JPH0565659A - Electroless copper-nickel alloy plating method - Google Patents
Electroless copper-nickel alloy plating methodInfo
- Publication number
- JPH0565659A JPH0565659A JP25436691A JP25436691A JPH0565659A JP H0565659 A JPH0565659 A JP H0565659A JP 25436691 A JP25436691 A JP 25436691A JP 25436691 A JP25436691 A JP 25436691A JP H0565659 A JPH0565659 A JP H0565659A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- copper
- nickel
- electroless copper
- alloy plating
- 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.)
- Granted
Links
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な無電解銅ニッケル
合金めっき方法に関する。FIELD OF THE INVENTION The present invention relates to a novel electroless copper-nickel alloy plating method.
【０００２】[0002]
【従来の技術】無電解めっき法は、金属等の導電物、樹
脂セラミック等の絶縁物表面上に金属被膜を形成する方
法として広く普及している。無電解めっき法によって析
出可能な金属としては、銅、ニッケル、コバルト、錫、
金、パラジウム等が挙げられるる、最近では上記金属の
合金をめっきすることも検討されるようになった。例え
ば、「金属表面技術」Ｖｏｌ．３８ ｐ．４２４ Ｓｅ
ｐ．（１９８７）の岡村らによる「耐熱性無電解Ｎｉ−
Ｃｕ−Ｐ合金めっき」に関する報告では、磁気ディスク
用の下地めっき層として耐熱性に優れた無電解銅ニッケ
ル合金めっき被膜の検討を行なっている。銅ニッケル合
金は、銅の優れた電気伝導性および熱伝導性とニッケル
の優れた耐食性、硬度および磁気特性等との組合わせ特
性を各々の組成比を適宜選択することによって任意に引
き出すことが可能である。2. Description of the Related Art The electroless plating method is widely used as a method for forming a metal coating on the surface of a conductive material such as metal or an insulating material such as resin ceramic. Metals that can be deposited by electroless plating include copper, nickel, cobalt, tin,
Recently, plating of alloys of the above metals such as gold and palladium has also been considered. For example, “Metal surface technology” Vol. 38 p. 424 Se
p. (1987) Okamura et al., "Heat-resistant electroless Ni-
In the report on "Cu-P alloy plating", an electroless copper-nickel alloy plating film having excellent heat resistance is studied as a base plating layer for a magnetic disk. Copper-nickel alloy can bring out the combined characteristics of copper's excellent electrical conductivity and thermal conductivity and nickel's excellent corrosion resistance, hardness, magnetic properties, etc. by selecting the composition ratio of each. Is.
【０００３】ところで、無電解銅ニッケル合金めっきに
用いられる無電解めっき液は一般に還元析出型であり、
各金属源、錯化剤および還元剤で構成されている。上記
報告の無電解銅ニッケル合金めっき液も例外ではなく同
様の構成となっている。また上記報告では金属源とし
て、硫酸銅５水和物と硫酸ニッケル６水和物を用いてお
り、めっき被膜中の銅とニッケルの組成比をめっき液に
添加する金属源の濃度比で調整することが記載されてい
る。By the way, the electroless plating solution used for electroless copper-nickel alloy plating is generally a reduction deposition type,
It is composed of each metal source, complexing agent and reducing agent. The electroless copper-nickel alloy plating solution reported above has the same structure without exception. In the above report, copper sulfate pentahydrate and nickel sulfate hexahydrate are used as the metal source, and the composition ratio of copper and nickel in the plating film is adjusted by the concentration ratio of the metal source added to the plating solution. Is described.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、上記報
告の方法では無電解銅ニッケル合金めっき被膜中の銅と
ニッケルの組成比をある程度変化させることが可能であ
るものの、得られる合金めっき被膜中の銅含有量が最大
で５５％に限られるので、厳密には任意に含有量を調節
し得るものとはいえない。そして、この銅５５％のもの
を、例えばテープ自動ボンディング（ＴＡＢ）テープ等
の電子部品の導電層として利用する場合に電気伝導性に
おいて信頼に欠けるという問題があり、したがってこの
方法によって得られた合金めっき層を電子部品における
導電層として用いることは不適当であるといわざるを得
ない。However, although it is possible to change the composition ratio of copper and nickel in the electroless copper-nickel alloy plating film to some extent by the method reported above, the copper in the obtained alloy plating film is changed. Since the content is limited to 55% at maximum, strictly speaking, it cannot be said that the content can be arbitrarily adjusted. And, when this 55% copper is used as a conductive layer of an electronic component such as a tape automatic bonding (TAB) tape, there is a problem that the electric conductivity is unreliable. Therefore, the alloy obtained by this method is present. It must be said that it is inappropriate to use the plating layer as a conductive layer in electronic parts.
【０００５】本発明の目的は、無電解銅ニッケル合金め
っきを施す際に、該合金被膜中の元素の組成比を銅の含
有量の如何に拘らず任意に変化させることが可能な新規
な無電解銅ニッケル合金めっき方法を提供することにあ
る。An object of the present invention is to provide a novel alloy which can be arbitrarily changed in the composition ratio of the elements in the alloy coating regardless of the content of copper when the electroless copper-nickel alloy plating is applied. An object is to provide an electrolytic copper-nickel alloy plating method.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記目的
を達成するための無電解銅ニッケル合金めっき方法につ
いて検討を重ねた結果、めっき条件に特定の変更を加え
ることにより、無電解銅ニッケル合金めっき被膜中の元
素の組成比を任意に変化させることが可能であることを
見出し本発明を完成するに至った。The inventors of the present invention have made extensive studies on electroless copper-nickel alloy plating methods for achieving the above-mentioned object, and as a result, by making certain changes in plating conditions, electroless copper The inventors have found that it is possible to arbitrarily change the composition ratio of elements in the nickel alloy plating film, and have completed the present invention.
【０００７】即ち上記課題を解決するための本発明は、
銅源、ニッケル源、錯化剤および還元剤を含有するめっ
き液を用いて無電解銅ニッケル合金めっきを施す工程に
おいて、めっき液のｐＨを調整することによって合金め
っき被膜中の各元素の組成比を任意に変化させることを
特徴とする無電解銅ニッケル合金めっき方法である。That is, the present invention for solving the above problems is
In the step of performing electroless copper-nickel alloy plating using a plating solution containing a copper source, a nickel source, a complexing agent and a reducing agent, the composition ratio of each element in the alloy plating film is adjusted by adjusting the pH of the plating solution. Is an arbitrary method of electroless copper-nickel alloy plating.
【０００８】[0008]
【作用】次に本発明の詳細並びにその作用について述べ
る。本発明において、めっき液のｐＨ調節は通常の無電
解めっき液において用いられるアルカリ金属水酸化物水
溶液や鉱酸水溶液等の添加により行なう。めっき液のｐ
Ｈと得られる合金めっき被膜の組成との関係は、使用す
るめっき液の組成によって異なるために一義的に特定す
ることはできない。よって、実操業に際して使用するめ
っき液について事前に所望の合金組成が得られるｐＨ値
を確認しておくことが必要である。Next, the details of the present invention and its operation will be described. In the present invention, the pH of the plating solution is adjusted by adding an aqueous solution of an alkali metal hydroxide or an aqueous solution of a mineral acid which is used in a usual electroless plating solution. P of plating solution
The relationship between H and the composition of the alloy plating film obtained cannot be uniquely specified because it depends on the composition of the plating solution used. Therefore, it is necessary to confirm in advance the pH value with which the desired alloy composition can be obtained for the plating solution used in actual operation.
【０００９】本発明において、めっき液のｐＨ値を変化
させることによって合金めっき被膜中の銅とニッケルの
組成比を変化させることができる理由については明らか
ではない。しかし、めっき液に含まれる錯化剤の種類が
異なると、めっき液のｐＨ値を同じにしても合金めっき
被膜中の銅とニッケルの組成比が変化してしまうことか
ら、めっき液中に含まれる錯化剤とこれによって銅およ
びニッケルが形成する錯イオンの安定性とに何らかの関
係があるものと推定される。In the present invention, it is not clear why the composition ratio of copper and nickel in the alloy plating film can be changed by changing the pH value of the plating solution. However, if the type of complexing agent contained in the plating solution is different, the composition ratio of copper and nickel in the alloy plating film will change even if the pH value of the plating solution is the same. It is presumed that there is some relationship between the complexing agent formed and the stability of complex ions formed by copper and nickel.
【００１０】本発明において、めっき液には従来から無
電解銅ニッケル合金めっき法において一般的に使用され
ているめっき液、つまり銅源、ニッケル源、錯化剤およ
び還元剤の適量づつを混合したものが用いられる。ちな
みに銅源としては、例えば硫酸銅、塩化銅、水酸化銅、
硫化銅等が挙げられ、ニッケル源としては、例えば硫酸
ニッケル、塩化ニッケル等が挙げられ、錯化剤として
は、例えばクエン酸、アラニン、グリシン、リンゴ酸、
コハク酸等が挙げられる。また、還元剤も一般的なもの
でよいが、中性領域で本発明の方法を実施する際には特
にホスフィン酸ナトリウムのようなホスフィン酸塩やジ
メチルアミンボラン等を用いることが好ましい。そし
て、一般にこれらの物質の添加量はその目的に応じて適
宜定められているが、本発明の方法においては、このよ
うにして調製された一般的なめっき液の何れについても
適用が可能である。In the present invention, a plating solution which has been generally used in the conventional electroless copper-nickel alloy plating method, that is, a copper source, a nickel source, a complexing agent and an appropriate amount of a reducing agent are mixed in the plating solution. Things are used. Incidentally, as a copper source, for example, copper sulfate, copper chloride, copper hydroxide,
Copper sulfide and the like, nickel sources such as nickel sulfate, nickel chloride and the like, complexing agents such as citric acid, alanine, glycine, malic acid,
Examples include succinic acid and the like. Further, the reducing agent may be a common one, but when the method of the present invention is carried out in the neutral region, it is particularly preferable to use a phosphinic acid salt such as sodium phosphinate or dimethylamine borane. And, generally, the addition amounts of these substances are appropriately determined according to the purpose, but in the method of the present invention, it is possible to apply to any of the general plating solutions thus prepared. ..
【００１１】本発明の方法においては無電解銅ニッケル
合金めっき時におけるめっき液の温度は特に限定はない
が、めっき液をある程度加温することにより還元剤の作
用を促進できるという一般的な傾向は本発明の方法の実
施に際してそのまま適用できる。また、本発明における
被めっき物には、通常この種の無電解めっきを実施する
に際して一般的に行なわれる前処理が適用されることは
言うまでもない。In the method of the present invention, the temperature of the plating solution during electroless copper-nickel alloy plating is not particularly limited, but there is a general tendency that the action of the reducing agent can be promoted by heating the plating solution to some extent. It can be applied as it is when carrying out the method of the present invention. Further, it goes without saying that the object to be plated in the present invention is generally subjected to a pretreatment which is generally carried out when carrying out this type of electroless plating.
【００１２】[0012]
【実施例】次に本発明の無電解銅ニッケル合金めっき方
法についての実施例を掲げる。EXAMPLES Next, examples of the electroless copper-nickel alloy plating method of the present invention will be described.
【００１３】ポリイミド樹脂表面に常法による無電解め
っき前処理を施した後、表１に示すめっき液を使用し
て、これを１０重量％水酸化ナトリウム水溶液を添加量
を変えて添加してめっき液のｐＨを５〜１０の間で種々
変化させ、表１のめっき条件によって無電解銅ニッケル
合金めっきを行なった。After the pretreatment of the electroless plating on the surface of the polyimide resin by the conventional method, the plating solution shown in Table 1 was used, and the plating solution was added by adding a 10% by weight sodium hydroxide aqueous solution in various amounts. The pH of the solution was variously changed between 5 and 10, and electroless copper-nickel alloy plating was performed under the plating conditions shown in Table 1.
【００１４】[0014]
【表１】 （めっき液組成） ＣｕＳＯ４・５Ｈ２Ｏ ：０．００２５モル／ｌ ＮｉＳＯ４・６Ｈ２Ｏ ：０．１ モル／ｌ クエン酸３ナトリウム２水和物 ：０．２ モル／ｌ ホスフィン酸ナトリウム１水和物 ：０．３ モル／ｌ （めっき条件） 温 度 ：８０ ℃ 時 間 ：１０ 分 ｐＨ ：５〜１０の間で変化 得られた銅ニッケル合金めっき被膜の銅、ニッケルおよ
びリンの含有量を化学分析により測定し、これらの元素
の組成比とめっき液のｐＨ値との関係を図１に示した。
図１において縦軸はめっき合金中の各元素の組成比を、
また横軸はめっき液のｐＨ値を表わす。TABLE 1 (Composition of the plating solution) CuSO 4 · 5H 2 O: 0.0025 mol / l NiSO 4 · 6H 2 O : 0.1 mol / l trisodium citrate dihydrate: 0.2 mol / l Sodium phosphinate monohydrate: 0.3 mol / l (plating conditions) Temperature: 80 ° C Time: 10 minutes pH: Change between 5 and 10 Copper, nickel and copper of the obtained copper-nickel alloy plating film The phosphorus content was measured by chemical analysis, and the relationship between the composition ratio of these elements and the pH value of the plating solution is shown in FIG.
In FIG. 1, the vertical axis represents the composition ratio of each element in the plated alloy,
The horizontal axis represents the pH value of the plating solution.
【００１５】図１に示されるように合金めっき被膜中の
各元素の組成比は、めっき液のｐＨ値の変化とともに変
化するので、めっき液のｐＨ値を適宜調整することによ
って所望の組成比の合金めっき被膜を得ることが可能と
なる。また、図１より本発明の方法によるときは銅含有
量が９０％を超えるような高い値であっても、ニッケル
との組成比を任意に調整することができるので、例えば
ＴＡＢテープのように高電気伝導率が要求されるような
電子部品の作成に使用される無電解めっき基板における
めっき被膜として使用することが十分可能であることが
判かる。As shown in FIG. 1, the composition ratio of each element in the alloy plating film changes with the change of the pH value of the plating solution. Therefore, by appropriately adjusting the pH value of the plating solution, the desired composition ratio can be obtained. It is possible to obtain an alloy plating film. Further, from FIG. 1, according to the method of the present invention, the composition ratio with nickel can be arbitrarily adjusted even if the copper content is as high as more than 90%. It can be seen that it can be sufficiently used as a plating film in an electroless plating substrate used in the production of electronic components that require high electrical conductivity.
【００１６】なお、図１より合金めっき被膜中のリンの
含有割合がニッケルの含有割合の増加に伴い、僅かづつ
増加することが示されているが、液組成との定量的な関
係は見出されていない。Although FIG. 1 shows that the phosphorus content in the alloy plating film increases little by little as the nickel content increases, a quantitative relationship with the liquid composition was found. It has not been.
【００１７】[0017]
【発明の効果】以上述べたように本発明の無電解銅ニッ
ケル合金めっき方法によるときは、合金めっき被膜層中
の銅の含有量如何に拘らず合金めっき元素の組成比を簡
単な方法で任意に変化させることができるので、優れた
電気伝導率と耐食性を兼ね具えた電気導通性めっき層を
有する基板を容易に提供することができるので電子部品
の作成に広く応用することができる。As described above, according to the electroless copper-nickel alloy plating method of the present invention, the composition ratio of the alloy plating elements can be arbitrarily set regardless of the content of copper in the alloy plating film layer. Since it can be changed to, it is possible to easily provide a substrate having an electrically conductive plating layer having both excellent electrical conductivity and corrosion resistance, and therefore it can be widely applied to the production of electronic parts.
【図１】本発明の無電解銅ニッケル合金めっき方法にお
ける合金めっき被膜中の各元素の組成比とめっき液のｐ
Ｈ値との関係を示す図面である。FIG. 1 shows the composition ratio of each element in the alloy plating film and p of the plating solution in the electroless copper-nickel alloy plating method of the present invention.
It is drawing which shows the relationship with H value.
Claims (1)
を含有するめっき液を用いて無電解銅ニッケル合金めっ
きを施す工程において、めっき液のｐＨ値を調整するこ
とによって合金めっき被膜中の各元素の組成比を任意に
変化させることを特徴とする無電解銅ニッケル合金めっ
き方法。1. In an alloy plating film by adjusting a pH value of a plating solution in a step of performing electroless copper-nickel alloy plating using a plating solution containing a copper source, a nickel source, a complexing agent and a reducing agent. 2. A method for electroless copper-nickel alloy plating, which comprises arbitrarily changing the composition ratio of each element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25436691A JPH06104902B2 (en) | 1991-09-06 | 1991-09-06 | Electroless copper nickel alloy plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25436691A JPH06104902B2 (en) | 1991-09-06 | 1991-09-06 | Electroless copper nickel alloy plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0565659A true JPH0565659A (en) | 1993-03-19 |
| JPH06104902B2 JPH06104902B2 (en) | 1994-12-21 |
Family
ID=17263993
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25436691A Expired - Fee Related JPH06104902B2 (en) | 1991-09-06 | 1991-09-06 | Electroless copper nickel alloy plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06104902B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006052460A (en) * | 2004-07-15 | 2006-02-23 | Sekisui Chem Co Ltd | Conductive microparticle, process for producing the same, and anisotropic conductive material |
| US7200474B2 (en) | 2003-12-16 | 2007-04-03 | Honda Motor Co., Ltd. | Vehicle occupant protection apparatus |
| US7507477B2 (en) | 2004-07-15 | 2009-03-24 | Sekisui Chemical Co., Ltd. | Conductive microparticle, process for producing the same and anisotropic conductive material |
| US20140076798A1 (en) * | 2010-06-30 | 2014-03-20 | Schauenburg Ruhrkunststoff Gmbh | Tribologically Loadable Mixed Noble Metal/Metal Layers |
| CN104975277A (en) * | 2015-06-10 | 2015-10-14 | 上海大学 | Preparation method of copper/nickel iron phosphorus alloy plating double-plating-layer fabric |
-
1991
- 1991-09-06 JP JP25436691A patent/JPH06104902B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7200474B2 (en) | 2003-12-16 | 2007-04-03 | Honda Motor Co., Ltd. | Vehicle occupant protection apparatus |
| JP2006052460A (en) * | 2004-07-15 | 2006-02-23 | Sekisui Chem Co Ltd | Conductive microparticle, process for producing the same, and anisotropic conductive material |
| US7507477B2 (en) | 2004-07-15 | 2009-03-24 | Sekisui Chemical Co., Ltd. | Conductive microparticle, process for producing the same and anisotropic conductive material |
| US20140076798A1 (en) * | 2010-06-30 | 2014-03-20 | Schauenburg Ruhrkunststoff Gmbh | Tribologically Loadable Mixed Noble Metal/Metal Layers |
| CN104975277A (en) * | 2015-06-10 | 2015-10-14 | 上海大学 | Preparation method of copper/nickel iron phosphorus alloy plating double-plating-layer fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06104902B2 (en) | 1994-12-21 |
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| LAPS | Cancellation because of no payment of annual fees |