CN107075684B - 用于金属化塑料部件的方法 - Google Patents
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Abstract
本发明涉及一种用于防止经金属化工艺处理的至少一个塑料部件的支撑件金属化的方法,所述方法依次包括如下步骤:所述部件的表面的氧化,氧化表面的活化以及金属在活化表面上的化学和/或电化学沉积,其特征在于,所述方法包括使所述支撑件在所述氧化阶段之前与包含至少一种特定金属化抑制剂的抑制溶液接触的步骤,所述金属化抑制剂选自亚硫酸钠、硫脲、硫醇、硫醚、带有至少一个硫醇和/或噻唑基基团的化合物和其混合物。本发明还涉及一种用于防止经金属化工艺处理的塑料部件的支撑件的金属化的方法,所述方法包括使所述支撑件和所述部件与所述抑制溶液接触,所述支撑件由与所述部件的材料不同的材料制成。
Description
技术领域
本发明涉及一种用于防止经金属化工艺处理的至少一个塑料部件的支撑件金属化的方法,所述方法依次包括如下阶段:所述部件的表面的氧化,氧化表面的活化以及金属在活化表面上的化学和/或电化学沉积,其特征在于,所述方法包括其中使所述支撑件在所述氧化阶段之前与包含至少一种特定金属化抑制剂的抑制溶液接触的阶段。本发明还涉及一种用于对与支撑件组合的塑料部件进行选择性金属化的方法,所述方法包括使所述部件与所述抑制溶液接触。
背景技术
为了在例如化妆品、纺织品、机动车辆、航空、电子或电气产品工业中使用塑料件的目的,对这些部件进行金属化以赋予它们特定的美学、电学或机械性能是已知的。由于待金属化的材料由不导电的聚合物组成,因此工业金属化工艺包括一系列旨在对其表面进行改性的阶段,以使得可沉积可以具有不同性质的金属涂层。这些阶段的目的在于提供塑料基材与金属之间的最佳粘附性,以便补偿塑料/金属界面处特别是由于膨胀系数差异而造成的张力累积,并因此防止可能的层离。
因此,常规的金属化工艺包括将基材依次浸渍在不同的浴液中,其旨在在样品的表面进行一个或多个化学反应。常规程序的实例包括以下阶段:
·样品的制备和清洁,以便提高其在下一阶段中的润湿性,
·通常使用含有铬(VI)的40-70℃的硫酸浴,对样品进行氧化侵蚀(缎面精整(satinage)),使得可以在表面产生微粗糙度,其促进金属的后续锚固,
·例如通过使用还原剂如肼进行还原,来中和过量的铬(VI)(其构成随后使用的催化剂的毒物),得到铬(III),
·通过催化剂的沉积来活化表面,所述催化剂通常是由显示Pd/Sn核被由Cl-离子中和的Sn2+离子壳体包围的粒子形成的钯/锡胶体:这些粒子扩散到塑料表面处存在的微孔中并且化学吸附于其中,使得可以催化后续的化学沉积反应,
·通过将样品浸入浴液中、特别是硫酸浴中来加速,使得可以氧化Sn(II)离子以得到Sn(IV)离子并释放吸附的钯粒子,
·通过将样品浸入包含还原剂如次磷酸钠的金属(例如铜或镍)盐的水溶液中来化学沉积金属层,使得可以在吸附的Pd/Sn种晶上并且然后在样品的整个表面上还原金属离子,
·通过电解途径使因此获得的金属层增厚。
另外,上述阶段之后各自可以跟着一个或多个用水或使用水溶液进行漂洗的中间阶段。此外,应当注意,一些“直接镀层”的金属化工艺不包括化学沉积阶段。
为了依次进行这些不同的处理,将部件放置在支撑件(或框架)上,支撑件(或框架)在不同的浴液之间移动,任选地同时通过中间漂洗阶段。通常,这些支撑件由覆盖有塑料(例如PVC)的金属芯构成。
塑料部件在支撑件上进行金属化期间遇到的问题之一由以下产生:塑料部件和支撑件同时暴露于所述阶段中的每个,这可能导致支撑件的金属化。然而,在工业上,部件的支撑件不被金属化是至关重要的。这是因为,如果支撑件被金属化,则将有必要提供后续的去金属化阶段,这导致不必要的成本,也会导致化学品的过多消耗。此外,在支撑件上存在金属导致出现与支撑件变得导电有关的金属化缺陷。这个额外阶段也会对金属化工艺的生产量产生负面影响。另外,其通常在碱性介质中使用盐酸、硝酸或电解剥离进行。据了解,这些处理中的一些可能对环境有毒。最后,当支撑体与部件同时被金属化时,不能正确地评估被涂覆的反应物的量,因为支撑件的覆盖程度是未知的,这可能导致部件表面沉积的金属层过薄。
此外,出于技术或审美原因,仅部分地将一些部件金属化可被证明是必要的,特别是当部件包括不得被金属化的印刷元件时情况如此。为了做到这一点,目前使用了几种方法。其中一种被称为“双射注塑成型”,其由如下步骤组成:在部件制造期间注入两种或更多种材料,其中一种材料的金属化不如另外一种或多种材料的金属化。另一种方法是基于使用抗蚀涂料,这使得可以将被覆盖的部件保持在原始状态。
目前,用于防止支撑件金属化的最常用的方法是在缎面精整浴中调适支撑件和待金属化的部件。这是因为,在通过缎面精整浴侵蚀或多或少冗长的一段时间后,通常由PVC制成的支撑件相比于待金属化的部件变得更粗糙。这种粗糙度使得可以将六价铬吸收到支撑件中,所述六价铬构成化学金属化浴液的毒物。因此,铬在化学沉积浴中充当支撑件的保护剂。
然而,环境和健康方面的限制和新的规定越来越多地限制了对人类和环境有毒的六价铬的使用,并且正在推动不涉及铬的替代性金属化工艺的利用。因此已经提出用高锰酸根离子溶液替代常规的缎面精整浴液。在这种情况下,因此还可以建议开发除了六价铬“中毒”之外的其它技术,使得可以避免支撑件的金属化。
专利申请WO 2013/135862描述了不利用铬金属化塑料表面的工艺,其中支撑件优选在所述工艺的晚期阶段用碘酸根离子处理,以防止它们被金属化。据了解,这个处理阶段可能会影响随后金属与部件的粘附,所述部件与支撑件成一体,同时进行处理,甚至事实上阻止部件的金属化。另外,在该工艺中,待金属化的部件也使用二醇衍生物如乙酸2-(2-乙氧基乙氧基)乙酯或丁氧基乙醇进行预处理。除了增加工艺成本和影响其环境冲击之外,这种预处理也能够促进支撑件的金属化。
因此,仍然需要有一种不产生挥发性有机化合物的简单和廉价的方法,其使得可以选择性地金属化不导电的塑料部件,也就是说,防止支撑件或这些部件的一部分的金属化,而不影响金属沉积物的质量或机械强度。
发明内容
令人惊讶的是,在申请人的公司看来,通过使用某些特定的化合物作为金属化抑制剂可以满足这一需求。另外,这些化合物可以无差别地用于存在或不存在铬的金属化工艺中,以及在塑料部件的表面活化阶段中使用或不使用钯的工艺中。
本发明涉及一种用于防止经金属化工艺处理的至少一个塑料部件的支撑体金属化的方法,所述方法依次包括如下阶段:所述部件的表面的氧化,氧化表面的活化以及金属在活化表面上的化学和/或电化学沉积,所述方法包括其中使所述支撑件在所述氧化阶段之前与包含至少一种金属化抑制剂的抑制溶液接触的阶段,所述金属化抑制剂选自亚硫酸钠、硫脲、硫醇、硫醚、带有至少一个硫醇和/或一个噻唑基基团的化合物和其混合物。
本发明还涉及一种用于对与支撑件组合的塑料部件进行选择性金属化的方法,所述方法依次包括如下阶段:所述部件的表面的氧化,氧化表面的活化以及金属在活化表面上的化学和/或电化学沉积,其特征在于,所述方法包括其中使所述部件在所述氧化阶段之前与包含至少一种金属化抑制剂的抑制溶液接触的阶段,所述金属化抑制剂选自亚硫酸钠、硫脲、硫醇、硫醚和其混合物。
具体实施方式
定义
根据本发明,“塑料部件”被理解为是指如下的物体,其表面由不导电的塑料(聚合物)组成。这些物体可以完全由一层或多层不导电的聚合物组成,或者它们可以由被一层或多层不导电的聚合物涂覆的金属和/或玻璃质材料和/或导电聚合物组成。
此外,术语“支撑件”或“框架”表示适合于使得可以进行用于部件或优选地同时用于大量部件的金属化工艺的至少一些阶段的金属体系。
根据本发明的金属化工艺中使用的塑料部件可以包括选自天然或合成来源的热塑性聚合物和热固性聚合物的不导电塑料,其选自环氧树脂,ABS(丙烯腈/丁二烯/苯乙烯共聚物);聚酰胺;聚碳酸酯;聚酯,例如聚(甲基丙烯酸甲酯)、聚(对苯二甲酸乙二醇酯)和聚(对苯二甲酸丁二醇酯);聚醚酰亚胺;聚(偏二氟乙烯);聚醚醚酮;聚烯烃,例如聚乙烯或聚丙烯;聚(甲醛);聚苯乙烯;聚(苯硫醚);和这些聚合物的共混物。特别地,不导电塑料可以是ABS、聚酰胺、聚碳酸酯或这些聚合物的共混物。更特别地,它由ABS或ABS/聚碳酸酯共混物组成。根据本发明的一个实施方式,除了构成其的一种或多种聚合物之外,该塑料还可以包含一种或多种特别是旨在对其进行增强的有机和/或无机填料,例如二氧化硅、碳纤维、玻璃纤维或芳族聚酰胺(特别是PPD-T)纤维。这些部件特别地用于机动车辆领域,但也用作化妆品或浴室组件的包装成分。
就其本身而言,支撑体由与形成所述部件的表面的塑料不同的塑料组成或被与形成所述部件的表面的塑料不同的塑料覆盖,通常由至少一种混合有一种或多种增塑剂的聚合物、特别是聚(氯乙烯)或PVC形成。
在一个实施方式中,塑料部件包含希望不被金属化的区域。在这种情况下,根据本发明使用的抑制溶液可以在掩蔽待保留部分之后与部件接触。在这种实施方式中,优选使用由PVC或相比于构成部件的塑料显示对抑制溶液具有更大亲和力的另一种材料制成的掩模。在可选形式中,部件的表面可包含由不同材料形成的至少两个区域,这些材料例如通过多注塑成型获得。然后这些材料对抑制溶液的亲和力差异导致部件的特定部分的选择性金属化。因此,可以将显示由包含ABS或ABS/聚碳酸酯共混物的塑料形成的表面部分和另一个包含聚碳酸酯的表面部分的部件选择性地金属化。多注塑成型工艺使得可以获得显示一个透明或半透明区域和一个不透明区域的部件,或者获得在经济上比机械组装的两个组件更有利的双组件部件。在另一个实施方式中,根据本发明使用抑制溶液,以防止塑料部件的支撑件的金属化。在这种情况下,在支撑件附接到部件之前或者一旦附接到部件上,就使抑制溶液与整个支撑件接触。这是因为已经观察到,根据本发明使用的抑制溶液对于构成支撑件的PVC表现出比对于形成待金属化的部件的表面的聚合物更大的亲和力,因此单独处理支撑件是毫无意义的。显然应理解,这两种实施方式可以组合。在实践中,优选地,将由部件和其支撑件形成的组合浸入根据本发明的抑制溶液中。这导致支撑件不存在金属化,也可以导致要保留的部件部分不存在金属化。
根据一个优选的实施方式,根据本发明的金属化方法依次包括以下阶段的组合:
a)将待金属化的部件附接至支撑件;
b)对部件进行清洁、特别是脱脂;
c)氧化所述部件的表面;
d)活化所述部件的表面;
e)任选地在所述表面上化学沉积金属;
f)电解沉积金属。
在这种情况下,在阶段(c)之前,任选地在阶段(b)之前,甚至在阶段(a)之前,进行包括使抑制溶液与部件和/或与支撑件接触的阶段。优选在上述阶段(b)和(c)之间进行该阶段。在可选形式中,它们可以在阶段(a)和/或(b)期间进行。
阶段(b)是本领域技术人员熟知的清洁或脱脂阶段;特别地可以使用微碱性浴液来进行。
上述阶段(c)由如下的氧化处理组成:使用特别是基于硝酸、盐酸或硫酸,基于高锰酸盐,基于氯酸盐,基于硝酸盐,基于过氧化物,基于芬顿(Fenton)试剂,基于六价铬和/或基于臭氧的氧化溶液进行氧化处理。在这个阶段优选不使用六价铬。更优选地,氧化溶液是高锰酸钠或高锰酸钾(有利的是高锰酸钠)溶液,其使得可以在支撑件和部件的表面赋予通常小于0.1μm的微细粗糙度,并且同时在部件的表面上产生基于氧的官能团,有利的是羧酸型螯合官能团。另外,氧化溶液优选表现出酸性pH,例如小于2,甚至小于1。该阶段可以通过将附接至部件的支撑件浸渍在氧化溶液浴中一段时间(例如1至60分钟,有利的是5至30分钟)来实施。浴温可以在20℃与40℃之间。
在阶段(d)中,在先前氧化的部件的表面产生催化金属的粒子。这些粒子可以选自铜、银、金、镍、铂、钯、铱、铑或钴粒子。根据本发明的一个优选实施方式,可以通过将含有上述金属之一(优选为铜或镍,呈与四氟硼酸根、硫酸根、溴离子、氟离子、碘离子、硝酸根、磷酸根或氯离子形成的盐的形式,例如优选地与硫酸根或氯离子形成的盐的形式)的溶液施用至待金属化的部件表面而在所述表面处产生这些粒子。该溶液的pH优选大于7并且有利地介于9与11之间、优选地介于10与11之间。优选通过向金属溶液中加入氨水而不是氢氧化钠来实现该pH。另外,根据本发明的一个优选实施方式,金属溶液不含有机络合剂。待金属化的部件可以浸渍于金属溶液中持续一分钟至一小时、例如10至20分钟的一段时间。在该阶段结束时,作为氧化处理的结果存在于部件表面的有机基团通过螯合或络合与阶段(d)中施加的金属离子相键合。
在本发明的另一个实施方式中,在阶段(d)中可以用金属胶体溶液覆盖待金属化的部件的表面。有利地使用通过通常在强酸如盐酸存在下使用氯化锡(II)还原氯化钯而获得的Pd/Sn胶体。在这种情况下,阶段(d)通常被分成上述活化子阶段,接着是加速子阶段,其包括将先前活化的待金属化的部件浸入浴液中,特别是硫酸浴液中,使得可以氧化Sn(II)离子以得到Sn(IV)离子并释放吸附的钯粒子。
在阶段(d)结束时,待金属化的部件表面被催化金属的种晶覆盖,并且因此可以任选地进行化学沉积阶段(e),或者也可以直接进行电化学沉积阶段(f)。在阶段(e)中,部件通常预先浸入含有至少一种还原剂如硼氢化钠、肼、次磷酸钠或二甲基氨基硼烷的碱性还原溶液中。另外,该溶液还可以含有待沉积在部件上的金属盐,或者接着是施加包含该盐的溶液的阶段。通常是选自银、金、钴、铜、铁、镍、钯和铂离子的金属阳离子的硫酸盐,本发明中优选镍和铜离子。在阶段(e)中使用的溶液还可以包含络合剂和/或pH调节剂。还原阶段优选在高碱性pH(通常在11和13之间)下以及介于30℃与50℃之间的温度下进行。
在阶段(e)结束时,获得金属化部件,其表面金属层可以根据阶段(f)遵循本领域技术人员熟知的方法通过电解增厚。在可选形式中,阶段(f)可以在阶段(d)之后直接进行。
在上述方法中使用的所有溶液都是水溶液。另外,阶段(b)、(c)、(d)和(e)是通过将部件和支撑件浸渍在包含适于进行各阶段的反应物的浴液中而进行的,但是在可选形式中可以通过喷雾施加上述溶液。
上述方法还可以包括其它中间阶段,例如漂洗部件的阶段,特别是利用已经任选地加入洗涤剂和/或碱的水;或者使用还原剂进行处理的阶段,特别是在阶段(c)与(d)之间,尤其是当氧化处理使用六价铬或碱金属高锰酸盐时情况如此。
如上所述,将抑制溶液施加到支撑件上,并且任选地施加到阶段(c)上游的部件。该溶液包含至少一种金属化抑制剂,其选自硫类化合物,并且特别地选自亚硫酸钠、硫脲、硫醇、硫醚、带有至少一个硫醇和/或一个噻唑基基团的化合物和其混合物。所列选项中优选的是有机硫化合物,更特别是硫醇、硫醚和带有至少一个硫醇和/或一个噻唑基基团的化合物。金属化抑制剂可任选地与至少一种选自以下的另外的抑制剂组合:草酸、铅盐、镉盐、锡盐、铝盐、脲、硝酸铊、4-硝基苯重氮四氟硼酸盐和4-氨基苯甲酸。呈盐形式的另外的抑制剂可以由有机或无机盐形成,特别是由硫酸盐、硝酸盐、草酸盐或乙酸盐形成,所列选项不具限制性。在上述金属化抑制剂中,优选使用硫醇和硫醚,特别是芳族杂环硫醚,例如巯基苯并噻唑。抑制溶液有利地包含相对于组合物的总体积以重量计浓度为0.01g/l(0.0001重量%)至10g/l(0.1重量%)、例如0.01g/l(0.0001重量%)至10g/l(0.1重量%)的抑制剂。
在一个实施方式中,所述包含金属化抑制剂的溶液具有在0.5和6之间、优选在1和3之间的pH。因此,所述溶液优选包含调节pH为该值的化合物,该化合物有利地选自磷酸、盐酸和硫酸。
在一个实施方式中,所述抑制溶液另外包含至少一种增粘剂,其可以特别选自水状胶体,例如纤维素衍生物,特别是羧甲基纤维素或羟丙基甲基纤维素;明胶;藻类提取物,例如琼脂、藻朊酸盐和角叉菜胶;合成聚合物,例如聚(乙烯醇)、丙烯酸和甲基丙烯酸聚酯,包括聚(甲基丙烯酸羟乙酯),以及聚(丙烯酸)和聚(甲基丙烯酸)的盐;淀粉和其衍生物;半乳甘露聚糖,例如瓜尔豆胶;和其混合物,所列选项不具限制性。
根据以下实施例将更好地理解本发明,所述实施例仅为了示例目的而给出,而不旨在限制本发明的范围。
实施例
实施例1:使用铬的金属化工艺(无钯活化)
通过将由ABS制成的对照部件附接到由PVC制成的常规支撑件来制备待金属化的样品。脱脂后,将所述样品(支撑件+部件)在含有40g/l巯基苯并噻唑、100ml/l硫酸(95%)和25g/l羧甲基纤维素的浴液中放置20分钟。该浴液被热调节为40℃。随后将样品浸渍在达到65℃的缎面精整浴液中持续10分钟,该浴液包含400g/l硫酸和400g/l铬酸,然后浸渍在10g/l肼溶液中。随后将其浸入保持在30℃的催化浴液中,该浴液中包含足以获得30ppm的钯浓度的量的Pd/Sn胶体,然后浸入基于硫酸的50℃加速浴液中。随后在包括10g/l硫酸镍、10g/l次磷酸钠、50g/l的33%氨水溶液的水溶液中进行镍的化学沉积,直到在部件表面上获得0.3μm的沉积物。
未观察到支撑件的金属化。
实施例2:无铬的金属化工艺(无钯活化)
将由ABS制成的部件以及显示ABS/PC区域和PC区域两者的双材料部件附接到由增塑PVC制成的支撑件。脱脂后,将组件浸入含有8g/l巯基苯并噻唑、100ml/l磷酸(85%)和25g/l羧甲基纤维素的溶液中持续15分钟。浴液调节为40℃。漂洗后,将组件浸入包含高锰酸钠和磷酸的缎面精整浴液中10分钟。漂洗后,将组件在包含五水合硫酸铜和氨水的活化浴液中浸渍5分钟,然后在新鲜漂洗后,浸渍在含有硼氢化钠和氢氧化钠的还原溶液中。为了精整,将组件浸入包含铜、EDTA、氢氧化钠和甲醛的化学镀铜浴液(来自ROHM&HAAS公司的Circuposit 3350-1)中。
在该工艺结束时,在支撑件上或在由共注塑成型部件的由聚碳酸酯制成的区域上没有观察到金属化的痕迹,而由ABS制成的参考部件和双材料部件的由ABS/PC制成的区域完全被金属化。
实施例3:无铬的金属化工艺(用钯活化)
将由ABS制成的部件以及显示ABS/PC区域和PC区域两者的双材料部件附接到由增塑PVC制成的支撑件。脱脂后,将组件浸渍在含有12g/l的(2-氯-1,3-噻唑-5-基)甲醇、100ml/l的磷酸(85%)和25g/l的羧甲基纤维素的溶液中持续15分钟。浴液调节为40℃。漂洗后,将组件浸入包含高锰酸钠和磷酸的缎面精整浴液中10分钟。漂洗后,将组件在包含250ml/l的盐酸和38ml/l的钯和氯化锡的混合物(来自ROHM&HAAS公司的催化剂9F)的用钯活化的浴液中浸渍3分钟。在新鲜漂洗后,将组件浸入基于硫酸的“加速”浴液中。
在该工艺结束时,在支撑件上或在由共注塑成型部件的由聚碳酸酯制成的区域上没有观察到金属化的痕迹,而由ABS制成的参考部件和双材料部件的由ABS/PC制成的区域完全被金属化。
实施例4(比较性):无铬的金属化工艺(无钯活化)
将由ABS制成的部件以及显示ABS/PC区域和PC区域两者的双材料部件附接到由增塑PVC制成的支撑件。脱脂后,将组件浸入包含高锰酸钠和磷酸的缎面精整浴液中持续10分钟。漂洗后,将组件在包含五水合硫酸铜和氨水的活化浴液中浸渍5分钟,然后在新鲜漂洗后,浸渍在含有硼氢化钠和氢氧化钠的还原溶液中。为了精整,将组件浸入包含铜、EDTA、氢氧化钠和甲醛的化学镀铜浴液(来自ROHM&HAAS的Circuposit 3350-1)中。
在该工艺结束时,发现支撑件的一部分被金属化并且在双材料部件的由聚碳酸酯制成的区域上也观察到金属化的痕迹。参考部件和双材料部件的由ABS/PC制成的区域完全被金属化。
实施例5(比较性):无铬的金属化工艺(用钯活化)
将由ABS制成的部件以及显示ABS/PC区域和PC区域两者的双材料部件附接到由增塑PVC制成的支撑件。脱脂后,将组件浸入包含高锰酸钠和磷酸的缎面精整浴液中持续10分钟。漂洗后,将组件在包含250ml/l的盐酸和38ml/l的钯和氯化锡的混合物(来自ROHM&HAAS公司的催化剂9F)的用钯活化的浴液中浸渍3分钟。在新鲜漂洗后,将组件浸入基于硫酸的“加速”浴液中。
在该工艺结束时,发现支撑件和部件的组件完全被金属化,包括双材料部件的由聚碳酸酯制成的不应该被金属化的区域也被金属化。
实施例6:不同金属化抑制剂的研究
在改变金属化抑制剂的性质的同时重现实施例2中描述的方案。对于所测试的不同抑制剂获得的结果列在下表中。
从上表可以看出,根据本发明的金属化抑制剂均可以将部件和待金属化的部件部分选择性地金属化,并保留支撑件和任选地待保留的部件部分。
Claims (7)
1.一种用于防止经金属化工艺处理的至少一个塑料部件的支撑件金属化的方法,其中所述支撑件被聚(氯乙烯)覆盖,并且所述塑料部件的表面由选自以下的材料形成:ABS、聚酰胺、聚碳酸酯、聚酯、聚醚酰亚胺、聚(偏二氟乙烯)、聚烯烃、聚苯乙烯、聚(苯硫醚)、和这些聚合物的混合物,所述方法依次包括如下阶段:
-所述部件的表面的氧化,
-通过在所述部件的表面产生催化金属的粒子而实现的氧化表面的活化,以及
-金属在活化表面上的化学和/或电化学沉积,
其特征在于,所述方法包括其中使所述支撑件在所述氧化阶段之前与包含至少一种金属化抑制剂的抑制溶液接触的阶段,所述金属化抑制剂选自亚硫酸钠、硫脲和硫醇。
2.根据权利要求1所述的方法,其特征在于,所述抑制溶液的pH在0.5和6之间。
3.根据权利要求2所述的方法,其特征在于,所述抑制溶液的pH在1和3之间。
4.根据权利要求2所述的方法,其特征在于,所述抑制溶液另外包含pH调节剂。
5.根据权利要求4所述的方法,其特征在于,所述pH调节剂选自硫酸和磷酸。
6.根据权利要求1至5中的任一项所述的方法,其特征在于,所述抑制溶液另外包含增粘剂。
7.根据权利要求6所述的方法,其特征在于,所述增粘剂选自纤维素衍生物;明胶;藻类提取物;合成聚合物;淀粉和其衍生物;半乳甘露聚糖;和其混合物。
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PCT/FR2015/052753 WO2016071598A1 (fr) | 2014-11-04 | 2015-10-13 | Procede de metallisation de pieces plastiques |
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ES2727075T5 (es) | 2015-02-23 | 2022-05-27 | Macdermid Enthone Inc | Composición inhibidora para bastidores cuando se utilizan mordientes exentos de cromo en un proceso de galvanizado sobre materiales plásticos |
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US3443988A (en) * | 1965-05-06 | 1969-05-13 | Photocircuits Corp | Printed circuits,work holders and method of preventing electroless metal deposition |
US5084145A (en) * | 1989-04-27 | 1992-01-28 | Sumitomo Metal Industries, Ltd. | Method for manufacturing one-sided electroplated steel sheet |
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US20170292191A1 (en) | 2017-10-12 |
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