CN102264812A - 用于金属镀的热塑性基底的无铬调理和蚀刻方法 - Google Patents

用于金属镀的热塑性基底的无铬调理和蚀刻方法 Download PDF

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CN102264812A
CN102264812A CN200980152330XA CN200980152330A CN102264812A CN 102264812 A CN102264812 A CN 102264812A CN 200980152330X A CN200980152330X A CN 200980152330XA CN 200980152330 A CN200980152330 A CN 200980152330A CN 102264812 A CN102264812 A CN 102264812A
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polymeric amide
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A·E·埃利亚
C·皮尔多梅尼科
M·泽布里
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Abstract

本文描述了使用溶于溶剂中的硫酸将用于金属镀的热塑性基底同时调理和蚀刻的改进方法。

Description

用于金属镀的热塑性基底的无铬调理和蚀刻方法
发明领域
用于金属镀的热塑性基底的同时调理和蚀刻的改进型无铬(VI)方法。
发明背景
用金属镀覆热塑性聚合物(TP)是本领域熟知的，并且应用于商业中。此类镀层用于美观用途(即铬镀)，用于改善聚合物基底的机械特性，并且用于提供其它改善的特性如电磁屏蔽。可采用多种方法将金属置于TP上，如非电的或电解镀、真空金属喷镀、不同的溅射方法、将金属箔层压在热塑性塑料上等。
无论使用上述哪一种方法，所得产品必须具有某些有用特性。一般而言，金属镀层应具有足够的粘附性，使得在使用期间它不与热塑性基底分离。如果产品必须经历温度循环，即，在环境温度之上和/或之下反复加热和冷却，这可能是尤其困难的。由于大多数热塑性组合物与大多数金属具有不相同的热膨胀系数，因此反复的加热和冷却循环可能使介于金属和TP之间的界面具有应力，导致TP和金属镀层间的粘合性变弱，最终导致TP与金属层分离。因此，需要用于改善TP与金属镀层粘附性，尤其是热循环环境中TP与金属镀层粘附性的加工方法和/或组合物。
通过在镀层之前对基底采用调理和/或蚀刻，能够改善对基底的粘附性。本领域已知的标准蚀刻材料是磺基铬酸。然而，铬VI的不利之处是对环境有害。已发现，使用适宜的溶剂中的不包含铬VI的硫酸，能够将TP基底同时调理和蚀刻，致使粘附性改善。
发明概述
本文描述的是将用于金属镀的热塑性聚合物基底的至少一部分或所有表面同时调理和蚀刻的方法，所述方法包括使所述基底的表面与在适宜溶剂中包含硫酸的溶液接触。
发明详述
本文描述的是将用于镀覆的热塑性聚合物基底的表面同时调理和蚀刻的方法，所述方法包括使所述基底的表面与在适宜溶剂中包含硫酸的溶液接触。所述方法能够在所述基底的所有或部分表面上进行。
所谓“热塑性聚合物”(TP)，通常是指不交联并且具有高于30℃的玻璃化转变温度(Tg)和/或熔点(Tm)的有机聚合材料。本文中，使用ASTM方法D3418-82，采用25℃/min的温度加热速率，来测定Tm和Tg。对二次热进行测量。将熔融吸热峰值取作Tm，而将转变拐点取作Tg。任何熔点的熔融热应为至少约1.0J/g才能被认为是Tm。
可用的TP可包括热塑性聚合物的共混物，包括两种或更多种半结晶或非晶态聚合物的共混物，或包含半结晶和非晶态热塑性聚合物的共混物。优选的非晶态TP是ABS(丙烯腈-丁二烯-苯乙烯)聚合物。
所谓“半结晶热塑性聚合物”，是指具有高于30℃的熔点和至少约2.0J/g，更优选至少约5.0J/g的熔融热的热塑性聚合物。
优选半结晶TP，并且包括聚合物如聚(氧亚甲基)及其共聚物；聚酯如聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸1，4-丁二醇酯)、聚(对苯二甲酸1，4-环己基二亚甲基酯)、和聚(对苯二甲酸1，3-丙二醇酯)；聚酰胺如尼龙-6，6、尼龙-6、尼龙-12、尼龙-11、尼龙-10、和部分芳基化的(共)聚酰胺；聚烯烃如聚乙烯(即所有类型，如低密度、直链低密度、高密度等)、聚丙烯，但是不限于这些。
优选的TP是聚酰胺，通常为部分芳族聚酰胺。所述聚酰胺还可包括脂族聚酰胺和部分芳族聚酰胺。
所谓“部分芳族聚酰胺”(PAP)，是指部分衍生自一种或多种芳族二元羧酸的聚酰胺，其中总芳族二元羧酸为至少50摩尔％，优选至少80摩尔％，并且更优选地，衍生出聚酰胺的基本上所有的一种或多种二元羧酸均是芳族二元羧酸。优选的芳族二元羧酸是对苯二甲酸和间苯二甲酸以及它们的组合。
所谓“脂族聚酰胺”(AP)，是指衍生自一种或多种脂族二胺和一种或多种二元羧酸，和/或一种或多种脂族内酰胺的聚酰胺，前提条件是总二元羧酸衍生出的单元以小于60％摩尔，更优选小于20％摩尔的量存在，并且尤其优选基本上不存在衍生自芳族二元羧酸的单元。
所谓“脂族二胺”，是指其中每个氨基结合到脂族碳原子上的化合物。可用的脂族二胺包括式H2N(CH2)nNH2的二胺，其中n为4至12，和2-甲基-1，5-戊二胺。
所谓“芳族二元羧酸”，是指其中每个羧基结合到作为芳环一部分的碳原子上的化合物。可用的二元羧酸包括对苯二甲酸、间苯二甲酸、4，4’-联苯二甲酸和2，6-萘二甲酸。
优选的PAP为包含衍生自一种或多种二元羧酸和一种或多种二胺的重复单元的那些，所述二元羧酸如间苯二甲酸、对苯二甲酸、己二酸，所述二胺如其中n为4至12的H2N(CH2)nNH2，和2-甲基戊二胺。应当了解，可形成这些重复单元的任何组合以形成优选的PAP。
优选的AP为包含衍生自其中m为2至12的式HO2C(CH2)mCO2H、间苯二甲酸和对苯二甲酸的一种或多种二元羧酸的重复单元的那些。尤其优选的二元羧酸为己二酸(m＝4)。在这些优选的AP中，包含优选的得自二胺的重复单元为衍生自其中n为4至12的H2N(CH2)nNH2，和2-甲基戊二胺，并且其中n为6的二胺是尤其优选的。应当了解，可形成这些重复单元的任何组合以形成优选的AP。尤其优选的特定AP是聚酰胺-6，6和聚酰胺-6[聚(ε-己内酰胺)]以及聚酰胺10。
在优选的PAP中，TP具有约90℃或更高，优选约140℃或更高，并且尤其优选约200℃或更高的Tg和/或Tm。TP优选占总组合物的至少30重量％，更优选占总组合物的至少50重量％。应当了解，所述组合物中可存在一种以上的TP，并且将存在的一种或多种TP的总量取作存在的TP的量。
待金属镀的TP组合物还可包含通常以常见量存在于热塑性TP组合物中的其它材料，如(注意，这些具体材料中某些的分类可能比较主观，并且有时这些材料可实现一种以上的功能)：增强剂，如玻璃纤维、碳纤维、芳族聚酰胺纤维、磨制玻璃、平板玻璃、和钙硅石；填料，如粘土、云母、炭黑、二氧化硅和其它硅酸盐矿物质；阻燃剂；颜料；着色剂；稳定剂(光的和/或热的)；抗氧化剂；润滑剂和/或脱模剂；粘附性促进剂(尤其是TP组合物和金属镀层之间的粘附性)；增韧剂，包括聚合物增韧剂，其它聚合物如聚酯和非晶态聚酰胺。优选的材料为增强剂，尤其为玻璃纤维和碳纤维。应当了解，可存在一种以上的每种类型的这些材料，并且还可存在上述材料一种以上的类型。
TP还可包含可蚀刻的填料。所谓“可蚀刻的填料”是指在不会显著不利地影响聚合物基底的条件下，通过适当(酸、碱、热、溶剂等)处理被至少部分移除和/或其表面被改变的填料。这是指经由所施加的处理，填料从聚合物部件表面上被部分或完全移除。例如，所述填料可以是能够被盐酸水溶液移除(蚀刻)的材料如碳酸钙或氧化锌，或可被碱水溶液移除的材料如氧化锌或柠檬酸，或能够在高温下解聚的材料如聚(甲基丙烯酸甲酯)，或能够被溶剂如水移除的柠檬酸或氯化钠。由于聚合基质通常不会因处理而受到很大的影响，因此一般仅聚合物部件表面附近的可蚀刻填料将受影响(被完全或部分移除)。根据蚀刻所用的条件来确定任何具体情形下何种材料将是可蚀刻的填料，所述条件包括用品如蚀刻剂(热、溶剂、化学制剂)和实施蚀刻时的物理条件。例如，就任何具体聚合物而言，蚀刻不应在足够高以造成基质聚合物大规模热降解的温度下实施，和/或基质聚合物不应接触广泛攻击聚合物基质的化学试剂和/或易于溶解所述聚合物基质的溶剂。对聚合物基质的某些非常轻微的“损伤”是可接受的，并且实际上，因对聚合物自身的“攻击”而造成的聚合物基质表面的少量蚀刻可用于改善(稍后)涂覆到聚合物表面上的任何涂层的粘附性。
可蚀刻填料是优选的成分，尤其是将通过非电的涂覆和/或电解的涂覆获得金属镀层时。TP可包含约0.5至约30重量％的可蚀刻填料。优选的可蚀刻填料是碱金属碳酸盐和碱土金属(第2族元素，IUPAC表示法)碳酸盐，并且尤其优选碳酸钙。可蚀刻填料的最小量优选为0.5重量％或更高，更优选约1.0重量％或更高，极优选约2.0重量％或更高，并且尤其优选约5.0重量％或更高。可蚀刻填料的最大含量优选为约30重量％或更低，更优选约15重量％或更低，并且尤其优选约10重量％或更低。这些重量百分比是基于总TP组合物计的。应当了解，任何这些最小重量百分比能够与任何最大重量百分比组合以形成可蚀刻填料的优选重量范围。可存在一种以上的可蚀刻填料，并且如果存在一种以上，则将存在的那些的总量取作可蚀刻填料的量。
TP组合物可由本领域通常用于制备TP组合物并且熟知的那些方法制得。最常见的是，在适宜的设备如单螺杆或双螺杆挤出机或捏合机中，使TP自身与各种成分熔融混合。为了防止扁平强化纤维长度大规模降解，在双螺杆挤出机中优选从“侧面加入”所述纤维，使得所述纤维不经历挤出机全程高剪切。
可通过TP组合物的常见形成方法，如注塑、挤出、吹塑、热成型、涂凝模塑等，来形成部件。同样，这些方法是本领域熟知的。
在本文所述的方法中，将酸蚀刻剂溶于适宜的溶剂中。适宜的溶剂是不会对TP基底有害，能够溶解所述酸蚀刻剂，并且在高于室温但是低于TP熔点的温度范围内能够部分溶解和/或溶胀所述TP的一种溶剂。聚酰胺的典型适宜溶剂包括苯酚如但不限于甲酚(甲基苯酚)和间甲酚，和乙二醇；并且还包括某些酸如甲酸、乙酸。酸蚀刻剂可以是硫酸、磷酸、亚磷酸、次磷酸、或它们的组合。
可在通风橱中，将酸蚀刻剂或酸蚀刻剂的水溶液逐渐加入到溶剂中，同时保持溶液温度低于标称80℃或其它安全温度，直至根据加入到溶剂体积中的酸水溶液的体积和浓度确定，溶剂中酸的浓度达到约180至约700g/L，或优选约200至约550g/L。通过用氢氧化钠滴定测得，搅拌后酸的最终浓度通常为约90至约350g/L，优选约100至约275g/L。
制备TP基底表面，并且通过在搅拌下使至少部分或所有表面与由此制得的酸蚀刻剂溶液接触来蚀刻。接触期间所述溶液的温度通常为约50℃至约100℃，或约70℃至约90℃，或约75℃至约85℃。
通常在约3至约25分钟，或约5至约20分钟，或约10分钟期间内，完成接触。
所述方法还可包括额外的一个或多个活化步骤，其中通过用通常为钯化合物的“催化剂”处理，能够活化部分或所有的TP基底表面，然后用非电镀溶液处理，将金属层如镍或铜层沉积在TP表面上。如果需要更厚和/或附加的金属层，则所述方法还可包括使用本领域已知的任何方法，使部分或所有表面被覆金属的步骤，所述方法如非电的、电解的、或它们的组合。适宜的催化剂和将金属镀层施加到TP基底上的其它方法是熟知的，参见例如美国专利5,762,777、6,299,942和6,570,085。可施加具有相同或不同组成的多个金属层。
可镀在TP上的可用金属包括铜、锰、锡、镍、铁、锌、金、铂、钴和磷、以及这些金属的合金。采用非电的和/或电解的镀覆方法易于镀上这些金属，而铝常用于真空金属喷镀中。所述镀层可具有各种镀层方法可达到的任何厚度，但是通常为约1至约300μm厚，优选约1至约100μm厚。沉积的金属的平均晶粒尺寸可在1nm至约15,000nm范围内。一种优选的平均晶粒尺寸范围是1nm至100nm。金属镀层的功效可为例如以下一种或多种：改善的美观性，改善的机械特性，增强的电磁屏蔽性，改善的TP保护性，以防备腐蚀环境和/或反复暴露于加热和快速冷却循环。
这些金属镀层组合物可用于多种制品中如机动车部件，尤其是具有任选地加热和冷却循环需求的高温环境中的机动车部件，手持装置中的电子器件、玩具、器具、动力工具、工业机械等。
实施例
本文的所有份数均为重量份。
所用的材料是：
聚酰胺组合物1
聚合物A       55％
填料1         40％
增韧剂        5％
聚酰胺组合物2
聚酰胺组合物3
Figure BPA00001390845700071
聚合物A-由对苯二甲酸、50摩尔％(按存在的总二胺计)的1，6-己二胺和50摩尔％的2-甲基-1，5-戊二胺制得的PAP。
聚合物B-脂族聚酰胺，较低分子量的聚酰胺-6，6，Elvamid
Figure BPA00001390845700072
8061，得自E.I.DuPont de Nemours&Co.，Inc.(Wilmington，DE 19899 USA)。
填料1-煅烧过的表面经处理的高岭土Translink
Figure BPA00001390845700073
445，得自BASF(Florham Park，N.J.)。
填料2-碳酸钙，Super-Pflex
Figure BPA00001390845700074
200，得自Specialty MineralInc.(NewYork，NY 10174，USA)。
填料3-钙硅石，NyadG10012，得自NYCO(Willsboro，New York12996 U.S.A)。
增韧剂-EPDM，得自E.I.DuPont de Nemourss&Co.，Inc.(Wilmington，DE 19899)
GF-短切玻璃纤维，PPG
Figure BPA00001390845700076
3660，得自PPG Industries(Pittsburgh，PA15272，USA)。
实施例通过在80C温度下使部分芳族聚酰胺(PAP)组合物1、2、3的整个表面与硫酸的乙二醇溶液接触10分钟将它们蚀刻，其中通过向10升乙二醇中逐渐加入3升98％的硫酸水溶液，制得硫酸的乙二醇溶液。随后经由表1中描述的方法，将由此表面处理的PAP活化并且用镍非电地镀覆，之后同样根据表1中描述的方法将它们用铜进行电镀。表2描述了同样用于在塑性表面和电镀的铜金属层间产生足够剥离强度的方法。如上所述用硫酸的乙二醇溶液实现蚀刻，而随后的活化和用镍非电的镀覆步骤不同，而铜的电镀相同。
由表3中的方法制得正向比较实施例，其中蚀刻溶液为磺基铬酸，而后续步骤与表2中的方法相同。
由表4中所示的方法制得负向比较实施例，其中蚀刻溶液包含盐酸的乙二醇溶液，并且后续步骤与表1中所述的方法相同。
表1
采用离子钯活化的方法
Figure BPA00001390845700081
a RT表示室温
b分钟(‘)和秒(”)
c得自Rohm&Haas Electronic Materials Europe(Coventry CV3 2RQ，GreatBritain)
表2
采用DP钯/锡活化的方法
Figure BPA00001390845700091
a RT表示室温
b分钟(‘)和秒(“)
c得自Rohm&Haas Electronic Materials Europe(Coventry CV3 2RQ，GreatBritain)
表3
正向比较实施例
Figure BPA00001390845700101
a如果没有列出添加剂，则使用水。
b如果没有列出温度，则使用室温。
c该材料得自Rohm&Haas Electronic Materials Europe(Coventry CV3 2RQ，GreatBritain)
表4
负向比较实施例
Figure BPA00001390845700111
a RT表示室温
b分钟(‘)和秒(‘)
c得自Rohm&Haas Electronic Materials Europe(Coventry CV3 2RQ，GreatBritain)
通过在30mm Werner&Pfleiderer双螺杆挤出机中搅拌各成分，制得实施例中的三种PAP组合物。所述PAP被输送至尾段，将玻璃纤维和一种或多种填料顺流添加到熔融的聚酰胺中。将圆筒保持在310℃的标称温度。在穿过股模离开挤出机的时候，所述组合物被制成粒状。接下来，将所述聚酰胺组合物注塑成6cm×6cm×0.2cm的块。注塑条件为在100℃干燥的空气中干燥6-8小时，熔融温度为320-330℃，并且模具温度为140-160℃。
剥离强度是采用ISO测试方法34-1，由具有2.5kN负载传感器的Zwick
Figure BPA00001390845700112
(或等同装置)Z005张力检验器测得的粘附力。用固定在滑台上的20-25μm金属(铜)标准原电池来电镀热塑性组合物块，所述滑台连接到张力检验器的一端。在金属表面进行两个间隔1cm的平行切割，以便在热塑性表面上形成1cm宽的金属带。所述滑台在平行于切割的方向上滑动。将所述1cm宽的铜条连接到机器的另一端，并将所述金属条以50mm/min(温度23℃，50％RH)测试速度(以直角)剥离。然后计算剥离强度，并且示于表4中。
表4
Figure BPA00001390845700121

Claims (12)

1.将用于金属镀的热塑性聚合物基底的至少一部分或所有表面同时调理和蚀刻的方法，所述方法包括使所述基底的表面与在适宜溶剂中包含硫酸的溶液接触。
2.权利要求1的方法，其中所述热塑性基底是聚酰胺。
3.权利要求2的方法，其中所述聚酰胺是部分芳族聚酰胺或部分芳族聚酰胺与脂族聚酰胺的组合。
4.权利要求2的方法，其中所述聚酰胺包含衍生自一种或多种二元羧酸和一种或多种二胺的重复单元，所述二元羧酸为间苯二甲酸、对苯二甲酸、己二酸，所述二胺是其中n为4至12的H2N(CH2)nNH2和2-甲基戊二胺。
5.权利要求1的方法，其中所述适宜溶剂是乙二醇。
6.权利要求1的方法，其中所述溶液的温度为约50℃至约100℃。
7.权利要求1的方法，其中所述接触在约3至约25分钟期间内完成。
8.权利要求1的方法，所述方法还包括一个或多个在催化剂的存在下活化的步骤。
9.权利要求1的方法，所述方法还包括金属镀步骤，其中所述金属镀为非电的、电解的、或它们的组合。
10.由权利要求1的方法制得的金属镀制品。
11.由权利要求1的方法制得的金属镀制品，其中所述金属选自铜、锰、锡、镍、铁、锌、金、铂、钴和磷、铝以及这些金属的合金。
12.权利要求10的金属镀制品，其中所述制品适用于高温应用、机动车部件、电子器件、玩具、器具、动力工具、或工业机械。
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