CN104471109A - 化学镀金处理方法和镀金覆盖材料 - Google Patents

化学镀金处理方法和镀金覆盖材料 Download PDF

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Publication number
CN104471109A
CN104471109A CN201380037493.XA CN201380037493A CN104471109A CN 104471109 A CN104471109 A CN 104471109A CN 201380037493 A CN201380037493 A CN 201380037493A CN 104471109 A CN104471109 A CN 104471109A
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gold
alloy layer
plating bath
gold plate
plating
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CN201380037493.XA
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CN104471109B (zh
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迎展彰
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/1803Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831Use of metal, e.g. activation, sensitisation with noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/01Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract

本发明提供一种化学镀金处理方法,该化学镀金处理方法具有如下工序:在基材上形成基底合金层的工序;以及使用非氰基系金镀浴、通过化学还原镀直接在所述基底合金层上形成金镀层的工序,该化学镀金处理方法的特征在于,所述基底合金层为M1-M2-M3合金(其中,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,M3是从P和B中选择出的至少一种元素。)。

Description

化学镀金处理方法和镀金覆盖材料
技术领域
本发明涉及化学镀金处理方法和镀金覆盖材料。
背景技术
以往,作为用于在连接器、开关或印刷电路板等所使用的电触点材料的表面形成金镀层的方法,使用了对金属基材的表面实施化学置换镀金处理的方法。
然而,这样的通过化学置换镀金形成金镀层的方法存在如下那样的问题。即,在进行化学置换镀时,存在这样的情况:作为被镀材的金属基材发生局部溶出,而在金属基材的表面产生微小的凹部,由此,在产生的凹部无法适当地析出金,而在形成的金镀层的表面产生针孔(日文:ピンホール)。然后,其结果,得到的电触点材料存在这样的问题:耐腐蚀性和导电性降低,并且在通过软钎料进行接合时,在电触点材料与软钎料之间的界面处发生剥离。
另一方面,为了解决这样的针孔问题,还采用了在通过化学置换镀金形成的金镀层上进一步实施化学还原镀金处理来覆盖针孔的方法,但存在这样的问题:为了通过化学还原镀金覆盖针孔,需要增厚金镀层的厚度,成本上不利。
对此,在专利文献1中公开了这样的方法:在基材上实施镀钯处理而形成钯镀层,之后,通过在钯镀层上进行化学还原镀金而形成金镀层。
现有技术文献
专利文献
专利文献1:日本特开2005-54267号公报
发明内容
发明要解决的问题
然而,在所述专利文献1的技术中,在形成金镀层时,使用氰基系金镀浴,因此存在这样的问题:需要处理毒性较高的氰基系废液,给作业环境、外部环境带来较大的负荷。并且,在代替氰基系金镀浴而使用非氰基系金镀浴在钯镀层上实施化学还原镀处理的情况下,存在这样的问题:得到的金镀层的覆盖率极低,而且,密合性明显降低。
本发明是鉴于这样的实际情况而做成的,其目的在于提供一种这样的化学镀金处理方法:能够形成密合性优良且抑制针孔的产生的金镀膜,并且能够改善带给作业环境、外部环境的负荷。
用于解决问题的方案
为了达到所述目的,本发明人进行了认真研究,结果发现,在基材上形成由规定元素构成的基底合金层,利用非氰基系金镀浴通过化学还原镀在该基底合金层上形成金镀层,由此能够达到所述目的,以至完成了本发明。
即,根据本发明,提供一种化学镀金处理方法,该化学镀金处理方法具有如下工序:在基材上形成基底合金层的工序;以及使用非氰基系金镀浴、通过化学还原镀直接在所述基底合金层上形成金镀层的工序,该化学镀金处理方法的特征在于,所述基底合金层为M1-M2-M3合金(其中,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,M3是从P和B中选择出的至少一种元素。)。
另外,根据本发明,提供一种镀金覆盖材料,该镀金覆盖材料具备:基材;基底合金层,其形成在所述基材上;以及金镀层,其形成在所述基底合金层上,该镀金覆盖材料的特征在于,所述基底合金层为M1-M2-M3合金(其中,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,M3是从P和B中选择出的至少一种元素。)。
发明的效果
采用本发明,能够提供一种这样的化学镀金处理方法:能够形成密合性优良且抑制针孔的产生的金镀膜,并且能够改善带给作业环境、外部环境的负荷。
附图说明
图1是在实施例和比较例中得到的镀金覆盖材料的表面的SEM照片。
图2是表示在实施例和比较例中得到的镀金覆盖材料的离子溶出浓度的图表。
具体实施方式
以下,说明本发明的化学镀金处理方法。
通过本发明的化学镀金处理方法得到的镀金覆盖材料在基材上具备基底合金层和金镀层,该镀金覆盖材料的特征在于,所述基底合金层为M1-M2-M3合金(其中,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,M3是从P和B中选择出的至少一种元素。)。
<基材>
作为基材,并不特别限定,能够列举出钢、不锈钢、Al、Al合金、Ti、Ti合金、Cu、Cu合金、Ni、Ni合金等。作为基材的形状,并不特别限定,能够根据使用用途适当地选择,例如能够使用如下基材:加工成线状、板状的导电性的金属部件、将板加工成凹凸状而成的导电性构件、以及加工成弹簧状、筒状的电子设备的部件等根据用途加工成需要的形状的基材。另外,基材的粗细(直径)、厚度(板厚)并不特别限定,能够根据使用用途适当地选择。
<基底合金层>
基底合金层是用于良好地形成金镀层的基底层,由M1-M2-M3合金形成。在此,M1-M2-M3合金由彼此不同的元素的M1、M2和M3构成,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,并且,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,而且,M3是从P和B中选择出的至少一种元素。
需要说明的是,形成基底合金层的方法并不特别限定,能够通过电解镀、化学镀、溅镀等形成。并且,如下述所示,特别优选通过化学镀形成。
M1-M2-M3合金中的M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,既可以单独使用其中的一种元素,也可以组合两种以上元素使用,例如Ni-Fe、Ni-Co、Ni-Cu等。构成M1的各元素是具有能够单独在基材上形成镀层这样的特性的元素,构成M1的各元素均具有使基底合金层紧密接合于基材的作用。需要说明的是,作为M1,从能够防止镀液自分解、提高镀液的稳定性这一点而言,优选使用从Ni和Co中选择出的至少一种元素,特别优选使用Ni。
另外,M1-M2-M3合金中的M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,既可以单独使用其中的一种元素,也可以组合两种以上元素使用。构成M2的各元素是具有自催化作用的元素,在析出于基材上时,均作为镀浴中的还原剂的反应的催化剂发挥作用,具有使金属析出反应连续地进行的作用。需要说明的是,作为M2,从能够抑制成本这一点而言,优选使用从Pd和Ag中选择出的至少一种元素,特别优选使用Pd。
此外,M1-M2-M3合金中的M3是从P和B中选择出的至少一种元素,既可以单独使用其中的一种元素,也可以组合两种以上元素使用,例如P-B。构成M3的各元素是构成用于形成基底合金层的镀浴中的还原剂的非金属(metalloid),通常,在形成基底合金层时构成M3的各元素会不可避免地进入到基底合金层。需要说明的是,作为M3,从能够防止镀液自分解、提高镀液的稳定性这一点而言,优选使用P。
另外,优选的是,M1-M2-M3合金中的各元素的比率为:M1:20原子%~50原子%,M2:30原子%~50原子%,M3:20原子%~30原子%。另外,若是能够在M1-M2-M3合金上适当地形成金镀层,防止在金镀层上产生未形成金镀层的部分、针孔的范围内,则M1-M2-M3合金也可以略微含有不可避免地混入的杂质。作为不可避免地混入的杂质,能够列举出例如作为防止镀液自分解、使镀液稳定的稳定剂而被添加的Pb、Tl、Bi等重金属。需要说明的是,从减轻环境负荷的观点而言,优选使用Bi作为这样的稳定剂。通过将M1-M2-M3合金的组成比设在所述范围内,能够在基材上良好地形成基底合金层,并且,金镀层也能够良好地形成在基底合金层上,能够减少金镀层上针孔的产生。
另外,作为M1-M2-M3合金,能够使用将各元素任意组合而成的组合物,但从能够防止镀液自分解、提高镀液的稳定性这一点而言,优选使用Ni-Pd-P合金、Co-Ag-P合金,特别优选使用Ni-Pd-P合金。
由M1-M2-M3合金形成的基底合金层是通过使用镀浴在基材上实施镀敷而形成的,所述镀浴为含有M1、M2和M3所示的元素且添加有还原剂、络合剂的镀浴(基底合金化学镀浴)。例如,在形成由Ni-Pd-P合金形成的基底合金层的情况下,能够将通常使用的镍镀浴和钯镀浴混合而得到的镀浴等用作基底合金化学镀浴。作为镍镀浴,例如,能够列举出由氯化镍、硫酸镍、硝酸镍、乙酸镍等镍盐、次磷酸盐等含有磷的还原剂以及柠檬酸等络合剂形成的镀浴等。作为钯镀浴,例如,能够列举出由次磷酸盐、亚磷酸盐等含有磷的还原剂、氯化钯等钯盐以及硫代乙醇酸等络合剂形成的镀浴等。需要说明的是,在将镍镀浴与钯镀浴混合来制作基底合金化学镀浴时,优选使用氯化镍作为镍盐、使用氯化钯作为钯盐。镍镀浴与钯镀浴的混合比率只要根据构成Ni-Pd-P合金的各元素的比率来适当地设定即可。另外,在以上所述中,例示了将基底合金层设为Ni-Pd-P合金的情况,但在基底合金层由Ni-Pd-P合金以外的合金构成的情况下,同样地,也只要使用通过适当调整含有M1、M2和M3的各元素且添加有还原剂、络合剂的镀浴而成的基底合金化学镀浴即可。
需要说明的是,优选的是,使用所述基底合金化学镀浴,在pH为4.0~7.0、浴温为30℃~50℃、时间为5分钟~20分钟的条件形成基底合金层。
另外,基底合金层的厚度优选为0.01μm~1.0μm,更优选为0.05μm~0.2μm。通过将基底合金层的厚度设在所述范围内,能够通过化学还原镀在基底合金层上良好地形成金镀层。
在本发明中,在将基底合金层形成于基材上时,可以直接在基材上形成基底合金层,但为了提高基材与基底合金层之间的密合性,也可以设置改性层。作为改性层,能够根据基材、基底合金层的特性适当地形成,但从提高与基底合金层之间的密合性这样的观点而言,优选为这样的层:含有与构成基底合金层的M1-M2-M3合金中的M1相同的元素。例如,在采用Ni-Pd-P合金作为基底合金层的情况下,作为改性层,优选是含有作为相当于M1的元素的Ni的Ni系层,在通过化学还原镀形成这样的Ni系层的情况下,能够列举出Ni-P镀层等。需要说明的是,改性层既可以只有一层,也可以是两层以上,并且,在改性层为两层以上的情况下,构成各层的成分可以不同,或者也可以相同。另外,形成改性层的方法并不特别限定,能够通过电解镀、化学镀、溅镀等方法来形成。
<金镀层>
金镀层是通过使用非氰基系金镀浴直接在基底合金层上实施化学还原镀敷处理而形成的层。
在本发明中,如所述那样,在基材上形成由M1-M2-M3合金构成的基底合金层,在此基础上,通过化学还原镀在该基底合金层上形成金镀层,从而能够形成没有针孔的良好的金镀层。因此,采用本发明,在将这样的形成有金镀层的镀金覆盖材料用于电触点材料等各种材料的情况下,能够有效地防止耐腐蚀性和导电性降低、在软钎焊时软钎料发生剥离。而且,采用本发明,通过形成由M1-M2-M3合金构成的层来作为基底合金层,能够使用非氰基系金镀浴而形成金镀层,因此能够减小带给作业环境、外部环境的负荷。即,不会发生在使用氰基系金镀浴时带给作业环境、外部环境的负荷的问题。
作为在形成金镀层时使用的非氰基系金镀浴,能够使用通常用于化学还原镀的非氰基系金镀浴,即,含有作为金盐的氯金酸盐、亚硫酸金盐、硫代硫酸金盐、金巯基苹果酸盐等中的一种以上的镀浴。优选利用含有所述金盐的非氰基系金镀浴,在pH为7.0~8.5、浴温为55℃~65℃的条件下形成金镀层。需要说明的是,在形成金镀层时,浸渍于金镀浴的浸渍时间并不特别限定,能够根据需要的金镀层的膜厚进行设定。
需要说明的是,作为在基材上形成金镀层的方法,以往使用了直接在基材上实施化学置换镀金处理来形成金镀层的方法。然而,在这样的实施化学置换镀金处理的方法中,存在这样的情况:作为被镀材的金属基材发生局部溶出,而在金属基材的表面产生凹部,由此,存在这样的问题:在产生的凹部无法适当地析出金,而在形成的金镀层的表面产生针孔。并且,为了覆盖像这样产生的针孔,还采用了在通过化学置换镀金处理形成金镀层之后进一步实施化学还原镀金处理的方法,但还存在这样的问题:为了覆盖针孔,需要增厚金镀层的厚度,成本上不利。
相对于此,采用本发明的化学镀金处理方法,通过形成由M1-M2-M3合金构成的层来作为基底合金层,通过化学还原镀敷处理来形成金镀层,而不需要实施化学置换镀金处理,从而能够解决这样的针孔问题。特别是,采用本发明,通过形成由M1-M2-M3合金构成的层来作为基底合金层,从而能够通过化学还原镀敷处理良好地形成金镀层,因此也不需要为了解决所述针孔问题而增厚金镀层的厚度。
另外,在所述专利文献1(日本特开2005-54267号公报)中公开的化学镀金处理方法,即,在基材上实施化学还原镀钯处理而形成钯镀层之后,通过化学还原镀金处理在钯镀层上形成金镀层的方法中,在形成金镀层时,使用氰基系金镀浴,因此,存在这样的问题:需要处理毒性较高的氰基系废液,带给作业环境、外部环境的负荷较大。
相对于此,采用本发明的化学镀金处理方法,能够使用非氰基系金镀浴来形成金镀层,从而能够减小带给作业环境、外部环境的负荷。
需要说明的是,金镀层的厚度优选为1nm~200nm,更优选为5nm~100nm。若金镀层的厚度过薄,则有可能无法在基底合金层上形成均匀的金镀层,而导致在用作镀金覆盖材料时耐腐蚀性、导电性和软钎焊性降低。另一方面,若金镀层的厚度过厚,则成本上不利。
采用本发明的化学镀金处理方法,在基材上形成由M1-M2-M3合金构成的基底合金层,在此基础上,通过化学还原镀在该基底合金层上形成金镀层,因此能够提供一种包括无小孔的良好的金镀层且具有优良的耐腐蚀性、导电性和软钎焊性的镀金覆盖材料。这样的本发明的镀金覆盖材料适合用作连接器、开关或印刷电路板等所使用的电触点材料。
另外,这样的本发明的镀金覆盖材料适合应用于作为燃料电池的构件的燃料电池用隔板。特别是,对于燃料电池用隔板而言,在其表面形成有作为燃料气体的流路、空气的流路而发挥作用的凹凸,承担使在电极产生的电子汇聚的任务,因此需要在凹凸部分良好地形成金镀层,而且,还要求耐腐蚀性和导电性。对此,本发明的镀金覆盖材料是通过化学还原镀而形成有金镀层的镀金覆盖材料,因此,即使是在凹凸部分,也良好地形成有金镀层,具有优良的耐腐蚀性、导电性,因此能够适合应用于这样的燃料电池用隔板。
实施例
以下,列举实施例,更具体地说明本发明,但本发明并不限定于这些实施例。
<实施例1>
准备好总厚度为1.27mm的基材,该基材是通过化学镀在由JIS H4000规定的5000系的5086铝合金(Si:0.4重量%,Fe:0.5重量%,Cu:0.1重量%,Mn:0.2重量%,Mg:3.5重量%,Zn:0.25重量%,Cr:0.25重量%,Al:其余部分)上形成有Ni-P层(P的含有比例为12重量%)而成的,该Ni-P层表面的算术平均粗糙度Ra为0.1nm、厚度为10μm。接着,对准备好的基材进行脱脂,之后,进行水洗,使用Ni-P镀浴(日本奥野制药工业公司制,ICPニコロンGM-NP),通过化学镀,在基材上形成了厚度为2μm的Ni-P镀层(P的含有比例为7重量%)。
接着,针对形成了Ni-P镀层的基材,使用将下述所示的Pd镀浴和Ni-P镀浴以Pd镀浴:Ni-P镀浴=3:1(体积比)的比例混合而成的镀浴,在浴温为40℃、时间为7分钟的条件下,实施镀敷处理,从而在Ni-P镀层上形成厚度为0.79μm的Ni-Pd-P合金层。需要说明的是,镀浴中的钯盐、还原剂和络合剂使用了以往公知的化合物。
<Pd镀浴>
钯盐:Pd镀浴中的Pd为0.15重量%的量
还原剂:1.8重量%
络合剂:0.63重量%
水:97.2重量%
pH:5.8
<Ni-P镀浴>
镍盐(氯化镍):1.8重量%
还原剂(次磷酸钠):2.4重量%
络合剂:2.4重量%
水:93.2重量%
pH:5.2
接着,针对形成了Ni-P镀层和Ni-Pd-P合金层的基材,使用非氰基系化学还原金镀浴(日本奥野制药工业公司制,セルフゴールドOTK),在浴温为60℃、时间为4分钟的条件下,通过实施化学还原镀敷处理,从而在Ni-Pd-P合金层上形成厚度为55nm的金镀层,而得到镀金覆盖材料。
接着,利用电感耦合等离子体发射光谱分析装置(日本岛津制作所公司制,ICPE-9000)测量得到的镀金覆盖材料,在Ni-Pd-P合金层的组成中,Ni:Pd:P=34:42:20(原子%),其余部分为不可避免的杂质。
金镀层的外观评价以及金的未析出部的确认
然后,利用肉眼和扫描型电子显微镜(日本日立ハイテクノロジーズ公司制,S-4800)观察通过如此得到的镀金覆盖材料,针对得到的镀金覆盖材料的表面,确认金镀层的外观以及是否存在金的未析出部。评价结果表示在表1中。
金镀层的密合性评价
接着,对镀金覆盖材料的金镀层进行密合性的评价。密合性的评价、具体而言为:在镀金覆盖材料的金镀层上粘贴粘合带(日本米其邦公司制,ナイスタック強力タイプ),之后,揭掉该粘合带,由此实施剥离试验,之后,观察金镀层的剥离状态,根据以下的基准进行评价。评价结果表示在表1中。
○:没有确认到金镀层发生剥离。
×:金镀层发生了剥离。
<实施例2>
使用厚度为50nm的Ni-Pt-P合金层代替所述Ni-Pd-P合金层,所述Ni-Pt-P合金层通过如下方式形成,使用将Pt镀浴(日本高纯度化学公司制,IM-PT)和在形成所述Ni-Pd-P合金层时使用的Ni-P镀浴以Pt镀浴:Ni-P镀浴=3:7(体积比)的比例混合而成的镀浴,在浴温为35℃、时间为10分钟、pH为4.0的条件下,通过实施镀敷处理,从而在Ni-P镀层上形成厚度为50nm的Ni-Pt-P合金层,并且,通过改变在形成金镀层时的化学还原镀敷处理中的浸渍时间等,来形成厚度为5nm的金镀层,除此以外,与实施例1同样地得到镀金覆盖材料,同样地进行评价。评价结果表示在表1中。
<实施例3>
使用厚度为50nm的Co-Pd-P合金层代替所述Ni-Pd-P合金层,所述Co-Pd-P合金层通过如下方式形成,使用将Pd镀浴(日本奥野制药工业公司制,パラトップ)和下述所示的Co镀浴以Pd镀浴:Co镀浴=1:6(体积比)的比例混合而成的镀浴,在浴温为60℃、时间为10分钟、pH为8.5的条件下,通过实施镀敷处理,从而在Ni-P镀层上形成厚度为50nm的Co-Pd-P合金层,之后,通过改变在形成金镀层时的化学还原镀敷处理中的浸渍时间等,来形成厚度为5nm的金镀层,除此以外,与实施例1同样地得到镀金覆盖材料,同样地进行评价。评价结果表示在表1中。
<Co镀浴>
钴盐(硫酸钴):10g/L
还原剂(次磷酸钠):25g/L
络合剂(柠檬酸三钠):30g/L
络合剂(酒石酸纳):30g/L
络合剂(甘氨酸):7.58g/L
乙酸铅:0.3ppm
<比较例1>
没有形成所述Ni-Pd-P合金层,而是使用非氰基系化学还原金镀浴(日本奥野制药工业公司制,セルフゴ一ルドOTK)直接在Ni-P镀层上实施化学还原镀敷处理,除此以外,与实施例1同样地得到镀金覆盖材料,同样地进行评价。评价结果表示在表1中。
<比较例2>
代替形成Ni-Pd-P合金层,而是使用Pd镀浴(日本奥野制药工业公司制,パラトツプ),通过化学镀,在Ni-P镀层上形成厚度为0.5μm的钯镀层,之后使用非氰基系化学还原金镀浴(日本奥野制药工业公司制,セルフゴ一ルドOTK)直接在形成的钯镀层上实施化学还原镀敷处理,除此以外,与实施例1同样地得到镀金覆盖材料,同样地进行评价。评价结果表示在表1中。
[表1]
金镀层的下层 外观评价 未析出部的有无 密合性评价
实施例1 Ni-Pd-P合金层 均匀且良好地形成有金镀层
实施例2 Ni-Pt-P合金层 均匀且良好地形成有金镀层
实施例3 Co-Pd-P合金层 均匀且良好地形成有金镀层
比较例1 Ni-P镀层 没有形成金镀层 无法测量
比较例2 Pd镀层 金镀层产生不均 ×
由表1的结果可知,在实施例1~3中形成的金镀层均匀且外观良好,也没有确认到金的未析出部,而且密合性也良好,其中,在实施例1~3中,利用本发明的化学镀金处理方法,分别形成Ni-Pd-P合金层、Ni-Pt-P合金层、Co-Pd-P合金层来作为基底合金层,之后,使用非氰基系金镀浴、通过化学还原镀直接在形成的基底合金层上形成金镀层。另一方面,在未形成这样的基底合金层的比较例1中,没有形成金镀层,因此,无法测量金镀层的密合性。另外,在形成了钯镀层来代替基底合金层的比较例2中,为这样的结果:金镀层的覆盖率极低,而且密合性较低。
在此,图1表示利用扫描型电子显微镜观察实施例1~3和比较例1、2的表面而得到的照片。需要说明的是,图1(A)与实施例1相对应,图1(B)与实施例2相对应,图1(C)与实施例3相对应,图1(D)与比较例1相对应,图1(E)与比较例2相对应。对于实施例1~3,如图1(A)~图1(C)所示,能够确认为均匀地形成有金镀层。另外,对于比较例1,如图1(D)所示,在Ni-P镀层上没有形成金镀层。对于比较例2,如图1(E)所示,金镀层(图1(E)中的白色部分)不均地形成,随处可见金的未析出部分。
<实施例4~6>
通过改变在形成金镀层时的化学还原镀中的浸渍时间等,使形成的金镀层的厚度为36nm(实施例4)、49nm(实施例5)和63nm(实施例6),除此以外,与实施例1同样地得到镀金覆盖材料。
<比较例3>
关于比较例3,没有形成Ni-Pd-P合金层,而是使用非氰基系化学置换金镀浴(日本奥野制药工业公司制,フラッシュゴールドNC),在浴温为55℃、时间为1分钟的条件下,直接在Ni-P镀层上实施化学置换镀敷处理,接着,使用非氰基系化学还原金镀浴(日本奥野制药工业公司制,セルフゴールドOTK),在浴温为60℃、时间为1分钟的条件下实施化学还原镀敷处理,形成厚度为35nm的金镀层,除此以外,与实施例1同样地得到镀金覆盖材料。
<比较例4~6>
改变在形成金镀层时的化学还原镀中的浸渍时间等,使形成的金镀层的厚度为78nm(比较例4)、132nm(比较例5)和186nm(比较例6),除此以外,与比较例3同样地得到镀金覆盖材料。
金镀层的耐腐蚀性评价
接着,对在实施例4~6和比较例3~6中得到的镀金覆盖材料进行耐腐蚀性的评价。耐腐蚀性的评价、具体而言为:利用聚酰亚胺胶带以镀金覆盖材料暴露纵长为35mm、横长为20mm的面积的方式遮蔽该镀金覆盖材料,在90℃的硫酸水溶液(体积为80ml,pH:1)中浸渍了50个小时,之后,取出镀金覆盖材料,利用电感耦合等离子体发射光谱分析装置(日本岛津制作所公司制,ICPE-9000)测量自镀金覆盖材料溶出到硫酸水溶液中的离子(Ni、Pd、P)的浓度。结果表示在图2中。需要说明的是,图2所示的结果示出的是以比较例3中的金镀层的厚度为35nm时的离子(Ni、Pd、P)溶出浓度为100时的相对值。
由图2中的结果可知,在使用了本发明的化学镀金处理方法的实施例4~6中,为这样的结果:即使在金镀层的厚度较薄的情况下,也能够有效地抑制离子的溶出,耐腐蚀性优良。另一方面,在没有形成基底合金层的比较例3~6中,为这样的结果:即使在金镀层形成得较厚的情况下,也无法抑制离子的溶出,金镀层的耐腐蚀性较差。

Claims (2)

1.一种化学镀金处理方法,该化学镀金处理方法具有如下工序:
在基材上形成基底合金层的工序;以及
使用非氰基系金镀浴、通过化学还原镀直接在所述基底合金层上形成金镀层的工序,该化学镀金处理方法的特征在于,
所述基底合金层为M1-M2-M3合金(其中,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,M3是从P和B中选择出的至少一种元素。)。
2.一种镀金覆盖材料,该镀金覆盖材料包括:
基材;
基底合金层,其形成在所述基材上;以及
金镀层,其形成在所述基底合金层上,该镀金覆盖材料的特征在于,
所述基底合金层为M1-M2-M3合金(其中,M1是从Ni、Fe、Co、Cu、Zn和Sn中选择出的至少一种元素,M2是从Pd、Re、Pt、Rh、Ag和Ru中选择出的至少一种元素,M3是从P和B中选择出的至少一种元素。)。
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