JP2003268586A - Gold plating electrolytic solution and gold plating method - Google Patents
Gold plating electrolytic solution and gold plating methodInfo
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- JP2003268586A JP2003268586A JP2002071428A JP2002071428A JP2003268586A JP 2003268586 A JP2003268586 A JP 2003268586A JP 2002071428 A JP2002071428 A JP 2002071428A JP 2002071428 A JP2002071428 A JP 2002071428A JP 2003268586 A JP2003268586 A JP 2003268586A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金より卑な金属素
材上に直接金めっきを行うにあたって、素材金属のめっ
き液への溶出を抑制し、長期間めっきを行っても金めっ
き皮膜の品質を良好な状態に維持することができる電解
金めっき液および金めっき方法に関する。TECHNICAL FIELD The present invention, when directly plating gold on a metal material that is less base than gold, suppresses the elution of the material metal into the plating solution, and the quality of the gold plating film is obtained even after long-term plating. The present invention relates to an electrolytic gold plating solution and a gold plating method capable of maintaining a good condition.
【０００２】[0002]
【従来の技術】金めっきは、古くから装飾用や洋食器等
に用いられるだけでなく、その優れた電気的特性と耐食
性から電子、電気部品等の工業分野においても広く利用
されている。電子部品分野においては、プリント配線板
やセラミック配線板、リードフレームとそれに搭載され
るＩＣチップの接続に用いられる。例えば、配線板等の
端子に金めっき又は銀めっきを施し、ＩＣ上の電極との
間をワイヤーボンディングで接続することにより回路形
成している。2. Description of the Related Art Gold plating has been used not only for decoration and Western dishes for a long time, but also widely used in the industrial fields such as electronic and electric parts due to its excellent electric characteristics and corrosion resistance. In the electronic component field, it is used for connecting printed wiring boards, ceramic wiring boards, lead frames and IC chips mounted thereon. For example, a circuit is formed by applying gold plating or silver plating to terminals such as a wiring board and connecting the electrodes on the IC by wire bonding.
【０００３】配線板の配線の材質は主に銅または銅合金
が使用されるが、金ワイヤとの十分な接合強度を得るた
めに当該配線上にまずニッケルめっきを行い、その上に
金めっきを行っている。Copper or a copper alloy is mainly used as the material of the wiring of the wiring board, but in order to obtain sufficient bonding strength with the gold wire, the wiring is first nickel-plated and then gold-plated. Is going.
【０００４】しかしながら、近年、電子機器の小型軽量
化、薄型化の要求に応えるために、軽量でかつ屈曲性に
優れ、細密な配線が可能なテープ素材上に銅配線を形成
したフレキシブルプリント配線板やＴＡＢテープに直接
ＩＣを接合する方法が広まっている。However, in recent years, in order to meet the demand for smaller, lighter and thinner electronic devices, a flexible printed wiring board which is lightweight, has excellent flexibility, and has copper wiring formed on a tape material capable of fine wiring. The method of directly joining ICs to TAB tape is becoming widespread.
【０００５】このようなテープ素材は、めっき後の配線
板製造工程中や電子機器への搭載時に折り曲げて使用さ
れることが多い。従来のような下地ニッケル層を有する
めっき構成では、折り曲げた際に硬いニッケルめっき皮
膜にクラックが入り、断線をはじめとする品質不良を引
き起こす。また、ワイヤボンディング強度、ハンダボー
ル接合強度が低下し、更には耐食性の低下による劣化と
いう致命的な不良を引き起こす可能性がある。Such a tape material is often bent and used during a wiring board manufacturing process after plating or when it is mounted on an electronic device. In the conventional plating structure having the underlying nickel layer, when bent, the hard nickel plating film is cracked, causing quality defects such as disconnection. Further, the wire bonding strength and the solder ball bonding strength are lowered, and further, there is a possibility of causing a fatal defect such as deterioration due to a reduction in corrosion resistance.
【０００６】これを避けるために、テープ素材に対して
は下地ニッケルめっきを行わず、銅系素材上に直接金め
っきを行う方法が採用されている。In order to avoid this, a method is adopted in which the base nickel plating is not applied to the tape material, but the copper material is directly plated with gold.
【０００７】しかしながら、銅系素材に直接金めっきを
行う場合、被めっき素材やめっき用治具がめっき液中に
浸漬された状態でめっきを行うため、銅イオンが金めっ
き液中に溶出し、めっき液の使用期間が長くなると、銅
イオンがめっき液中に蓄積する。However, when gold plating is performed directly on a copper-based material, the plating is performed while the material to be plated and the plating jig are immersed in the plating solution, so that copper ions are eluted in the gold plating solution. When the plating solution is used for a long period of time, copper ions are accumulated in the plating solution.
【０００８】その結果、銅イオンが金めっき皮膜中に金
属として共析し、析出皮膜結晶の粗大化、皮膜外観の変
色、密着不良、ワイヤボンディング強度の低下等を引き
起こす。As a result, copper ions are codeposited as a metal in the gold plating film to cause coarsening of the crystals of the deposited film, discoloration of the film appearance, poor adhesion, and a decrease in wire bonding strength.
【０００９】この不具合を防止するため、金めっき液中
の銅イオンが限界濃度以上になるとめっき液を全量更新
する必要があるが、全量更新を行うとめっきのコストが
上昇する。更に、めっき液の交換に伴って生産性も阻害
される。In order to prevent this problem, it is necessary to renew the whole amount of the plating solution when the copper ion concentration in the gold plating solution exceeds the limit concentration. However, if the total amount is renewed, the cost of plating will increase. Further, the productivity is impaired as the plating solution is replaced.
【００１０】以上、銅系素材の場合を例にとって説明し
たが、鉄やニッケルなど銅以外の金属または合金素材で
あっても、あるいは硬質金めっきのように金を主成分と
する合金めっきにおいても、被めっき素材等が金より卑
な金属の場合には金属成分が溶出して金めっき液が汚染
される。このため、金めっき皮膜の品質保持のために銅
系素材と同様に短期間でめっき液の更新が必要となる。In the above description, the case of a copper-based material has been described as an example. However, even in the case of a metal or alloy material other than copper such as iron or nickel, or in alloy plating containing gold as a main component such as hard gold plating. When the material to be plated is a metal that is baser than gold, the metal components are eluted and the gold plating solution is contaminated. Therefore, in order to maintain the quality of the gold plating film, it is necessary to renew the plating solution in a short period of time like the copper-based material.
【００１１】[0011]
【発明が解決しようとする課題】本発明の目的とすると
ころは、金より卑な金属または合金素材上に直接金めっ
きを行う場合に、素材金属のめっき液への溶出を抑制
し、金めっき皮膜を長期間にわたって良好な状態で形成
することができる電解金めっき液及び金めっき方法を提
供することにある。SUMMARY OF THE INVENTION An object of the present invention is to suppress the elution of a raw material metal into a plating solution when directly performing gold plating on a metal or alloy material that is less base than gold, and to achieve gold plating. An object of the present invention is to provide an electrolytic gold plating solution and a gold plating method capable of forming a film in a good state for a long period of time.
【００１２】[0012]
【課題を解決するための手段】本発明者は上記問題を解
決するために種々検討した結果、金めっき液中に、含窒
素複素環化合物、またはメルカプト基が直接結合した芳
香環もしくは複素環を有する化合物を下地金属溶出抑制
剤として使用すれば、金より卑な金属よりなる素材や治
具からめっき液中への金属の溶出を抑制することができ
ることを見出した。Means for Solving the Problems As a result of various investigations for solving the above-mentioned problems, the present inventor has found that a nitrogen-containing heterocyclic compound or an aromatic ring or heterocyclic ring to which a mercapto group is directly bonded is contained in a gold plating solution. It has been found that the use of the compound having as a base metal elution suppressor can suppress the elution of the metal into the plating solution from a material or jig made of a metal less base than gold.
【００１３】すなわち、上記課題を解決する本発明は以
下に記載するものである。That is, the present invention which solves the above problems is described below.
【００１４】〔１〕 下地金属溶出抑制剤を含有するこ
とを特徴とする電解金めっき液。[1] An electrolytic gold plating solution containing an underlayer metal elution inhibitor.
【００１５】〔２〕 下地金属溶出抑制剤が、含窒素複
素環化合物、またはメルカプト基が直接結合した芳香環
もしくは複素環を有する化合物である〔１〕記載の電解
金めっき液。[2] The electrolytic gold plating solution according to [1], wherein the base metal elution suppressor is a nitrogen-containing heterocyclic compound or a compound having an aromatic ring or a heterocycle to which a mercapto group is directly bonded.
【００１６】〔３〕 下地金属溶出抑制剤を含有するこ
とを特徴とする金ストライクめっき液。[3] A gold strike plating solution containing an underlayer metal elution inhibitor.
【００１７】〔４〕 〔１〕または〔２〕記載の金めっ
き液に素材を浸漬して電解めっきを行う金めっき方法。[4] A gold plating method in which a material is immersed in the gold plating solution according to [1] or [2] to perform electrolytic plating.
【００１８】〔５〕 〔３〕記載の金ストライクめっき
液に素材を浸漬して薄付け電解金めっきを行った後、厚
付け電解金めっきを行う金めっき方法。[5] A gold plating method in which a material is immersed in the gold strike plating solution described in [3] to perform thin electrolytic gold plating, and then thick electrolytic gold plating.
【００１９】〔６〕 素材を下地金属溶出抑制剤を含む
水溶液に浸漬した後電解金ストライクめっきまたは電解
金めっきを行う金めっき方法。[6] A gold plating method in which the raw material is immersed in an aqueous solution containing a metal underlayer elution inhibitor, and then electrolytic gold strike plating or electrolytic gold plating is performed.
【００２０】[0020]
【発明の実施の形態】本発明で使用する下地金属溶出抑
制剤は、めっき液中で金属素材の表面に吸着して皮膜を
形成するものであればいずれの抑制剤でも用いることが
できるが、具体的には下記の化合物を用いることが好ま
しい。BEST MODE FOR CARRYING OUT THE INVENTION The base metal elution inhibitor used in the present invention may be any inhibitor as long as it adsorbs on the surface of a metal material in a plating solution to form a film. Specifically, it is preferable to use the following compounds.
【００２１】（１） 含窒素複素環化合物（イ）
化合物（イ）は、窒素をヘテロ原子とする複素環を有す
る化合物であり、例えば、ピリジン、キノリン、トリア
ゾール、ベンゾトリアゾール、プリンおよびその誘導体
を挙げることができる。中でも、アデニン、２，２’−
ジピリジル、ベンゾトリアゾール、８−キノリノールま
たはその塩およびこれらの誘導体を用いることが好まし
い。(1) Nitrogen-containing heterocyclic compound (a) The compound (a) is a compound having a hetero ring having nitrogen as a hetero atom, and includes, for example, pyridine, quinoline, triazole, benzotriazole, purine and its derivatives. Can be mentioned. Among them, adenine, 2,2'-
It is preferable to use dipyridyl, benzotriazole, 8-quinolinol or salts thereof and derivatives thereof.
【００２２】（２） メルカプト基が直接結合した芳香
環または複素環を有する化合物（ロ）
メルカプト基が直接結合する芳香環および複素環として
は、ベンゼン、チアゾール、ベンゾチアゾール、イミダ
ゾール、ベンゾイミダゾール、ピリミジン等を挙げるこ
とができる。化合物（ロ）としては、中でもチオサリチ
ル酸、２−メルカプトベンゾチアゾール、２−メルカプ
トベンゾイミダゾール、２−チオウラシル、２−チオバ
ルビツール酸またはその塩およびこれらの誘導体が好ま
しい。(2) A compound having an aromatic ring or a heterocycle directly bonded to a mercapto group (b) Examples of the aromatic ring and the heterocycle directly bonded to a mercapto group include benzene, thiazole, benzothiazole, imidazole, benzimidazole and pyrimidine. Etc. can be mentioned. As the compound (II), thiosalicylic acid, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-thiouracil, 2-thiobarbituric acid or a salt thereof and derivatives thereof are preferable.
【００２３】下地金属溶出抑制剤の添加量は、金めっき
液に対する溶解度および溶出抑制効果を示す濃度がそれ
ぞれの溶出抑制剤により異なるので一義的に定めること
は出来ないが、概ね５ｍｇ／ｌ程度添加すれば十分な溶
出防止効果を示すのでこれ以上の添加量が好ましい。The addition amount of the base metal elution inhibitor cannot be uniquely determined because the solubility in the gold plating solution and the concentration exhibiting the elution inhibitory effect differ depending on each elution inhibitor, but about 5 mg / l is added. If this is done, a sufficient elution preventing effect is exhibited, so an addition amount above this is preferred.
【００２４】本抑制剤は、それぞれの溶出抑制剤の溶解
度の範囲内で多量に添加しても溶出防止効果が損なわれ
ることは無いが、微量でも十分な効果が得られ、また薬
品価格および濃度管理の容易さから、１０〜１０００ｍ
ｇ／ｌの範囲が好ましい。The present inhibitor does not impair the elution preventing effect even if added in a large amount within the solubility range of each elution inhibitor, but a sufficient effect can be obtained even with a small amount, and the drug price and concentration 10 to 1000m due to easy management
A range of g / l is preferred.
【００２５】また、２−メルカプトベンゾチアゾールの
ようにめっき液に対する溶解性の低い化合物は、カリウ
ム塩またはナトリウム塩などの塩として使用すれば容易
に溶解する。A compound having a low solubility in a plating solution, such as 2-mercaptobenzothiazole, is easily dissolved when used as a salt such as a potassium salt or a sodium salt.
【００２６】上記の下地金属溶出抑制剤を金めっき液に
添加すると、硫黄や窒素などのヘテロ原子が銅素材等の
表面にすみやかに吸着することにより皮膜を形成する。
この皮膜がめっき反応の初期過程において銅素材等とめ
っき液の接触を阻害し、銅がイオンとして金めっき液中
に溶出することを抑制すると考えられる。When the above-described base metal elution suppressor is added to the gold plating solution, heteroatoms such as sulfur and nitrogen are quickly adsorbed on the surface of the copper material or the like to form a film.
It is considered that this film inhibits the contact between the copper material and the plating solution in the initial stage of the plating reaction and suppresses the elution of copper as ions into the gold plating solution.
【００２７】これらの下地金属溶出抑制剤は、金めっき
液が純金めっき液であるか金を主成分とする合金めっき
液であるかによらず、被めっき素材やめっき治具に銅な
どの金より卑な金属が使われている場合に効果がある。These base metal elution suppressors are used for the material to be plated and the plating jig such as copper regardless of whether the gold plating solution is a pure gold plating solution or an alloy plating solution containing gold as a main component. It is effective when a more base metal is used.
【００２８】本発明において、下地金属溶出抑制剤が添
加される金めっき液は特に制限がなく、従来用いられて
いる金めっき液がそのまま使用できる。In the present invention, the gold plating solution to which the base metal elution inhibitor is added is not particularly limited, and the gold plating solution conventionally used can be used as it is.
【００２９】本発明の金めっき液の金イオン源として
は、可溶性の金化合物であれば使用できるが、入手の容
易さ、溶解性、安定性を考慮すると、シアン化金、シア
ン化第一金カリウム、亜硫酸金カリウム、チオ硫酸金か
ら選ばれるものが特に好ましい。As the gold ion source of the gold plating solution of the present invention, any soluble gold compound can be used, but in view of easy availability, solubility and stability, gold cyanide and primary gold cyanide are used. Those selected from potassium, potassium gold sulfite, and gold thiosulfate are particularly preferable.
【００３０】また、使用する金化合物に応じて、めっき
液中での金イオンの安定性を制御する目的で金と錯イオ
ンを形成する錯化剤を合わせて添加してもよい。Further, a complexing agent which forms a complex ion with gold may be added together for the purpose of controlling the stability of the gold ion in the plating solution, depending on the gold compound used.
【００３１】金めっき液に伝導塩として加える有機酸塩
および／または無機酸塩は、クエン酸、酒石酸、リン
酸、亜硫酸等のアルカリ金属塩が好ましく、またこれら
の２種以上を組み合わせて使用してもよい。The organic acid salt and / or inorganic acid salt added to the gold plating solution as a conductive salt is preferably an alkali metal salt such as citric acid, tartaric acid, phosphoric acid, and sulfurous acid, and two or more kinds of them are used in combination. May be.
【００３２】さらに、ｐＨ緩衝剤として、例えば、ホウ
酸、コハク酸、フタル酸、酒石酸、クエン酸、リン酸、
亜硫酸またはその塩を１種又は２種以上添加してもよ
い。これらのｐＨ緩衝剤を添加すると、ｐＨが大きく変
動することがなく一定に維持することが容易になり、め
っき液の長期間の使用に一層好ましいものとなる。Further, as a pH buffering agent, for example, boric acid, succinic acid, phthalic acid, tartaric acid, citric acid, phosphoric acid,
You may add 1 type, or 2 or more types of sulfurous acid or its salt. Addition of these pH buffers makes it easier to maintain the pH constant without largely changing, and it becomes more preferable for long-term use of the plating solution.
【００３３】また、金皮膜の電解析出形態を調整するた
めに、金めっき液にタリウム、砒素、セレンの可溶性塩
を添加してもよい。これらを添加すると、金めっきの電
解析出形態に大きな変動が生じにくくなり、長期間のめ
っきを行うに際して一定の品質を維持することが容易に
なる。Further, in order to adjust the electrolytic deposition form of the gold coating, a soluble salt of thallium, arsenic or selenium may be added to the gold plating solution. The addition of these makes it difficult for the electrolytic plating morphology of gold plating to largely fluctuate, and makes it easy to maintain a certain quality during long-term plating.
【００３４】本発明の電解金めっき液を用いて金めっき
処理を行う場合、下記の条件で電解めっきを行うことが
好ましい。When gold plating is carried out using the electrolytic gold plating solution of the present invention, it is preferable to carry out electrolytic plating under the following conditions.
【００３５】金めっき液のｐＨ値は、緩衝剤と伝導塩の
濃度調整によりｐＨ５．０〜８．０の範囲とするのが好
ましく、この範囲であれば析出する金めっきの外観にム
ラ等の異常が発生しない。The pH value of the gold plating solution is preferably in the range of pH 5.0 to 8.0 by adjusting the concentrations of the buffer agent and the conductive salt. Within this range, the appearance of the gold plating deposited will be uneven. No abnormality occurs.
【００３６】金めっき液のｐＨが５．０未満になるとめ
っき外観にムラが生じやすく、一方、被めっき物にフォ
トレジストが被覆されている場合、ｐＨが８．０を超え
るとこれを溶解し易い。このため、得られる金めっき部
分の形状が初期の形状から歪んだり、溶解したレジスト
成分が金めっき液中で不純物として蓄積し、電解めっき
に際してめっき皮膜中に取り込まれ、めっき皮膜の品質
が低下する。When the pH of the gold plating solution is less than 5.0, the plating appearance tends to be uneven, while when the object to be plated is coated with photoresist, it dissolves when the pH exceeds 8.0. easy. Therefore, the shape of the obtained gold-plated portion is distorted from the initial shape, or the dissolved resist component accumulates as an impurity in the gold-plating solution and is taken into the plating film during electrolytic plating, which deteriorates the quality of the plating film. .
【００３７】めっきを行う際の金めっき液の液温は２０
〜７０℃が好ましい。２０℃未満では実質上温度制御が
容易でなく、めっき処理のばらつきが大きくなるため操
業に適さず、７０℃を超えると析出する金めっきの光沢
に影響を与えるとともに、操業中のめっき液の蒸発によ
る容量減少が大きく、めっき液中の各成分の濃度の維持
が困難になる。The liquid temperature of the gold plating solution during plating is 20
~ 70 ° C is preferred. If the temperature is lower than 20 ° C, it is not easy to control the temperature and the dispersion of the plating process becomes large, which makes it unsuitable for operation. If the temperature exceeds 70 ° C, it affects the luster of the gold plating deposited and evaporation of the plating solution during operation. As a result, the capacity decreases greatly, and it becomes difficult to maintain the concentration of each component in the plating solution.
【００３８】また、電解時の電流密度は０．１〜４．５
Ａ／ｄｍ2が好ましい。この範囲においては当該めっき
液のｐＨ値、液温、金濃度を適宜選択することにより、
良好な状態で金めっきができる。The current density during electrolysis is 0.1 to 4.5.
A / dm 2 is preferred. In this range, by appropriately selecting the pH value of the plating solution, the solution temperature, and the gold concentration,
Gold can be plated in good condition.
【００３９】通常のめっき工程においては、めっき皮膜
の密着性を向上させ、被めっき素材から金めっき液に不
純物金属イオンが混入してめっき液が早期に汚染される
ことを防ぐために、金めっきの前に金ストライクめっき
と称するごく薄い金めっきを行う場合が多い。In the usual plating process, in order to improve the adhesion of the plating film and prevent the impurity metal ions from mixing with the material to be plated into the gold plating solution to contaminate the plating solution early, Very thin gold plating called gold strike plating is often performed before.
【００４０】このような場合には、金ストライクめっき
液に下地金属溶出抑制剤を添加することにより、金スト
ライクめっき液中の下地金属イオンの蓄積が低減され
る。ひいては厚付け金めっき浴へ持ち込まれ混入する下
地金属イオンの蓄積量も低減されるので、金ストライク
めっき液と厚付け金めっき液の両者の使用可能期間を延
ばすことができる。In such a case, by adding a base metal elution inhibitor to the gold strike plating solution, the accumulation of base metal ions in the gold strike plating solution is reduced. As a result, the amount of base metal ions that are brought into and mixed with the thick gold plating bath is also reduced, so that the usable period of both the gold strike plating solution and the thick gold plating solution can be extended.
【００４１】下地金属溶出抑制剤を添加した金ストライ
クめっき液は、金イオン源である金化合物の添加量が少
ないほかは、上記の金めっき液と同様の条件のものが好
ましい。下地金属溶出抑制剤を添加する金ストライクめ
っき液自体は公知のものを適宜利用できる。The gold strike plating solution to which the base metal elution inhibitor has been added preferably has the same conditions as the above gold plating solution except that the amount of the gold compound as the gold ion source added is small. As the gold strike plating solution itself to which the base metal elution inhibitor is added, a known one can be appropriately used.
【００４２】金ストライクめっき液に下地金属溶出抑制
剤を添加する場合、金ストライクめっきに引き続き行う
厚付け金めっきのめっき液に溶出抑制剤を添加してもよ
いが、添加しない場合においても厚付け金めっき液への
下地金属イオン溶出を抑制することができる。When the base metal elution suppressor is added to the gold strike plating solution, the elution suppressor may be added to the plating solution for the thick gold plating that is performed subsequently to the gold strike plating. It is possible to suppress the elution of underlying metal ions into the gold plating solution.
【００４３】金ストライクめっきあるいは厚付け金めっ
きの処理をする前工程として、下地金属溶出抑制剤の水
溶液に素材を浸漬することによっても下地金属溶出抑制
剤の効果を得ることができる。The effect of the base metal elution inhibitor can also be obtained by immersing the raw material in an aqueous solution of the base metal elution inhibitor as a pre-process for the treatment of gold strike plating or thick gold plating.
【００４４】この方法による場合、下地金属溶出抑制剤
の水溶液中の濃度は、金めっき液に添加する場合と同程
度とすることが好ましい。また、この水溶液に伝導塩等
を添加することにより、前処理液が後に続く金めっき液
に持ち込まれて希釈される影響を弱めることができる。
前処理液に伝導塩等の添加を行っても、下地金属の溶出
を防止する効果は影響されず、有効である。In this method, it is preferable that the concentration of the underlayer metal elution inhibitor in the aqueous solution be approximately the same as that in the case of adding it to the gold plating solution. Further, by adding a conductive salt or the like to this aqueous solution, it is possible to reduce the influence of the pretreatment liquid being brought into the subsequent gold plating liquid and being diluted.
Even if a conductive salt or the like is added to the pretreatment liquid, the effect of preventing the elution of the underlying metal is not affected and is effective.
【００４５】また、この方法の場合においても、前処理
に引き続き行うストライク金めっきあるいは厚付け金め
っきのめっき液に溶出抑制剤を添加してもよいが、添加
しない場合においてもめっき液への下地金属イオン溶出
を抑制することができる。Also in the case of this method, an elution inhibitor may be added to the plating solution for the strike gold plating or the thick gold plating, which is carried out subsequent to the pretreatment. Elution of metal ions can be suppressed.
【００４６】[0046]
【実施例】以下、実施例を用いて本発明を更に詳細に説
明する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００４７】実施例１〜１２及び比較例１
シアン化金カリウム１０ｇ／ｌ、クエン酸三カリウム１
００ｇ／ｌ、リン酸水素二カリウム３０ｇ／ｌを含む金
めっき液に各種の下地金属溶出抑制剤を添加し、水酸化
カリウム水溶液でｐＨ６．０に調整した液１００ｍｌを
温度６５℃に維持した。この液に、面積０．２ｄｍ2の
銅板を２０分間浸漬した後、金めっき液中のＣｕイオン
濃度を測定した結果を「銅溶出量」として表１に示す。Examples 1 to 12 and Comparative Example 1 Potassium gold cyanide 10 g / l, tripotassium citrate 1
Various base metal elution inhibitors were added to a gold plating solution containing 00 g / l and 30 g / l dipotassium hydrogen phosphate, and 100 ml of a solution adjusted to pH 6.0 with an aqueous potassium hydroxide solution was maintained at a temperature of 65 ° C. A copper plate having an area of 0.2 dm 2 was immersed in this solution for 20 minutes, and the Cu ion concentration in the gold plating solution was measured. The results are shown in Table 1 as “copper elution amount”.
【００４８】下地金属溶出抑制剤を添加した場合の銅溶
出量は、添加しない比較例１の１／５以下に低減され
た。The amount of copper eluted when the base metal elution inhibitor was added was reduced to 1/5 or less of that of Comparative Example 1 in which no copper metal elution inhibitor was added.
【００４９】下地金属溶出抑制剤を多量に添加した場合
には、多くの場合に銅溶出量がさらに低減されたが、大
幅な低減ではなく、溶出抑制剤の添加濃度は操業上管理
し得る範囲の微量で十分な効果を発揮することがわかっ
た。When a large amount of the base metal elution inhibitor was added, the copper elution amount was further reduced in many cases, but it was not a significant reduction, and the concentration of the elution inhibitor added was within a range that could be controlled in operation. It was found that even a small amount of can exert a sufficient effect.
【００５０】なお、実施例２，３，１０の如く添加量が
増加すると溶出量が若干多くなるものがあったが、これ
は、銅表面に吸着した溶出抑制剤が吸着した銅イオンと
ともにめっき液中に解離したためと推測される。この場
合でも、添加しない場合に比べて十分な溶出防止効果が
認められた。As in Examples 2, 3 and 10, the elution amount increased a little when the addition amount increased. This is because the elution inhibitor adsorbed on the copper surface and the copper ion adsorbed on the plating solution It is speculated that it was dissociated inside. Even in this case, a sufficient elution preventing effect was recognized as compared with the case where no addition was made.
【００５１】また、これらの金めっき液を用いて、電流
密度０．５Ａ／ｄｍ2の条件で銅板に約１μｍ厚の金め
っきを行った結果、それぞれの金めっき液から析出した
金めっき皮膜の外観は、下地金属溶出抑制剤を添加しな
い比較例１と同じく金色の良好な外観を示した。Using these gold plating solutions, a copper plate was gold-plated to a thickness of about 1 μm at a current density of 0.5 A / dm 2 , and as a result, gold plating films deposited from the respective gold plating solutions were formed. As for the appearance, the same gold-colored appearance as that of Comparative Example 1 in which the base metal elution inhibitor was not added was exhibited.
【００５２】さらに、これらのめっき液を使い、金塩を
補充しながら５ターンまで継続使用した。１ターンは、
金めっき皮膜として析出した金量に相当する金塩を補充
しながらめっきを行い、初期の金めっき液中の金含有量
がすべて金めっき皮膜として消費された状態のめっき処
理量をいう。比較例１では２ターン経過時以後、金めっ
き液中に溶出した銅イオンが金めっき皮膜に共析して赤
色を帯びたが、溶出抑制剤を添加した場合には初期の皮
膜と変わらず良好な外観を示した。Further, using these plating solutions, gold salt was replenished and continuously used for 5 turns. One turn
Plating is performed while replenishing with gold salt corresponding to the amount of gold deposited as a gold plating film, and the plating treatment amount is a state in which all the gold content in the initial gold plating solution is consumed as a gold plating film. In Comparative Example 1, after 2 turns, copper ions eluted in the gold plating solution were co-deposited on the gold plating film to give a reddish color, but when an elution inhibitor was added, it was as good as the initial film. It showed a nice appearance.
【００５３】また、これらのめっき皮膜のワイヤボンデ
ィング性を、２５μｍ径のワイヤを使用したワイヤプル
試験により評価した結果を合わせて表１中に示す。実施
例１〜１２から得られた金めっき皮膜では、建浴直後も
５ターン後も十分なワイヤプル強度が得られたが、比較
例１の５ターン経過後の皮膜では著しく低下した。Table 1 also shows the results of evaluating the wire bondability of these plating films by a wire pull test using a wire having a diameter of 25 μm. With the gold-plated coatings obtained from Examples 1 to 12, sufficient wire pull strength was obtained immediately after the construction bath and after 5 turns, but the coating after 5 turns of Comparative Example 1 was significantly reduced.
【００５４】[0054]
【表１】 [Table 1]
【００５５】実施例１３
シアン化金カリウム２ｇ／ｌ、クエン酸三カリウム１０
０ｇ／ｌ、ｐＨ５．５の金ストライクめっき液に、下地
金属溶出抑制剤としてベンゾトリアゾールを２００ｍｇ
／ｌを添加した液を用いて、面積０．２ｄｍ2の銅板に
厚さ約０．０５〜０．１μｍの金ストライクめっきを行
った。その後、表１の比較例１に示す金めっき液を用い
て電流密度０．５Ａ／ｄｍ2において約１μｍ厚の金め
っきを行った。Example 13 Potassium gold cyanide 2 g / l, tripotassium citrate 10
200 mg of benzotriazole as a base metal elution inhibitor in a gold strike plating solution of 0 g / l and pH 5.5
A copper plate having an area of 0.2 dm 2 was subjected to gold strike plating with a thickness of about 0.05 to 0.1 μm by using the liquid added with / l. After that, the gold plating solution shown in Comparative Example 1 in Table 1 was used to perform gold plating with a thickness of about 1 μm at a current density of 0.5 A / dm 2 .
【００５６】この操作を繰り返し、めっきにて消費され
る金量に相当する金塩を補充しながら５ターンまでめっ
きを行った後の厚付け金めっき液中のＣｕイオン濃度を
測定した結果、厚付け金めっき液中に蓄積した銅イオン
量は２．１ｍｇ／ｌであった。This operation was repeated to measure the Cu ion concentration in the thick gold plating solution after plating for 5 turns while replenishing the gold salt corresponding to the amount of gold consumed in the plating. The amount of copper ions accumulated in the gold plating solution was 2.1 mg / l.
【００５７】このとき、５ターン経過後も金めっき皮膜
は初期と変わらず良好な外観を示し、ワイヤプル強度も
９０ｍＮと十分な強度が得られた。At this time, even after 5 turns, the gold plating film showed a good appearance, which was the same as the initial state, and the wire pull strength was 90 mN, which was a sufficient strength.
【００５８】比較例２
比較として、下地金属溶出抑制剤を含まないほかは実施
例１３と同工程、同じ金めっき液組成で銅板に金めっき
を行った。Comparative Example 2 For comparison, a copper plate was gold-plated using the same process and the same gold plating solution composition as in Example 13 except that the base metal elution inhibitor was not included.
【００５９】蓄積銅イオン量は１０４．２ｍｇ／ｌであ
り、約２ターン経過時から金めっき皮膜が赤色を帯び
た。The amount of accumulated copper ions was 104.2 mg / l, and after about 2 turns, the gold plating film became reddish.
【００６０】また、２ターン後のワイヤプル強度は３７
ｍＮと初期に比べて著しく低い値であった。The wire pull strength after 2 turns is 37
The value was mN, which was significantly lower than the initial value.
【００６１】以上のことから、金ストライクめっき液に
溶出抑制剤を添加することにより金めっき液中への銅イ
オンの混入、蓄積を抑えることが確認できた。また、長
期間にわたって外観およびワイヤボンディング性が良好
な金めっき皮膜を作製可能であることが確認できた。From the above, it has been confirmed that addition of an elution inhibitor to the gold strike plating solution suppresses the mixing and accumulation of copper ions in the gold plating solution. In addition, it was confirmed that a gold plating film having a good appearance and wire bondability could be produced for a long period of time.
【００６２】実施例１４
下地金属溶出抑制剤としてベンゾトリアゾールを２００
ｍｇ／ｌを溶解した水溶液に面積０．２ｄｍ2の銅板を
浸漬した。その後、シアン化金カリウム２ｇ／ｌ、クエ
ン酸三カリウム１００ｇ／ｌ、ｐＨ５．５の金ストライ
クめっき液を用いて厚さ約０．０５〜０．１μｍの薄付
け金めっきを行い、さらに、表１の比較例１に示す金め
っき液を用いて約１μｍ厚の金めっきを行った。Example 14 200% of benzotriazole was used as a base metal elution inhibitor.
A copper plate having an area of 0.2 dm 2 was immersed in an aqueous solution in which mg / l was dissolved. After that, thin gold plating with a thickness of about 0.05 to 0.1 μm was performed using a gold strike plating solution of potassium gold cyanide 2 g / l, tripotassium citrate 100 g / l, pH 5.5, and Using the gold plating solution shown in Comparative Example 1 of No. 1, gold plating with a thickness of about 1 μm was performed.
【００６３】この操作を繰り返し、厚付け金めっき液に
金塩を補充しながら５ターンまでめっきを行った後の厚
付け金めっき液中のＣｕイオン濃度を測定した結果、厚
付け金めっき液中に蓄積した銅イオン量は２．５ｍｇ／
ｌであった。This operation was repeated to measure the Cu ion concentration in the thick gold plating solution after performing plating for 5 turns while supplementing the thick gold plating solution with gold salt. The amount of copper ions accumulated in 2.5 mg /
It was l.
【００６４】このとき、５ターン経過後も金めっき皮膜
外観は初期と変わらず良好な色調と光沢を維持してお
り、また、ワイヤプル強度は９２ｍＮと十分な強度を示
した。At this time, the appearance of the gold plating film remained the same as that of the initial state even after 5 turns, and maintained a good color tone and luster, and the wire pull strength was 92 mN, which was a sufficient strength.
【００６５】比較例３
比較として、下地金属溶出抑制剤の水溶液に浸漬しない
ほかは実施例１４と同工程および同じ金めっき液組成で
銅板にめっきを行った。５ターン経過後の厚付け金めっ
き液中の蓄積銅イオン量は９８．２ｍｇ／ｌであり、約
２ターン経過時から金めっき皮膜が赤色を帯びた。Comparative Example 3 For comparison, a copper plate was plated in the same process as in Example 14 and in the same gold plating solution composition except that it was not immersed in an aqueous solution of an underlayer metal elution inhibitor. The amount of accumulated copper ions in the thick gold plating solution after 5 turns was 98.2 mg / l, and the gold plating film became reddish after about 2 turns.
【００６６】金めっきの前処理として素材を下地金属溶
出抑制剤水溶液に浸漬することにより金めっき液中への
銅イオンの混入、蓄積を抑えることが確認できた。ま
た、長期間にわたって良好な品質の金めっき皮膜を作製
可能であることが確認できた。It was confirmed that, as a pretreatment for gold plating, the raw material was dipped in an aqueous solution of a metal elution inhibitor to suppress the mixing and accumulation of copper ions in the gold plating solution. It was also confirmed that a gold plating film of good quality could be produced over a long period of time.
【００６７】[0067]
【発明の効果】本発明によれば、金めっき時の素材や治
具等に使われている銅等の金より卑な金属の金めっき液
への金属イオンの溶出が抑制できる。また、素材上にめ
っきした皮膜に銅等が共析せず、素材へ直接金めっきを
行っても長期間にわたって皮膜を良好な状態に維持した
まま電解金めっきを行うことができる。According to the present invention, it is possible to suppress the elution of metal ions into a gold plating solution of a metal that is less base than gold, such as copper, which is used in materials and jigs during gold plating. Further, copper or the like does not co-deposit on the film plated on the material, and even if the material is directly gold-plated, electrolytic gold plating can be performed while maintaining the film in a good state for a long period of time.
【００６８】本発明は、装飾用、洋食器用等の広い分野
において用いることができるが、特に電子、電気機器分
野において、ＩＣと配線材料を接続するための表面処理
を行う際に有用である。The present invention can be used in a wide range of fields such as decoration and Western tableware, but is particularly useful in the field of electronic and electric equipment when performing a surface treatment for connecting an IC and a wiring material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 博之 東京都港区浜松町２丁目４番１号 世界貿 易センタービル24Ｆ エヌ・イー ケムキ ャット株式会社内 (72)発明者 塩川 和彦 静岡県沼津市一本松678番地 エヌ・イー ケムキャット株式会社内 Ｆターム(参考） 4K023 AA25 BA11 BA17 BA18 BA24 CA08 CA09 CB03 DA02 DA03 DA07 DA08 4K024 AA11 BA01 BA02 BA09 CA02 CA03 CA04 CA06 DA09 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hiroyuki Yamaguchi 2-4-1 Hamamatsucho, Minato-ku, Tokyo World Trade Yasu Center Building 24F NE Chemki Inside the company (72) Inventor Kazuhiko Shiokawa 647 Ipponmatsu, Numazu City, Shizuoka Prefecture Within Chemcat Corporation F term (reference) 4K023 AA25 BA11 BA17 BA18 BA24 CA08 CA09 CB03 DA02 DA03 DA07 DA08 4K024 AA11 BA01 BA02 BA09 CA02 CA03 CA04 CA06 DA09
Claims (6)
徴とする電解金めっき液。1. An electrolytic gold plating solution containing an underlayer metal elution inhibitor.
合物、またはメルカプト基が直接結合した芳香環もしく
は複素環を有する化合物である請求項１記載の電解金め
っき液。2. The electrolytic gold plating solution according to claim 1, wherein the base metal elution suppressor is a nitrogen-containing heterocyclic compound or a compound having an aromatic ring or a heterocycle to which a mercapto group is directly bonded.
徴とする金ストライクめっき液。3. A gold strike plating solution containing an underlayer metal elution inhibitor.
材を浸漬して電解めっきを行う金めっき方法。4. A gold plating method in which a material is immersed in the gold plating solution according to claim 1 or 2 to perform electrolytic plating.
素材を浸漬して薄付け電解金めっきを行った後、厚付け
電解金めっきを行う金めっき方法。5. A gold plating method in which a material is immersed in the gold strike plating solution according to claim 3 to perform thin electrolytic gold plating, and then thick electrolytic gold plating.
に浸漬した後電解金ストライクめっきまたは電解金めっ
きを行う金めっき方法。6. A gold plating method in which electrolytic gold strike plating or electrolytic gold plating is performed after the material is immersed in an aqueous solution containing an underlayer metal elution inhibitor.
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| JP2008270265A (en) * | 2007-04-16 | 2008-11-06 | Sumitomo Metal Mining Package Materials Co Ltd | Substrate for semiconductor device and its production process |
| JP2009007656A (en) * | 2007-06-29 | 2009-01-15 | Japan Pure Chemical Co Ltd | Electrolytic gold-plating solution and gold plated film obtained using the same |
| JP2010255010A (en) * | 2009-04-21 | 2010-11-11 | C Uyemura & Co Ltd | Electroless gold plating bath |
| KR101223861B1 (en) | 2005-09-30 | 2013-01-17 | 메타로 테쿠노로지 쟈판 가부시키가이샤 | Method for manufacturing gold bump or gold line |
| WO2016208340A1 (en) * | 2015-06-26 | 2016-12-29 | メタローテクノロジーズジャパン株式会社 | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
| US11142826B2 (en) | 2018-09-20 | 2021-10-12 | Mk Chem & Tech Co., Ltd | Substitution-type electroless gold plating solution containing purine or pyrimidine-based compound having carbonyl oxygen and substitution-type electroless gold plating method using the same |
| KR102670599B1 (en) * | 2015-06-26 | 2024-05-29 | 이이쟈 가부시키가이샤 | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
-
2002
- 2002-03-15 JP JP2002071428A patent/JP4129363B2/en not_active Expired - Lifetime
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| JP2007092156A (en) * | 2005-09-30 | 2007-04-12 | Ne Chemcat Corp | Non-cyanogen based gold electroplating bath for forming bump |
| KR101223861B1 (en) | 2005-09-30 | 2013-01-17 | 메타로 테쿠노로지 쟈판 가부시키가이샤 | Method for manufacturing gold bump or gold line |
| KR101319745B1 (en) | 2005-09-30 | 2013-10-17 | 메타로 테쿠노로지 쟈판 가부시키가이샤 | Non-cyanogen type electrolytic gold plating bath for bump forming |
| JP2008270265A (en) * | 2007-04-16 | 2008-11-06 | Sumitomo Metal Mining Package Materials Co Ltd | Substrate for semiconductor device and its production process |
| JP2009007656A (en) * | 2007-06-29 | 2009-01-15 | Japan Pure Chemical Co Ltd | Electrolytic gold-plating solution and gold plated film obtained using the same |
| JP2010255010A (en) * | 2009-04-21 | 2010-11-11 | C Uyemura & Co Ltd | Electroless gold plating bath |
| WO2016208340A1 (en) * | 2015-06-26 | 2016-12-29 | メタローテクノロジーズジャパン株式会社 | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
| CN107709628A (en) * | 2015-06-26 | 2018-02-16 | 美泰乐科技(日本)股份有限公司 | Anti-displacement dose for electrolytic hard gold plating solution and the electrolytic hard gold plating solution comprising it |
| JPWO2016208340A1 (en) * | 2015-06-26 | 2018-04-12 | メタローテクノロジーズジャパン株式会社 | Displacement inhibitor for electrolytic hard gold plating solution and electrolytic hard gold plating solution containing the same |
| US10577704B2 (en) | 2015-06-26 | 2020-03-03 | Metalor Technologies Corporation | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
| KR102670599B1 (en) * | 2015-06-26 | 2024-05-29 | 이이쟈 가부시키가이샤 | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
| US11142826B2 (en) | 2018-09-20 | 2021-10-12 | Mk Chem & Tech Co., Ltd | Substitution-type electroless gold plating solution containing purine or pyrimidine-based compound having carbonyl oxygen and substitution-type electroless gold plating method using the same |
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