JPH0711477A - Noble metal plated article - Google Patents
Noble metal plated articleInfo
- Publication number
- JPH0711477A JPH0711477A JP17859793A JP17859793A JPH0711477A JP H0711477 A JPH0711477 A JP H0711477A JP 17859793 A JP17859793 A JP 17859793A JP 17859793 A JP17859793 A JP 17859793A JP H0711477 A JPH0711477 A JP H0711477A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- noble metal
- test
- plating layer
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 23
- 238000007747 plating Methods 0.000 claims abstract description 92
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 18
- 239000000956 alloy Substances 0.000 claims abstract description 18
- 229910020994 Sn-Zn Inorganic materials 0.000 claims abstract description 10
- 229910009069 Sn—Zn Inorganic materials 0.000 claims abstract description 10
- 239000010970 precious metal Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 229910001128 Sn alloy Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 31
- 230000007797 corrosion Effects 0.000 abstract description 31
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 40
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229910000906 Bronze Inorganic materials 0.000 description 21
- 239000010974 bronze Substances 0.000 description 21
- 239000010931 gold Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910000679 solder Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910052737 gold Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 229910017755 Cu-Sn Inorganic materials 0.000 description 4
- 229910017927 Cu—Sn Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000833 kovar Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 1
- 229940119523 thallium sulfate Drugs 0.000 description 1
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は優れた耐食性を有する貴
金属めっき品に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plated precious metal product having excellent corrosion resistance.
【0002】[0002]
【従来の技術】貴金属めっきは価格が高いことから、貴
金属の使用量を減らすために、なるべくめっき厚を小さ
くするための努力がなされている。すなわち、めっき厚
を小さくしても、貴金属めっき本来の性能が損なわれな
いようにするための研究が行われている。そのための研
究は各分野において様々なテーマで行われているが、本
願発明は下地めっき層の改善に関連して提案されたもの
である。貴金属めっきの厚さが0.5μm以下の仕様が
多くなっている現状では、下地めっきが貴金属めっき皮
膜に大きな影響を及ぼすと考えられる。2. Description of the Related Art Since precious metal plating is expensive, efforts have been made to reduce the plating thickness as much as possible in order to reduce the amount of precious metal used. That is, research is being conducted to prevent the original performance of precious metal plating from being impaired even when the plating thickness is reduced. Research for that purpose has been carried out under various themes in various fields, but the present invention has been proposed in relation to the improvement of the undercoat layer. Under the present circumstances where the thickness of the noble metal plating is 0.5 μm or less, it is considered that the base plating has a great influence on the noble metal plating film.
【0003】現在のところ、貴金属めっきの下地めっき
としてNiめっきが多用されている。しかし、下地めっ
きとしてNiめっきだけを行った場合は、貴金属めっき
の厚の減少に伴って耐食性も低下してしまい、前述の如
き貴金属めっき厚を減少させる要請に応じられない。そ
こで、本願出願人は、Niめっきに代わる下地めっきと
してのブロンズめっき(Cu−Sn−Zn)をすでに発
表している〔信学技報TECHNICAL REPORT OF IEICE.EMD9
2-72(1992-10) 〕。このブロンズめっきを下地めっきと
した場合は、Niめっきに比較して、良好な耐食性が得
られることが判明している。At present, Ni plating is often used as a base plating for precious metal plating. However, when only Ni plating is performed as the base plating, the corrosion resistance decreases as the thickness of the precious metal plating decreases, and the above-described request for reducing the thickness of the precious metal plating cannot be met. Therefore, the applicant of the present application has already announced bronze plating (Cu-Sn-Zn) as an undercoating alternative to the Ni plating [TECHNICAL REPORT OF IEICE.EMD9
2-72 (1992-10)]. It has been found that better corrosion resistance can be obtained when this bronze plating is used as the base plating, as compared with Ni plating.
【0004】[0004]
【発明が解決しようとする課題】ところが、このような
ブロンズめっきを下地めっきとした貴金属めっき品にあ
っても、すべての腐食環境において優れた耐食性を示す
ものではなかった。すなわち、耐食性試験としては、
(1) 塩水噴霧試験、(2) 硝酸バッキ試験、(3) SO2 ・
H2 S混合ガス試験などがあるが、そのうち、(1) 塩水
噴霧試験と(3) SO2 ・H2 S混合ガス試験に関して
は、Ni下地めっきに比べて、良好な耐食性を示すもの
の、(2) 硝酸バッキ試験に関しては耐食性の改善が見ら
れなかった。However, even the noble metal plated product using such bronze plating as the undercoat has not exhibited excellent corrosion resistance in all corrosive environments. That is, as a corrosion resistance test,
(1) Salt spray test, (2) Nitric acid back test, (3) SO 2 ·
Although there are H 2 S mixed gas tests, among them, (1) salt spray test and (3) SO 2 · H 2 S mixed gas test show better corrosion resistance than Ni undercoat, but ( 2) No improvement in corrosion resistance was observed in the nitric acid back test.
【0005】また、Ni下地めっきに代えて、ブロンズ
めっきにした場合は、前述のようにある一定の耐食性が
向上する反面、耐熱性や半田ぬれ性がNi下地めっきの
場合よりも低下することが判明した。従って、このよう
な特性が要求されないめっき品、例えば装飾品等への適
用は好ましいが、リードフレームの如き耐熱性や半田ね
れ性が要求される電子部品への適用は不適であった。Further, when the bronze plating is used instead of the Ni undercoat, the corrosion resistance is improved to a certain extent as described above, but the heat resistance and the solder wettability are lower than those of the Ni undercoat. found. Therefore, it is preferable to apply to plated products that do not require such characteristics, for example, decorative products, but it is not suitable to electronic components such as lead frames that require heat resistance and solderability.
【0006】この発明はこのような従来の技術に着目し
てなされたものであり、広範囲な腐食環境下において良
好な耐食性を示す貴金属めっき品、及びそれに加えて耐
熱性や半田ねれ性も具備した貴金属めっき品を提供する
ものである。The present invention has been made by paying attention to such a conventional technique, and is provided with a noble metal-plated product exhibiting good corrosion resistance in a wide range of corrosive environments, and in addition, has heat resistance and solderability. It provides a plated precious metal product.
【0007】[0007]
【課題を解決するための手段】この発明の貴金属めっき
品は、素材の表面に、Cu−Sn−Zn合金の下地めっ
き層を形成し、その上に貴金属めっき層を形成してなる
貴金属めっき品において、前記下地めっき層中のSn比
率が25wt%以上であることを要旨としている。The noble metal plated product of the present invention is formed by forming a Cu-Sn-Zn alloy undercoat plating layer on the surface of a raw material and then forming a noble metal plating layer thereon. In the above, the gist is that the Sn ratio in the base plating layer is 25 wt% or more.
【0008】すなわち、ブロンズめっき(Cu−Sn−
Zn)中におけるSn比率を変えて耐食試験((1) 塩水
噴霧試験、(2) 硝酸バッキ試験、(3) SO2 ・H2 S混
合ガス試験)を行ったところ、Sn比率を25wt%以
上にすることにより、(1) 塩水噴霧試験、(2) 硝酸バッ
キ試験、(3) SO2 ・H2 S混合ガス試験の全てにおい
て、良好な耐食性が得られる。但し、耐熱性や半田ねれ
性は低下する。従って、装飾品等への用途には適してい
るが、電子部品等への用途は不適である。That is, bronze plating (Cu-Sn-
When the corrosion resistance test ((1) salt spray test, (2) nitric acid back test, (3) SO 2 · H 2 S mixed gas test) was conducted by changing the Sn ratio in Zn), the Sn ratio was 25 wt% or more. According to the above, good corrosion resistance can be obtained in all of (1) salt spray test, (2) nitric acid back test, and (3) SO 2 · H 2 S mixed gas test. However, heat resistance and solderability deteriorate. Therefore, it is suitable for applications such as ornaments, but is not suitable for applications such as electronic parts.
【0009】また、別の発明に係る貴金属めっき品は、
前記Cu−Sn−Zn合金に代えて、Cu−Sn合金の
下地めっき層を形成したものである。下地めっき層中の
Sn比率が25wt%以上であれば、Cu−Sn−Zn
合金に代えて、Cu−Sn合金の下地めっき層を形成し
ても、同等の耐食性が得られる。A noble metal-plated product according to another invention is
Instead of the Cu-Sn-Zn alloy, a Cu-Sn alloy base plating layer is formed. If the Sn ratio in the underlying plating layer is 25 wt% or more, Cu-Sn-Zn
Even if a Cu-Sn alloy base plating layer is formed instead of the alloy, the same corrosion resistance can be obtained.
【0010】更に、別の発明に係る貴金属めっき品は、
前記下地めっき層と貴金属めっき層との間にNiめっき
層を形成したものである。該Niめっき層を形成するこ
とにより、前記の如き耐食性と共に、耐熱性や半田ねれ
性も具備した貴金属めっき品が得られる。従って、装飾
品でも、電子部品でも、どのような用途にも適してい
る。尚、このNiめっきの厚さは0.5〜3μmが好適
である。Further, a noble metal plated product according to another invention is
A Ni plating layer is formed between the base plating layer and the noble metal plating layer. By forming the Ni plating layer, it is possible to obtain a noble metal-plated product having the above-mentioned corrosion resistance as well as heat resistance and solderability. Therefore, it is suitable for any application, whether it is a decorative article or an electronic component. The thickness of this Ni plating is preferably 0.5 to 3 μm.
【0011】以上において、「素材」とは、42合金や
コバール等の鉄・ニッケル合金、真ちゅうやリン青銅等
のCu合金、ABSやエポキシ等のプラスチックが好適
である。尚、素材の表面にレベリング用のCuめっき等
を予め施しておいても良い。In the above, the "material" is preferably an iron / nickel alloy such as 42 alloy or Kovar, a Cu alloy such as brass or phosphor bronze, or a plastic such as ABS or epoxy. The surface of the material may be preliminarily plated with Cu for leveling.
【0012】「貴金属めっき」とは、Au、Ag、P
d、Rh、Ru、Ptめっき、又はこれらの合金めっき
を意味する。"Precious metal plating" means Au, Ag, P
It means d, Rh, Ru, Pt plating, or alloy plating of these.
【0013】[0013]
【実施例】以下、本発明を実施例に基づいて具体的に説
明する。EXAMPLES The present invention will be specifically described below based on examples.
【0014】実施例1 図1はこの実施例1に係る貴金属めっき品を示す図であ
り、Au合金めっきを施したインテリア製品である。素
材1はCu製で、面積4×2cm2 、厚さ0.3mmの
テストピースである。この素材1の上にCu−Sn−Z
n合金の下地めっき層2を形成し、更にこの下地めっき
層2の上に、Au合金による貴金属めっき層3を形成し
たものである。 Example 1 FIG. 1 is a view showing a noble metal-plated product according to this Example 1, which is an interior product plated with an Au alloy. The raw material 1 is a test piece made of Cu and having an area of 4 × 2 cm 2 and a thickness of 0.3 mm. Cu-Sn-Z on this material 1
The undercoating layer 2 of n alloy is formed, and the noble metal plating layer 3 of Au alloy is further formed on the undercoating layer 2.
【0015】めっき浴条件は以下の表1の通りである。
表1から分かるように、ブロンズめっきの場合は、めっ
きを行う浴組成や電流密度により、合金組成が変化す
る。尚、この表1は、実施例1だけでなく、後述する実
施例2、3で使用するめっき浴条件も記載してある。The plating bath conditions are shown in Table 1 below.
As can be seen from Table 1, in the case of bronze plating, the alloy composition changes depending on the bath composition for plating and the current density. In addition, Table 1 also describes the plating bath conditions used not only in Example 1 but also in Examples 2 and 3 described later.
【0016】[0016]
【表1】 [Table 1]
【0017】表1中に記載されためっき浴の具体的組成
は以下の通りである。 〔ブロンズめっき(Cu−Sn−Zn合金)〕 めっき浴組成(アルカリシアン浴) ・シアン化第一銅 20g/l(表1の(1) (2) 用) 30g/l(〃(3) (4) (5) 用) ・スズ酸カリウム 50g/l(〃(1) (2) 用) 15g/l(〃(3) (4) (5) 用) ・シアン化亜鉛 5g/l(〃(1) (2) 用) 14g/l(〃(3) (4) (5) 用) ・シアン化カリウム 80g/l(〃(1) (2) 用) 90g/l(〃(3) (4) (5) 用) ・光沢剤 5ml/l((1) 〜(5) 共通) ・pH 12.5(〃(1) (2) 用) 11.5(〃(3) (4) (5) 用) ・温度 50℃ ((1) 〜(5) 共通)The specific composition of the plating bath shown in Table 1 is as follows. [Bronze plating (Cu-Sn-Zn alloy)] Plating bath composition (alkali cyan bath) -Cuprous cyanide 20 g / l (for (1) and (2) in Table 1) 30 g / l (〃 (3) ( 4) (5))-Potassium stannate 50g / l (for 〃 (1) (2)) 15g / l (for 〃 (3) (4) (5)) ・ Zinc cyanide 5g / l (for 〃 ( 1) (for 2)) 14g / l (for 〃 (3) (4) (5)) ・ Potassium cyanide 80g / l (for 〃 (1) (2)) 90g / l (for 〃 (3) (4) ( 5)) ・ Brightener 5ml / l (common to (1) to (5)) ・ pH 12.5 (for 〃 (1) (2)) 11.5 (for 〃 (3) (4) (5) ) ・ Temperature 50 ℃ ((1)-(5) common)
【0018】 〔ブロンズめっき(Cu−Sn合金)〕 めっき浴組成(アルカリシアン浴) ・シアン化第一銅 17g/l(〃(6) (7) 用) 25g/l(〃(8) (9) (10)用) ・スズ酸カリウム 50g/l(〃(6) (7) 用) 15g/l(〃(8) (9) (10)用) ・シアン化カリウム 75g/l(〃(6) (7) 用) 85g/l(〃(8) (9) (10)用) ・光沢剤 5ml/l((6) 〜(10)共通) ・pH 12.5((6) 〜(10)共通) ・温度 50℃(〃(6) (7) 用) 45℃(〃(8) (9) (10)用)[Bronze plating (Cu-Sn alloy)] Plating bath composition (alkali cyan bath) -Cuprous cyanide 17 g / l (for 〃 (6) (7)) 25 g / l (〃 (8) (9 ) (For 10))-Potassium stannate 50g / l (for 〃 (6) (7)) 15g / l (for 〃 (8) (9) (10)) ・ Cyanide 75g / l (for 〃 (6) ( For 7)) 85g / l (for 〃 (8) (9) (10)) ・ Brightener 5ml / l (common to (6) to (10)) ・ pH 12.5 (common to (6) to (10)) ) ・ Temperature 50 ℃ (for 〃 (6) (7)) 45 ℃ (for 〃 (8) (9) (10))
【0019】 〔ニッケルめっき(Ni)〕 めっき浴組成(スルファミン酸浴) ・スルファミン酸ニッケル 340g/l(〃(11)用) ・塩化ニッケル 15g/l(〃(11)用) ・ホウ酸 40g/l(〃(11)用) ・光沢剤 20ml/l(〃(11)用) ・pH 3 (〃(11)用) ・温度 55℃ (〃(11)用)[Nickel plating (Ni)] Plating bath composition (sulfamic acid bath): Nickel sulfamate 340 g / l (for 〃 (11)) ・ Nickel chloride 15 g / l (for 〃 (11)) ・ Boric acid 40 g / l (for 〃 (11)) ・ Brightener 20ml / l (for 〃 (11)) ・ pH 3 (for 〃 (11)) ・ Temperature 55 ℃ (for 〃 (11))
【0020】〔硬質金めっき(Au合金)〕 めっき浴組成(弱酸性シアン浴、金−コバルト系) ・シアン化カリウム 15g/l((12)〜
(15)共通) ・硫酸コバルト 2.5g/l((12)〜
(15)共通) ・クエン酸塩 100g/l((12)〜
(15)共通) ・有機光沢剤 50ml/l((12)〜
(15)共通) ・pH 5 ((12)〜
(15)共通) ・温度 40℃ ((12)〜
(15)共通)[Hard Gold Plating (Au Alloy)] Plating Bath Composition (Weakly Acidic Cyan Bath, Gold-Cobalt System) Potassium Cyanide 15 g / l ((12) to
(15) Common) ・ Cobalt sulfate 2.5 g / l ((12) ~
(15) Common ・ Citrate 100 g / l ((12) ~
(15) common) ・ Organic brightener 50ml / l ((12) ~
(15) Common) ・ pH 5 ((12) ~
(15) Common ・ Temperature 40 ℃ ((12) 〜
(15) Common)
【0021】〔純金めっき(Au)〕 めっき浴組成(中性シアン浴) ・シアン化カリウム 12g/l((16)(1
7)共通) ・クエン酸塩 150g/l((16)(1
7)共通) ・リン酸塩 25g/l((16)(1
7)共通) ・硫酸タリウム 15mg/l((16)(1
7)共通) ・pH 6 ((16)(1
7)共通) ・温度 60℃ ((16)(1
7)共通)[Pure gold plating (Au)] Plating bath composition (neutral cyanide bath): Potassium cyanide 12 g / l ((16) (1
7) Common) ・ Citrate 150 g / l ((16) (1
7) Common) ・ Phosphate 25g / l ((16) (1
7) Common) ・ Thallium sulfate 15 mg / l ((16) (1
7) Common) ・ pH 6 ((16) (1
7) Common) ・ Temperature 60 ℃ ((16) (1
7) Common)
【0022】次に、各評価試験について説明する。耐食性試験 (塩水噴霧試験) ・試験方法 JIS Z 2371に準じて試験を行っ
た。 ・試験条件 NaCl 5% 温度35℃ 時間7
2時間 ・評価方法 試験後の腐食状態を肉眼にて観察した。 (硝酸バッキ試験) ・試験方法 3リットルデシケータの底部に硝酸(61
%)100mlを入れ、上部に試験片をつるした。 ・試験条件 温度25℃ 時間60分 ・評価方法 試験後の腐食状態を肉眼にて観察した。 (SO2・H2S混合ガス試験) ・試験方法 山崎精機社製ガス試験機を使用。 ・試験条件 ガス濃度 SO2 10ppm H2S 3ppm 温度40℃ 湿度75% 時間96時間 ・評価方法 試験後の腐食状態を肉眼にて観察した。 結果は以下の表2の通りであった。Next, each evaluation test will be described. Corrosion resistance test (salt spray test) -Test method A test was performed according to JIS Z2371.・ Test conditions NaCl 5% Temperature 35 ° C Time 7
2 hours-Evaluation method The corrosion state after the test was visually observed. (Nitric acid back test) ・ Test method Nitric acid (61
%) 100 ml was put and the test piece was hung on the upper part. -Test conditions Temperature 25 ° C Time 60 minutes-Evaluation method The corrosion state after the test was visually observed. (SO 2 · H 2 S mixed gas test) ・ Test method A gas tester manufactured by Yamazaki Seiki Co., Ltd. is used.・ Test conditions Gas concentration SO 2 10ppm H 2 S 3ppm Temperature 40 ° C Humidity 75% Time 96 hours ・ Evaluation method The corrosion state after the test was visually observed. The results are shown in Table 2 below.
【0023】[0023]
【表2】 [Table 2]
【0024】表2の通り、Sn比率が24wt%以下の
場合は、硝酸バッキ試験ではほとんど耐食性に差異が認
められなかったが、塩水噴霧、SO2 ・H2 S混合ガス
試験では、ブロンズめっきの方がNiめっきより優れた
耐食性を示した。そして、Sn比率が25wt%以上に
なると、硝酸バッキ試験も含めた全ての項目において優
れた耐食性を示した。このように、ブロンズめっきの耐
食性がNiめっきよりも優れている理由としては、Au
とNiの電位差に比べ、Auとブロンズの電位差が小さ
いことから、局部電池作用によるピンホールを通じての
下地めっきの腐食が抑制されるためと考えられる。As shown in Table 2, when the Sn ratio was 24 wt% or less, almost no difference was found in the corrosion resistance in the nitric acid back test, but in the salt spray and the SO 2 · H 2 S mixed gas test, the bronze plating was used. Showed better corrosion resistance than Ni plating. When the Sn ratio was 25 wt% or more, excellent corrosion resistance was exhibited in all items including the nitric acid back test. Thus, the reason why the corrosion resistance of the bronze plating is superior to that of the Ni plating is Au.
Since the potential difference between Au and bronze is smaller than the potential difference between Ni and Ni, it is considered that the corrosion of the undercoat through the pinhole due to the local cell action is suppressed.
【0025】実施例2 図2はこの実施例2に係る貴金属めっき品を示す図であ
り、下地めっき層4をCu−Sn合金にした。それ以外
は、実施例1と同じである。めっき浴条件は前記の表1
の通りである。結果は以下の表3の通りであった。 Example 2 FIG. 2 is a diagram showing a noble metal-plated product according to Example 2, in which the undercoat plating layer 4 was a Cu—Sn alloy. Other than that, it is the same as the first embodiment. The plating bath conditions are shown in Table 1 above.
Is the street. The results are shown in Table 3 below.
【0026】[0026]
【表3】 [Table 3]
【0027】表3の通り、Sn比率を25wt%以上に
すると、実施例1と同様に、硝酸バッキ試験も含めた全
ての項目において優れた耐食性を示した。As shown in Table 3, when the Sn ratio was 25 wt% or more, excellent corrosion resistance was exhibited in all the items including the nitric acid backlit test, as in Example 1.
【0028】実施例3 図3はこの実施例3に係る貴金属めっき品を示す図であ
り、電子部品としてのリードフレームの表面に金めっき
を施したものである。素材5は42合金(Fe/Ni合
金)製である。この素材5の上にCu−Sn−Zn合金
の下地めっき層2を形成し、更にこの下地めっき層2の
上に、1μmのNiめっき層6を形成し、最後にAu
(純金)による貴金属めっき層7を形成したものであ
る。尚、Niめっき層6は比較例と同じめっき状態で形
成した。次に、各評価試験について説明する。 Embodiment 3 FIG. 3 is a view showing a noble metal-plated product according to this embodiment 3, in which the surface of a lead frame as an electronic component is gold-plated. The material 5 is made of 42 alloy (Fe / Ni alloy). A Cu-Sn-Zn alloy base plating layer 2 is formed on the material 5, and a 1 μm Ni plating layer 6 is further formed on the base plating layer 2, and finally Au.
The noble metal plating layer 7 is formed of (pure gold). The Ni plating layer 6 was formed in the same plating state as the comparative example. Next, each evaluation test will be described.
【0029】耐熱性試験 ・試験方法 米国TRANS TEMP社製電気炉(ゴールドファ
ーネス)を使用。 ・試験条件 温度250℃ 時間60分 大気雰囲気 ・評価方法 加熱後の腐食状態を肉眼にて観察した。ま
た、加熱前後の接触抵抗を測定した。 結果は以下の表4の通りであった。 Heat resistance test / test method An electric furnace (Gold Furnace) manufactured by TRANS TEMP of the United States is used. -Test conditions Temperature 250 ° C Time 60 minutes Air atmosphere-Evaluation method The corrosion state after heating was visually observed. Moreover, the contact resistance before and after heating was measured. The results are shown in Table 4 below.
【0030】[0030]
【表4】 [Table 4]
【0031】表4の通り、加熱前後の接触抵抗を測定し
たところ、下地めっき層としてブロンズめっきのみ(実
施例1)を形成した場合は、加熱後の接触抵抗が著しく
増加したが、実施例3のように、下地めっき層をブロン
ズめっき+Niめっきにしたところ、Sn比率に係わら
ず、従来のNiめっきのみの場合と同様に接触抵抗の増
加がわずかであった。また、加熱後の腐食状態を肉眼で
観察したところ、ブロンズめっきのみ(実施例1)の場
合は、金表面が著しく変色したが、ブロンズめっき+N
iめっきの場合は、従来のNiめっきのみの場合と同様
に金表面の変色は確認できなかった。以上のことは、ブ
ロンズめっきのみでは、ブロンズの成分であるCu、S
n、ZnがNiに比べて金中へ拡散し易く、金表面で酸
化膜を形成するためと思われる。尚、表中において(1)
(2) のものは、Sn比率が25wt%以上になるため、
前記の耐熱性と共に耐食性も向上している。加えて、ブ
ロンズめっきをCu−Sn−Zn合金に代えて、Cu−
Snにしても同等の結果が得られる。また、素材の表面
にレベリング用のCuめっきを予め施しておいても同様
の結果が得られる。As shown in Table 4, the contact resistance before and after heating was measured. When only the bronze plating (Example 1) was formed as the underlying plating layer, the contact resistance after heating was remarkably increased. As described above, when the base plating layer was bronze plating + Ni plating, regardless of the Sn ratio, the contact resistance slightly increased as in the case of the conventional Ni plating alone. Further, when the corrosion state after heating was visually observed, in the case of only bronze plating (Example 1), the gold surface was significantly discolored, but bronze plating + N
In the case of i plating, discoloration of the gold surface could not be confirmed as in the case of conventional Ni plating alone. What has been described above is that if only bronze plating is used, the components of bronze are Cu and S.
It is considered that n and Zn are more likely to diffuse into gold than Ni and form an oxide film on the gold surface. In the table, (1)
In the case of (2), the Sn ratio is 25 wt% or more,
In addition to the above heat resistance, corrosion resistance is also improved. In addition, instead of bronze plating with a Cu-Sn-Zn alloy, Cu-
Even if Sn is used, the same result can be obtained. Similar results can be obtained even if the surface of the material is preliminarily plated with Cu for leveling.
【0032】半田ぬれ性 ・試験方法 日本アルファメタルズ社製フラックス ソ
ルボンド R100-40に浸漬後、日本電熱計器社製半田槽
に2秒間浸漬し、半田ぬれ面積を調べた。 ・試験条件 半田組成 Sn63% Pb37% 温度
230℃ 結果は以下の表5の通りであった。 Solder Wettability / Test Method After dipping in flux sol bond R100-40 manufactured by Nippon Alpha Metals Co., Ltd., it was immersed in a solder bath manufactured by Nippon Denki Keiki Co., Ltd. for 2 seconds, and the solder wetted area was examined. -Test conditions Solder composition Sn63% Pb37% Temperature 230 ° C The results are shown in Table 5 below.
【0033】[0033]
【表5】 [Table 5]
【0034】表5の通り、半田ぬれ性の試験をしたとこ
ろ、下地めっき層としてブロンズめっきのみ(実施例
1)を形成した場合は、はじきの現象がみられ、半田ぬ
れ面積は30〜60%程度であった。これに対し、実施
例3のように、下地めっき層をブロンズめっき+Niめ
っきにしたところ、従来のNiめっきのみの場合と同様
に半田ぬれ面積が95%以上の良好な半田ぬれ性を示し
た。ブロンズめっきのみが、半田ぬれ性に劣る原因とし
ては、皮膜中の炭素、窒素の吸蔵が考えられる。尚、こ
の表5に関しても、(1) (2) のものは、Sn比率が25
wt%以上になるため、前記の半田ぬれ性と共に耐食性
も向上している。As shown in Table 5, when the solder wettability test was conducted, when only the bronze plating (Example 1) was formed as the undercoat layer, a repellency phenomenon was observed and the solder wettability area was 30 to 60%. It was about. On the other hand, when the underplating layer was bronze-plated + Ni-plated as in Example 3, good solder-wettability with a solder-wet area of 95% or more was exhibited as in the case of only conventional Ni-plating. The reason why only the bronze plating is inferior in solder wettability is considered to be the occlusion of carbon and nitrogen in the film. In addition, also in Table 5, the Sn ratio of (1) and (2) is 25
Since it is more than wt%, the solder wettability and the corrosion resistance are improved.
【0035】[0035]
【発明の効果】請求項1及び2記載の発明に係る貴金属
めっき品は、以上説明してきた如き内容のものであっ
て、(1) 塩水噴霧試験、(2) 硝酸バッキ試験、(3) SO
2 ・H2S混合ガス試験の全てに関して優れた耐食性を
示す。従って、住宅関連用品、仏具、洋食器などのエク
ステリア(及びインテリア)製品、時計、メガネ、ジュ
エリー、文具、ボタンなどの装飾品、への用途に適して
いる。EFFECTS OF THE INVENTION The noble metal plated product according to the inventions of claims 1 and 2 has the contents as described above, and comprises (1) a salt spray test, (2) a nitric acid back test, and (3) SO.
Excellent corrosion resistance for all 2 · H 2 S mixed gas tests. Therefore, it is suitable for home-related products, exterior (and interior) products such as Buddhist fittings and Western dishes, and ornaments such as watches, glasses, jewelry, stationery and buttons.
【0036】請求項3記載の発明に係る貴金属めっき品
は、前記耐食性に加えて、耐熱性及び半田ぬれ性にも優
れるため、接点、コネクター、リードフレーム、プリン
ト基板、などの電子部品への用途に適している。Since the noble metal plated product according to the third aspect of the present invention is excellent in heat resistance and solder wettability in addition to the corrosion resistance, it is used for electronic parts such as contacts, connectors, lead frames, and printed circuit boards. Suitable for
【図1】第1実施例の貴金属めっき品を示す拡大断面図
である。FIG. 1 is an enlarged cross-sectional view showing a noble metal plated product of a first embodiment.
【図2】第2実施例の貴金属めっき品を示す拡大断面図
である。FIG. 2 is an enlarged cross-sectional view showing a noble metal plated product of a second embodiment.
【図3】第3実施例の貴金属めっき品を示す拡大断面図
である。FIG. 3 is an enlarged sectional view showing a noble metal-plated product of a third embodiment.
1、5 素材 2、4 下地めっき層 3、7 貴金属めっき層 6 Niめっき層 1, 5 Material 2, 4 Base plating layer 3, 7 Noble metal plating layer 6 Ni plating layer
Claims (3)
下地めっき層を形成し、その上に貴金属めっき層を形成
してなる貴金属めっき品において、前記下地めっき層中
のSn比率が25wt%以上であることを特徴とする貴
金属めっき品。1. A noble metal-plated product having a Cu-Sn-Zn alloy undercoat plating layer formed on the surface of a material and a noble metal plating layer formed thereon, wherein the Sn ratio in the undercoat plating layer is 25 wt. % Precious metal plated product.
Sn合金の下地めっき層を形成した請求項1記載の貴金
属めっき品。2. Cu— instead of the Cu—Sn—Zn alloy
The noble metal plated product according to claim 1, wherein a base plating layer of Sn alloy is formed.
Niめっき層を形成した請求項1又は2記載の貴金属め
っき品。3. The noble metal plated product according to claim 1, wherein a Ni plating layer is formed between the undercoat plating layer and the noble metal plating layer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17859793A JPH0711477A (en) | 1993-06-28 | 1993-06-28 | Noble metal plated article |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17859793A JPH0711477A (en) | 1993-06-28 | 1993-06-28 | Noble metal plated article |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0711477A true JPH0711477A (en) | 1995-01-13 |
Family
ID=16051243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17859793A Pending JPH0711477A (en) | 1993-06-28 | 1993-06-28 | Noble metal plated article |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0711477A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5694411A (en) * | 1995-04-07 | 1997-12-02 | Kabushiki Kaisha Toshiba | Ultraviolet range laser and method for manufacturing the same |
JP2002161393A (en) * | 2000-11-22 | 2002-06-04 | Bikutoria:Kk | Method for plating noble metal having corrosion resistance and noble metal plate accessories |
JP2005537394A (en) * | 2002-10-11 | 2005-12-08 | エンソーン インコーポレイテッド | Bronze electrodeposition method |
JP2008210584A (en) * | 2007-02-23 | 2008-09-11 | Fujikura Ltd | Flexible flat cable terminal |
JP2014022460A (en) * | 2012-07-13 | 2014-02-03 | Tatsuta Electric Wire & Cable Co Ltd | Shield film and shield printed wiring board |
-
1993
- 1993-06-28 JP JP17859793A patent/JPH0711477A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5694411A (en) * | 1995-04-07 | 1997-12-02 | Kabushiki Kaisha Toshiba | Ultraviolet range laser and method for manufacturing the same |
JP2002161393A (en) * | 2000-11-22 | 2002-06-04 | Bikutoria:Kk | Method for plating noble metal having corrosion resistance and noble metal plate accessories |
JP2005537394A (en) * | 2002-10-11 | 2005-12-08 | エンソーン インコーポレイテッド | Bronze electrodeposition method |
JP2008210584A (en) * | 2007-02-23 | 2008-09-11 | Fujikura Ltd | Flexible flat cable terminal |
JP2014022460A (en) * | 2012-07-13 | 2014-02-03 | Tatsuta Electric Wire & Cable Co Ltd | Shield film and shield printed wiring board |
US9888619B2 (en) | 2012-07-13 | 2018-02-06 | Tatsuta Electric Wire & Cable Co., Ltd | Shield film and shield printed wiring board |
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