的至少一个或若干个单、双、三、四、五、六齿或桥联配体。
3.根据权利要求2所述的制剂的用途,其中所述配体在以下中找到:甲酸盐、乙酸盐、丙酸盐、丁酸盐、苯甲酸盐、苯乙酸盐、苯丙酸盐、氰酸盐、苯甲酸烷基盐、丙酮酸盐、乙酰丙酸盐、柠檬酸盐、异柠檬酸盐、乌头酸盐、偏苯三酸盐、甘氨酸盐、缬氨酸盐、亮氨酸盐、苏氨酸盐、赖氨酸盐、色氨酸盐、组氨酸盐、苯基丙氨酸盐、异亮氨酸盐、精氨酸盐、蛋氨酸盐、丙氨酸盐、脯氨酸盐、丝氨酸盐、半胱氨酸盐、天冬酰胺盐、谷氨酰氨酸盐、酪氨酸盐、天冬氨酸盐、聚天冬氨酸盐、谷氨酸盐、半胱氨酸盐、同型半胱氨酸盐、鸟氨酸盐、烟酸盐、草酸盐、丙二酸盐、丁二酸盐、戊二酸盐、己二酸盐、马来酸盐、富马酸盐、邻苯二甲酸盐、间苯二甲酸盐、对苯二甲酸盐、酒石酸盐、衣康酸盐、中康酸盐、柠康酸盐、乙醇酸盐、乳酸盐、扁桃酸盐、水杨酸盐、葡萄糖酸盐、乙二胺四乙酸盐、次氮基三乙酸盐、亚氨基二琥珀酸盐、乙二胺丁二酸氢盐、甲基甘氨酸二醋酸盐、N,N,谷氨酸二乙酸盐、亚环己基二次氮基四乙酸酯、二亚乙基三胺五乙酸盐、氨基乙基乙基乙二醇四乙酸盐、三乙基四氨基六乙酸盐、二氢甲基甘氨酸盐、亚氨基二乙酸盐、草氨酸盐、次氮基三丙酸盐、乙二胺二丙酸盐、硫代二丙酸盐、二硫代二丙酸盐、氨基丙酸盐、氨基戊酸盐、氨基己酸盐、2-氨基苯甲酸盐、3-氨基苯甲酸盐、4-氨基苯甲酸盐、3-环己胺-丙胺、乙二胺、1,3-丙二胺、二甲基氨基丙胺、二乙基氨基丙胺、双(3-氨基丙基)-甲胺、二乙烯三胺、二丙烯三胺、三乙烯四胺、四乙烯戊胺、多胺、3-(2-氨基乙基)氨基丙胺、N,N′-双(3-氨基丙基)乙二胺、新戊烷二胺、环己二胺、1,6-己二胺、咪唑、1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、N-(3-氨基丙基)-咪唑、吡唑、烟酰胺、联吡啶、菲咯啉,优选地为:甲酸盐、乙酸盐、丙酸盐、甘氨酸盐、精氨酸盐、天冬氨酸盐、聚天冬氨酸盐、谷氨酸盐、烟酸盐、草酸盐、丙二酸盐、丁二酸盐、戊二酸盐、己二酸盐、马来酸盐、富马酸盐、邻苯二甲酸盐、水杨酸盐、酒石酸盐、柠檬酸盐、乙醇酸盐、乳酸盐、葡萄糖酸盐、乙二胺四乙酸盐、次氮基三乙酸盐、2-氨基苯甲酸盐,更优选地为草酸盐、丙二酸盐、丁二酸盐、马来酸盐、富马酸盐、邻苯二甲酸盐、乙醇酸盐、乳酸盐、水杨酸盐、甘氨酸盐、谷氨酸盐或其共混物。
4.根据权利要求1至3所述的制剂的用途,其中存在的Cr(III)络合物的浓度在2mM至2M的范围内,并且更优选地在5mM和1M之间,并且甚至更优选地在0.01M和0.4M之间。
5.根据权利要求1至4所述的使用酸蚀刻的制剂对聚合物材料进行金属化或有机涂覆的用途,其中所述酸能够为硫酸、氨基硫酸(氨基磺酸)、磷酸、二磷酸、偏磷酸、多磷酸、甲磺酸、乙磺酸、丙磺酸、苯磺酸、甲苯磺酸、异丙苯磺酸、烷基苯磺酸、单烷基磷酸、二烷基磷酸、羟乙磺酸、高氯酸、氯酸、硝酸、三氟甲磺酸、三氟乙酸、四氟硼酸、六氟磷酸、六氟硅酸、氢氟酸、硼酸或其共混物;优选地是硫酸、氨基硫酸(氨基磺酸)、磷酸、二磷酸、偏磷酸、多磷酸、甲磺酸、乙磺酸、丙磺酸、苯磺酸、甲苯磺酸、异丙苯磺酸、烷基苯磺酸、单烷基磷酸、二烷基磷酸或其共混物,并且更优选地是硫酸、磷酸或其共混物。
6.根据权利要求1至5所述的使用酸蚀刻的制剂对聚合物材料进行金属化或涂覆的用途,其中所述酸的重量百分比在20%和98%之间,更优选地在40%和95%之间,并且甚至更优选地在55%和92%之间。
7.根据权利要求1至6所述的制剂的用途,其中工作温度在10℃和95℃之间,更优选地在15℃和80℃之间,并且甚至更优选地在20℃和70℃之间。
8.根据权利要求1至7所述的制剂的用途,其中蚀刻时间在30秒和1小时之间,更优选地在1分钟和45分钟之间,并且甚至更优选地在2分钟和30分钟之间。
9.根据权利要求1至8所述的制剂的用途,其中对聚合物材料的有机涂覆通过油漆、清漆或其他有机涂层进行。
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