JPH05311495A - Hole sealing treatment of noble metal plated material - Google Patents
Hole sealing treatment of noble metal plated materialInfo
- Publication number
- JPH05311495A JPH05311495A JP34315891A JP34315891A JPH05311495A JP H05311495 A JPH05311495 A JP H05311495A JP 34315891 A JP34315891 A JP 34315891A JP 34315891 A JP34315891 A JP 34315891A JP H05311495 A JPH05311495 A JP H05311495A
- Authority
- JP
- Japan
- Prior art keywords
- sealing treatment
- sealing
- acid
- metal
- plated material
- 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.)
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Links
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- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は貴金属めっき電気接点の
封孔処理液、封孔処理方法及び封孔処理されたコネクタ
接触子に関する。特に潤滑、防錆及び電気的接続性が長
期的に安定して優れる封孔処理液、封孔処理方法及び封
孔処理されたコネクタ接触子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing treatment liquid for noble metal plated electrical contacts, a sealing treatment method, and a sealed connector contact. In particular, the present invention relates to a sealing treatment liquid, a sealing treatment method, and a connector contact having a sealing treatment, which are excellent in lubricity, rust prevention, and electrical connectivity and are stable for a long period of time.
【０００２】[0002]
【従来の技術】電子機器用接続部品としてコネクタは最
も代表的なものであり、多種多様のコネクタが実用化さ
れている。電算機や電信用機器等高度の信頼性が要求さ
れるいわゆる産業用電子機器に使用されるコネクタは、
りん青銅、ベリリウム銅等のバネ用銅合金を母材とし、
貴金属めっきをしたものが一般に利用されている。しか
し、貴金属は高価であるため、コネクタ製造コストを下
げる目的で様々な方法が採られてきた。その代表的な方
法が貴金属めっきの厚みを薄くする方法であるが、貴金
属めっきの厚みを薄くするとともに被膜のピンホールが
指数関数的に増え、耐食性が著しく低下するという問題
を抱えている。この問題を解決する方法のひとつに封孔
処理がある。すなわち、各種の無機性あるいは有機性の
薬品で貴金属めっき表面を処理し、ピンホールを塞ぎ、
耐食性を向上させようとするものである。封孔処理には
水系と有機系がある。水系はクロメート法が代表的であ
り、効果はあるが接触抵抗が上昇する場合があり、ま
た、環境汚染の問題がある。有機系は、一般的にはハロ
ゲン系有機溶剤が溶媒が使われているが環境汚染の問題
がある。環境汚染性において水系の方が有利であるが、
クロメート法以外では効果が低い。2. Description of the Related Art A connector is the most typical one as a connecting part for electronic equipment, and various types of connectors have been put to practical use. Connectors used for so-called industrial electronic devices that require a high degree of reliability, such as computers and electronic credit devices,
Base material is a spring copper alloy such as phosphor bronze or beryllium copper,
Those plated with noble metal are generally used. However, since precious metals are expensive, various methods have been adopted in order to reduce the manufacturing cost of connectors. A typical method therefor is to reduce the thickness of the noble metal plating. However, there is a problem that the thickness of the noble metal plating is reduced and the number of pinholes in the coating increases exponentially, resulting in a significant decrease in corrosion resistance. One of the methods for solving this problem is a sealing treatment. That is, the precious metal plating surface is treated with various inorganic or organic chemicals to block the pinholes,
It is intended to improve the corrosion resistance. There are water-based and organic-based sealing treatments. The chromate method is typically used for the water system, and although it is effective, the contact resistance may increase and there is a problem of environmental pollution. As the organic type, a halogen type organic solvent is generally used, but there is a problem of environmental pollution. Water is more advantageous in terms of environmental pollution,
The effect is low except for the chromate method.
【０００３】[0003]
【発明が解決しようとする課題】封孔処理、特に有機性
薬品による封孔処理は、貴金属めっき被膜の厚みの低減
に対し、耐食性を維持する効果が優れている。しかし、
上記のように有機性封孔処理液は、一般的に溶媒がハロ
ゲン系有機溶剤であるため、環境汚染性に問題がある。
環境汚染性においては有機系よりも溶媒が水である水系
の方が有利であるが、クロメート法以外では効果が低
く、封孔効果が不十分である。そこで、環境汚染性に問
題が無く、かつ従来と同等もしくはそれ以上の封孔効果
を有する封孔処理液及び封孔処理方法が必要となってい
る。The sealing treatment, particularly the sealing treatment with an organic chemical, has an excellent effect of maintaining the corrosion resistance against the reduction of the thickness of the noble metal plating film. But,
As described above, since the organic sealing treatment liquid is generally a halogen-based organic solvent, it has a problem in environmental pollution.
In terms of environmental pollution, an aqueous system in which the solvent is water is more advantageous than an organic system, but other than the chromate method, the effect is low and the sealing effect is insufficient. Therefore, there is a need for a sealing treatment liquid and a sealing treatment method which have no problem of environmental pollution and have a sealing effect equal to or higher than conventional ones.
【０００４】本発明は、このような要求を満たすことの
できる改善された封孔処理液及びそれを用いる封孔処理
方法を提供することを目的とし、あわせてそれによって
処理されたコネクタを提供することを目的とするもので
ある。An object of the present invention is to provide an improved sealing treatment liquid and a sealing treatment method using the same which can meet such requirements, and also to provide a connector treated therewith. The purpose is that.
【０００５】[0005]
【課題を解決するための手段】かかる状況に鑑み、本発
明者等は鋭意研究を行った結果、以下に示す封孔処理方
法及び封孔処理されためっき材及びコネクタを発明する
に至った。すなわち、本発明は、（１）金、銀、ロジウ
ム、パラジウム、ルテニウム及びこれらの合金めっき材
を、その下地金属または下地金属成分の１種もしくは２
種以上について腐食抑制効果を有する有機化合物を含有
する水溶液中で、超音波を照射しながら該めっき材を陽
極として直流電解する貴金属めっき材の封孔処理方法、
（２）前記封孔処理法により封孔処理されためっき材、
及び（３）前記処理方法により封孔処理された接触子で
ある。In view of the above situation, the inventors of the present invention have made earnest studies and, as a result, have invented a sealing treatment method, and a plated material and a connector subjected to the sealing treatment described below. That is, the present invention provides (1) gold, silver, rhodium, palladium, ruthenium, or an alloy plating material thereof, as a base metal or a base metal component thereof, or 2
In an aqueous solution containing an organic compound having a corrosion inhibition effect for more than one species, a method for sealing a noble metal plated material, in which direct current electrolysis is performed while irradiating ultrasonic waves with the plated material as an anode,
(2) A plated material that has been subjected to a sealing treatment by the sealing treatment method,
And (3) the contactor which has been subjected to a sealing treatment by the above treatment method.
【０００６】本発明における下地金属とは、貴金属めっ
きの下地めっき及び素材金属までも包含するものであ
る。本発明は、被処理材を陽極として直流電解すること
で貴金属めっきピンホール内部の被処理材の下地金属を
溶出し、下地金属及び溶出した金属と有機成分が反応
し、強固な被膜を作成し、封孔処理をもたせる処理方法
である。封孔処理水溶液のｐＨは、７．０より大である
ことが好ましい。これは封孔処理の際、電解によって被
処理材表面のｐＨは液中のｐＨより低くなり、封孔処理
液のｐＨが７．０以下の場合、被処理材表面のｐＨが低
くなり過ぎて下地金属の溶出量が多く、また、有機成分
の配位力が弱くなるため好ましくないからである。ｐＨ
調整は、公知の緩衝溶液を用いて行ない、その緩衝溶液
については何等制限されない。陽極電流密度は、０．３
Ａ／ｄｍ2以上が好ましい。０．３Ａ／ｄｍ2未満の場
合、下地金属の溶出が小さいため強固な封孔処理被膜が
得られないからである。通電量は、０．１５クーロン／
ｄｍ2以上が好ましい。０．１５クーロン／ｄｍ2未満で
は、封孔処理被膜が充分に形成されないため、封孔処理
効果が小さいからである。封孔処理の処理温度は何等制
限されないが、高温の方が乾燥が容易であるため６０〜
８０℃程度が望ましい。The base metal in the present invention includes a base metal of noble metal plating and a raw material metal. The present invention elutes the base metal of the material to be treated inside the noble metal plated pinhole by subjecting the material to be treated as an anode to direct current electrolysis, and the base metal and the eluted metal react with the organic component to form a strong coating. This is a treatment method that has a sealing treatment. The pH of the sealing treatment aqueous solution is preferably higher than 7.0. This is because during the sealing treatment, the pH of the surface of the material to be treated becomes lower than the pH in the liquid due to electrolysis, and when the pH of the sealing treatment liquid is 7.0 or less, the pH of the surface of the material to be treated becomes too low. This is because the amount of the base metal eluted is large and the coordinating force of the organic component becomes weak, which is not preferable. pH
The adjustment is performed using a known buffer solution, and the buffer solution is not limited in any way. Anode current density is 0.3
A / dm 2 or more is preferable. If it is less than 0.3 A / dm 2 , the elution of the base metal is small and a strong sealing film cannot be obtained. The amount of electricity is 0.15 coulomb /
dm 2 or more is preferable. If it is less than 0.15 coulomb / dm 2 , the sealing treatment film is not sufficiently formed, so that the sealing treatment effect is small. Although the treatment temperature of the sealing treatment is not limited in any way, the higher temperature is easier to dry, so
About 80 ° C is desirable.
【０００７】本発明において使用する腐食抑制効果を有
する有機化合物としては、以下に示す有機化合物が好ま
しい。The following organic compounds are preferable as the organic compound having a corrosion inhibiting effect used in the present invention.
【０００８】すなわち、含窒素環式化合物、イミノ酸誘
導体、エチレンジアミン、エチレンジアミン四酢酸、グ
ルコン酸、ニトロトリ酢酸、ヒドロオキシエチル、エチ
レンジアミン三酢酸、ジエチレントリアミン五酢酸、炭
素数６〜３０を有し、かつα位にＯＨ基を有するモノカ
ルボン酸、及びその誘導体、炭素数６〜３０を有する高
級脂肪酸の金属塩、アルキル置換ナフタレンスルフォン
酸塩、炭素数６〜３０を有するアミンの１種もしくは２
種以上である。That is, it has a nitrogen-containing cyclic compound, an imino acid derivative, ethylenediamine, ethylenediaminetetraacetic acid, gluconic acid, nitrotriacetic acid, hydroxyethyl, ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, a carbon number of 6 to 30, and α One or two of monocarboxylic acid having OH group at the position and its derivative, metal salt of higher fatty acid having 6 to 30 carbon atoms, alkyl-substituted naphthalene sulfonate, amine having 6 to 30 carbon atoms
It is more than a seed.
【０００９】含窒素環式化合物としては、As the nitrogen-containing cyclic compound,
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】（上記各式中、Ｒ1は水素、アルキル、置
換アルキルを表し、Ｒ2はアルカリ金属、水素、アルキ
ル、置換アルカリを表す）等を挙げることができる。(In the above formulas, R 1 represents hydrogen, alkyl or substituted alkyl, and R 2 represents alkali metal, hydrogen, alkyl or substituted alkali) and the like.
【００１２】ベンゾトリアゾール系としては、ベンゾト
リアゾール（Ｒ1、Ｒ2ともに水素）、１−メチルベンゾ
トリアゾール（Ｒ1が水素、Ｒ2がメチル）、１−（Ｎ，
Ｎ−ジオクチルアミノメチル）ベンゾトリアゾール（Ｒ
1が水素、Ｒ2がＮ，Ｎ−ジオクチルアミノメチル）、ト
リルトリアゾール（Ｒ1がメチル、Ｒ2が水素）、ソディ
ウムトリルトリアゾール（Ｒ1がメチル、Ｒ2がナトリウ
ム）等が望ましい。The benzotriazole type compounds include benzotriazole (both R 1 and R 2 are hydrogen), 1-methylbenzotriazole (R 1 is hydrogen, R 2 is methyl), 1- (N,
N-dioctylaminomethyl) benzotriazole (R
1 is hydrogen, R 2 is N, N-dioctylaminomethyl), tolyltriazole (R 1 is methyl, R 2 is hydrogen), sodium tolyltriazole (R 1 is methyl, R 2 is sodium) and the like are preferable.
【００１３】インダゾール系としては、例えばインダゾ
ール（Ｒ1、Ｒ2ともに水素）、２−メチルインダゾール
（Ｒ1が水素、Ｒ2がメチル）、２−ベンジルインダゾー
ル（Ｒ1が水素、Ｒ2がＣ6Ｈ5ＣＨ2）、１−アセチルイ
ンダゾール（Ｒ1が水素、Ｒ2がＣＯＣＨ3）等が好まし
い。Examples of the indazole type include indazole (both R 1 and R 2 are hydrogen), 2-methylindazole (R 1 is hydrogen, R 2 is methyl), 2-benzylindazole (R 1 is hydrogen, R 2 is C). 6 H 5 CH 2 ), 1-acetylindazole (R 1 is hydrogen, R 2 is COCH 3 ) and the like are preferable.
【００１４】ベンズイミダゾール系としては、例えばベ
ンズイミダゾール（Ｒ1、Ｒ2ともに水素）、Ｎ−アセチ
ルベンズイミダゾール（Ｒ1が水素、Ｒ2がＣＯＣ
Ｈ3）、Ｎ−ベンゾイルベンズイミダゾール（Ｒ1が水
素、Ｒ2がＣＯＣ6Ｈ5）等が好ましい。Examples of the benzimidazole type compounds include benzimidazole (both R 1 and R 2 are hydrogen), N-acetylbenzimidazole (R 1 is hydrogen, R 2 is COC).
H 3), N-benzoyl benzimidazole (R 1 is hydrogen, R 2 is COC 6 H 5) are preferred.
【００１５】インドール系としては、例えばインドール
（Ｒ1、Ｒ2ともに水素）、インドール−１−カルボン酸
（Ｒ1が水素、Ｒ2がＣＯＯＨ）、１−メチルインドール
（Ｒ1が水素、Ｒ2がＣＨ3）等が好ましい。Examples of the indole system include indole (both R 1 and R 2 are hydrogen), indole-1-carboxylic acid (R 1 is hydrogen, R 2 is COOH), 1-methylindole (R 1 is hydrogen, R 2 Is preferably CH 3 ).
【００１６】また、１，３，５−トリアジン系化合物と
しては、例えば６−置換−１，３，５−トリアジンチオ
ール−ナトリウム塩The 1,3,5-triazine compound is, for example, 6-substituted-1,3,5-triazinethiol-sodium salt.
【００１７】[0017]
【化２】 [Chemical 2]
【００１８】（Ｒは−ＳＨ、またはアルキル基又はアリ
ール基で置換されたアミノ基で、たとえば−ＮＨＣ
Ｈ3、−ＮＨＣ2Ｈ5、−Ｎ（ＣＨ3）2、−Ｎ（Ｃ
2Ｈ5）2、−ＮＨＣ6Ｈ5、−Ｎ（Ｃ4Ｈ9）2、−Ｎ（Ｃ8
Ｈ17）2、−Ｎ（Ｃ12Ｈ24）2、−Ｎ（ＣＨ2ＣＨ＝Ｃ
Ｈ2）2、−ＮＨＣ8Ｈ16ＣＨ＝ＣＨＣ8Ｈ17等が好まし
い。）シアヌル酸（２，４，６−トリオキシ−１，３，
５−トリアジン）、(R is --SH, or an amino group substituted with an alkyl group or an aryl group, for example --NHC.
H 3, -NHC 2 H 5, -N (CH 3) 2, -N (C
2 H 5) 2, -NHC 6 H 5, -N (C 4 H 9) 2, -N (C 8
H 17) 2, -N (C 12 H 24) 2, -N (CH 2 CH = C
H 2) 2, etc. -NHC 8 H 16 CH = CHC 8 H 17 are preferable. ) Cyanuric acid (2,4,6-trioxy-1,3,3
5-triazine),
【００１９】[0019]
【化３】 [Chemical 3]
【００２０】メラミン系化合物（２置換−４，６ジアミ
ノ−１，３，５−トリアジン）Melamine compound (2-substituted-4,6 diamino-1,3,5-triazine)
【００２１】[0021]
【化４】 [Chemical 4]
【００２２】｛Ｒは−ＮＨ2、{R is --NH 2 ,
【００２３】[0023]
【化５】 [Chemical 5]
【００２４】（Ｒ’はＣＨ3、Ｃ2Ｈ5、Ｃ11Ｈ23等のア
ルキル基）｝を挙げることができる。(R ′ is an alkyl group such as CH 3 , C 2 H 5 and C 11 H 23 )}.
【００２５】イミノ酸誘導体としては、イミノジアセト
ニトリル｛ＮＨ−（ＣＨ2ＣＮ）2｝、イミノジカルボン
酸｛ＮＨ−（ＣＯＯＨ）2｝、イミノジ酢酸｛ＮＨ−
（ＣＨ2ＣＯＯＨ）2｝等が好ましい。Examples of the imino acid derivative include imino diacetonitrile {NH- (CH 2 CN) 2 }, imino dicarboxylic acid {NH- (COOH) 2 }, imino diacetic acid {NH-
(CH 2 COOH) 2 } and the like are preferable.
【００２６】又、エチレンジアミン、エチレンジアミン
四酢酸（ＥＤＴＡ）、グルコン酸、ニトロトリ酢酸（Ｎ
ＴＡ）、ヒドロキシエチルエチレンジアミン三酢酸（Ｈ
ＥＤＴＡ）、ジエチレントリアミン五酢酸（ＤＴＰＡ）
等も本発明に使用する封孔処理液成分として有効であ
る。Further, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), gluconic acid, nitrotriacetic acid (N
TA), hydroxyethyl ethylenediamine triacetic acid (H
EDTA), diethylenetriaminepentaacetic acid (DTPA)
Etc. are also effective as a component of the sealing treatment liquid used in the present invention.
【００２７】本発明封孔処理液の成分として有効である
炭素数６〜３０を有し、かつα位にＯＨを有するモノカ
ルボン酸の一般式は、The general formula of a monocarboxylic acid having 6 to 30 carbon atoms and having OH at the α-position, which is effective as a component of the sealing treatment liquid of the present invention, is as follows:
【００２８】[0028]
【化６】 [Chemical 6]
【００２９】で示される。例えばマレイン酸、オレイン
酸、ナフテン酸等を挙げることができる。Ｃ6〜Ｃ30か
つα位にＯＨを有するモノカルボン酸の誘導体として
は、ヌカ油マレイン化物、ナフテン酸ナトリウム等を挙
げることができる。It is shown by. Examples thereof include maleic acid, oleic acid, naphthenic acid and the like. Examples of the monocarboxylic acid derivative having C 6 to C 30 and OH in the α-position include maleic oil of nuka oil and sodium naphthenate.
【００３０】炭素数６〜３０を有する高級脂肪酸の金属
塩としては、例えばステアリン酸金属塩、ラウリン酸金
属塩、リシノレン酸金属塩、ミリスチン酸金属塩、オレ
イン酸金属塩、ナフテン酸金属塩及びナフテン酸金属塩
等を挙げることができ、また、その金属塩としては制限
はないが、カルシウム、アルミニウム、バリウム、鉛塩
等が好ましい。Examples of metal salts of higher fatty acids having 6 to 30 carbon atoms include metal stearates, metal laurates, ricinolenic acid metal salts, myristic acid metal salts, oleic acid metal salts, naphthenic acid metal salts and naphthenes. Examples thereof include acid metal salts, and the metal salts are not particularly limited, but calcium, aluminum, barium, lead salts and the like are preferable.
【００３１】アルキル置換ナフタレンスルフォン酸塩と
しては、ジノリルナフタレンスルフォン酸バリウム塩、
ジノリルナフタレンスルフォン酸カルシウム塩、ジノリ
ルナフタレンスルフォン酸亜鉛塩、ジノリルナフレンス
ルフォン酸バリウム塩基性塩、ジノリルナフタレンスル
フォン酸エチレンジアミン塩、ジノリルナフタレンスル
フォン酸ナトリウム塩、ジノリルナフタレンスルフォン
酸リチウム塩、ジノリルナフタレンスルフォン酸鉛塩、
ジノリルナフタレンスルフォン酸アンモニウム塩、ジノ
リルナフタレンスルフォン酸トリエタノールアミン塩等
を挙げることができる。Alkyl-substituted naphthalene sulfonates include barium dinolyl naphthalene sulfonates,
Calcium salt of dinolylnaphthalene sulfonic acid, zinc salt of dinolyl naphthalene sulfonic acid, basic salt of dinolyl naphthalene sulfonic acid barium salt, dinolyl naphthalene sulfonic acid ethylenediamine salt, dinolyl naphthalene sulfonic acid sodium salt, dinolyl naphthalene sulfonic acid lithium salt, Dinolyl naphthalene sulfonic acid lead salt,
Examples thereof include ammonium dinolylnaphthalene sulfonic acid, triethanolamine dinolyl naphthalene sulfonic acid, and the like.
【００３２】炭素数６〜３０を有するアミンとしては、
オクタデシルアミン、ドデシルアミン、デシルアミン、
オクチルアミン及びシクロヘキシルアミン等を挙げるこ
とができる。As the amine having 6 to 30 carbon atoms,
Octadecylamine, dodecylamine, decylamine,
Examples thereof include octylamine and cyclohexylamine.
【００３３】本発明封孔処理液の成分として界面活性剤
を添加することは、本発明封孔処理液と被処理材との湿
潤性を向上させることに有効であり、何等制限されな
い。また、本発明封孔処理液の成分として潤滑剤を添加
することは、本発明封孔処理材の摩擦軽減に有効であ
り、何等制限されない。The addition of a surfactant as a component of the sealing treatment liquid of the present invention is effective in improving the wettability between the sealing treatment liquid of the present invention and the material to be treated, and is not limited in any way. Further, addition of a lubricant as a component of the sealing treatment liquid of the present invention is effective in reducing the friction of the sealing treatment material of the present invention and is not limited in any way.
【００３４】めっき品をプレス加工後に本発明の封孔処
理液及び封孔処理方法で封孔処理することも有効であ
る。めっき後封孔処理した金属材料であっても、その後
のプレス加工で付着したプレス油を洗浄する工程におい
て、封孔処理の効果が低下する。そこで再度の封孔処理
が有効となる。It is also effective to perform a pore-sealing treatment with the pore-sealing liquid and the pore-sealing method of the present invention after pressing the plated product. Even with a metal material that has been subjected to a pore-sealing treatment after plating, the effect of the pore-sealing treatment decreases in the step of washing the press oil that has adhered in the subsequent press working. Therefore, the sealing treatment again becomes effective.
【００３５】その後のコネクタの加工工程においても、
最終の電子機器組立まで、めっき品の洗浄工程があれば
同様に封孔処理効果は低下するため、適宜本発明により
封孔処理することが有効である。さらには電子機器に組
み込まれた後、使用量に伴い封孔処理効果が低下する場
合、適宜本発明方法によって処理することができる。従
って、本発明は本発明封孔処理方法によって処理された
コネクタも包含するものである。Also in the subsequent connector processing steps,
If there is a step of washing the plated product until the final electronic device is assembled, the effect of the sealing treatment is similarly reduced. Therefore, it is effective to appropriately perform the sealing treatment according to the present invention. Furthermore, when the sealing treatment effect decreases with the amount used after being incorporated in an electronic device, it can be appropriately treated by the method of the present invention. Therefore, the present invention also includes a connector processed by the sealing method of the present invention.
【００３６】なお、本発明におけるめっき母材となる金
属材料は、銅、黄銅、りん青銅、チタン銅、ベリリウム
銅等の各種銅合金、鉄、ステンレス鋼、高ニッケル合金
等のコネクタ等のめっき材の要求特性に従い、適宜選択
でき、何等制限されない。又、下地めっきについては、
ニッケル、ニッケル−コバルト、パラジウム−ニッケ
ル、錫−ニッケル、銀等が用いられ、特にニッケルが好
ましい。めっき材のめっき方法については、電気メッ
キ、無電解めっき、あるいはＣＶＤ、ＰＶＤ等の乾式め
っき等の公知のものを適用でき、制限されない。The metal material used as the plating base material in the present invention is copper, brass, phosphor bronze, titanium copper, beryllium copper, or other various copper alloys, iron, stainless steel, high nickel alloys, or other plating materials such as connectors. Can be appropriately selected according to the required characteristics of, and is not limited in any way. Also, regarding the base plating,
Nickel, nickel-cobalt, palladium-nickel, tin-nickel, silver or the like is used, and nickel is particularly preferable. A known plating method such as electroplating, electroless plating, or dry plating such as CVD or PVD can be applied to the plating method of the plating material, and is not limited.
【００３７】[0037]
【実施例】以下に実施例を挙げて本発明を更に詳細に説
明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
【００３８】バネ用りん青銅（Ｃ５２１０−Ｈ）の厚み
０．２ｍｍの冷間圧延材を用い、雄及び雌の連続端子を
それぞれプレス成形した。これらをリール・ツウ・リー
ルの連続電気めっきラインを通して電気めっきを施し
た。めっきラインにおいては、脱脂、酸洗後、ワット浴
により１μｍのニッケルめっきを行ない、その上に金を
０．１μｍの厚みで接点部に部分めっきした。また、連
続めっきラインでは、金めっき後に封孔処理工程を設
け、連続端子を通入することにより７０℃で封孔処理を
施した。封孔処理液のｐＨは、緩衝溶液を用いて調整し
た。Male and female continuous terminals were press-molded using a 0.2 mm-thick cold rolled material of spring phosphor bronze (C5210-H). These were electroplated through a reel-to-reel continuous electroplating line. In the plating line, after degreasing and pickling, 1 μm nickel plating was performed in a Watts bath, and gold was partially plated on the contact portion with a thickness of 0.1 μm. Further, in the continuous plating line, a sealing treatment step was provided after gold plating, and the continuous terminal was inserted to perform the sealing treatment at 70 ° C. The pH of the sealing treatment liquid was adjusted using a buffer solution.
【００３９】こうして表面処理をした雄と雌の端子をキ
ャリアー部から切断しリード線を圧着した後、それぞれ
を嵌合し評価試験に供した。After the surface-treated male and female terminals were cut from the carrier and the lead wires were crimped, they were fitted together and subjected to an evaluation test.
【００４０】接触抵抗は直流１０ｍｍＡ、開放電圧５０
ｍｍＶで測定した。腐食条件は次の条件で行った。Contact resistance is DC 10 mmA, open voltage 50
It was measured in mmV. The corrosion conditions were as follows.
【００４１】ガス組成：Ｈ2Ｓ ３ｐｐｍ ＳＯ2 １０ｐｐｍ 温 度 ：４０±２℃ 湿 度 ：８０±５％ＲＨ 時 間 ：２４０時間 結果を表１に示す。Gas composition: H 2 S 3 ppm SO 2 10 ppm Temperature: 40 ± 2 ° C. Humidity: 80 ± 5% RH time: 240 hours The results are shown in Table 1.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】注１）ただし、表中封孔処理液の略号は以
下の通りである。Note 1) However, the abbreviations of the sealing treatment liquid in the table are as follows.
【００４５】Ａ−１：ベンゾトリアゾール Ａ−２：１−メチルベンゾトリアゾール Ａ−３：トリルトリアゾール Ａ−４：インダゾール Ａ−５：ベンズイミダゾール Ａ−６：インドール Ａ−７：１，３，５−トリアジン−２，４，６−トリチ
オールモノナトリウム Ａ−８：６−ジメチルアミノ−１，３，５−トリアジン
−２，４−ジチオールモノナトリウム Ａ−９：シアヌル酸 Ａ−１０：メラミン Ａ−１１：イミノジアセトニトリル Ａ−１２：イミノジカルボン酸 Ａ−１３：イミノジ酢酸 Ａ−１４：エチレンジアミン Ａ−１５：エチレンジアミン四酢酸 Ａ−１６：ニトロトリ酢酸 Ａ−１７：ヒドロオキシエチル、エチレンジアミン三酢
酸 Ａ−１８：ジエチレントリアミン五酢酸 Ｂ−１：マレイン酸 Ｂ−２：オレイン酸 Ｂ−３：ナフテン酸 Ｂ−４：ステアリン酸バリウム Ｂ−５：ラウリル酸バリウム Ｂ−６：オレイン酸カルシウム Ｂ−７：ナフテン酸カルシウム Ｂ−８：ジノリルナフタレンスルフォン酸バリウム Ｂ−９：ジノリルナフタレンスルフォン酸リチウム Ｂ−１０：ジノリルナフタレンスルフォン酸トリエタノ
ールアミン Ｂ−１１：オクタデシルアミン Ｂ−１２：ドデシルアミン Ｂ−１３：デシルアミン 注２）試験の判定基準は次のとおりである。A-1: benzotriazole A-2: 1-methylbenzotriazole A-3: tolyltriazole A-4: indazole A-5: benzimidazole A-6: indole A-7: 1,3,5- Triazine-2,4,6-trithiol monosodium A-8: 6-Dimethylamino-1,3,5-triazine-2,4-dithiol monosodium A-9: Cyanuric acid A-10: Melamine A-11 : Iminodiacetonitrile A-12: iminodicarboxylic acid A-13: iminodiacetic acid A-14: ethylenediamine A-15: ethylenediaminetetraacetic acid A-16: nitrotriacetic acid A-17: hydroxyethyl, ethylenediaminetriacetate A-18: Diethylenetriamine pentaacetic acid B-1: Maleic acid B-2: Oleic acid B-3: Na Tenic acid B-4: Barium stearate B-5: Barium laurate B-6: Calcium oleate B-7: Calcium naphthenate B-8: Barium dinolylnaphthalene sulfonate B-9: Lithium dinolynaphthalene sulfonate B-10: Triethanolamine dinolylnaphthalene sulfonic acid B-11: Octadecylamine B-12: Dodecylamine B-13: Decylamine Note 2) The criteria for the test are as follows.
【００４６】 初期接触抵抗、腐食試験後の接触抵抗
（ｎ＝５の平均値） Ａ ：１０ｍｍΩ以下 Ｂ ：１０〜２０ｍｍΩ Ｃ ：２０〜５０ｍｍΩ Ｄ ：５０〜１００ｍｍΩ Ｅ ：１００ｍｍΩ以上 腐食試験後の外観 Ａ ：腐食生成物なし Ｂ ：腐食生成物点在 Ｃ ：腐食点が全面に認められるInitial contact resistance, contact resistance after corrosion test (average value of n = 5) A: 10 mmΩ or less B: 10 to 20 mmΩ C: 20 to 50 mmΩ D: 50 to 100 mmΩ E: 100 mmΩ or more Appearance after corrosion test A : No corrosion products B: Corrosion products scattered C: Corrosion points are observed on the entire surface
【００４７】[0047]
【発明の効果】以上述べたように、本発明により封孔処
理された貴金属めっき材は、封孔処理直後の接触抵抗が
低く、過酷な腐食環境においても優れた耐食性を示し、
接触抵抗が上昇せず、接触性能が安定しているという利
点を有する。As described above, the noble metal plating material which has been subjected to the sealing treatment according to the present invention has a low contact resistance immediately after the sealing treatment and exhibits excellent corrosion resistance even in a severe corrosive environment.
It has advantages that the contact resistance does not increase and the contact performance is stable.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２５Ｄ 5/48 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location C25D 5/48
Claims (5)
ウム及びこれらの合金めっき材を、その下地金属または
下地金属成分の１種もしくは２種以上について腐食抑制
効果を有する有機化合物を含有する水溶液中で、超音波
を照射しながら該めっき材を陽極として直流電解するこ
とを特徴とする貴金属めっき材の封孔処理方法。1. An aqueous solution containing gold, silver, rhodium, palladium, ruthenium and an alloy plating material thereof, which contains an organic compound having a corrosion-inhibiting effect on the underlying metal or one or more of the underlying metal components. A method for sealing a noble metal plating material, which comprises subjecting the plating material to direct current electrolysis using the plating material as an anode while irradiating ultrasonic waves.
７．０より大である請求項１記載の封孔処理方法。2. The sealing treatment method according to claim 1, wherein the pH of the aqueous solution containing the organic compound is higher than 7.0.
ｍ2以上、通電量が０．１５クーロン／ｄｍ2以上で実施
する請求項１記載の封孔処理方法。3. A direct current electrolysis with an anode current density of 0.3 A / d
The sealing method according to claim 1, wherein the sealing treatment is performed at m 2 or more and an energization amount of 0.15 coulomb / dm 2 or more.
により封孔処理されためっき材。4. A plated material which has been subjected to a sealing treatment by the sealing treatment method according to claim 1, 2 or 3.
により封孔処理されたコネクタ接触子。5. A connector contact which has been subjected to a sealing treatment by the sealing treatment method according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34315891A JPH05311495A (en) | 1991-12-25 | 1991-12-25 | Hole sealing treatment of noble metal plated material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34315891A JPH05311495A (en) | 1991-12-25 | 1991-12-25 | Hole sealing treatment of noble metal plated material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05311495A true JPH05311495A (en) | 1993-11-22 |
Family
ID=18359365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34315891A Pending JPH05311495A (en) | 1991-12-25 | 1991-12-25 | Hole sealing treatment of noble metal plated material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05311495A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5863611A (en) * | 1997-05-27 | 1999-01-26 | Lilly Industries (Usa), Inc. | Iminodiacetonitrile mirror back coating corrosion inhibitor |
| WO2005073435A1 (en) * | 2004-01-30 | 2005-08-11 | Nippon Mining & Metals Co., Ltd. | Sealing agent, method of sealing and printed circuit board treated with the sealing agent |
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-
1991
- 1991-12-25 JP JP34315891A patent/JPH05311495A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5863611A (en) * | 1997-05-27 | 1999-01-26 | Lilly Industries (Usa), Inc. | Iminodiacetonitrile mirror back coating corrosion inhibitor |
| WO2005073435A1 (en) * | 2004-01-30 | 2005-08-11 | Nippon Mining & Metals Co., Ltd. | Sealing agent, method of sealing and printed circuit board treated with the sealing agent |
| US9576693B2 (en) | 2011-09-20 | 2017-02-21 | Jx Nippon Mining & Metals Corporation | Metal material for electronic component and method for manufacturing the same |
| US9580783B2 (en) | 2011-10-04 | 2017-02-28 | Jx Nippon Mining & Metals Corporation | Electronic component metal material and method for manufacturing the same |
| US9728878B2 (en) | 2012-02-03 | 2017-08-08 | Jx Nippon Mining & Metals Corporation | Press-fit terminal and electronic component using the same |
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