JP2003277942A - Electroless gold plating solution - Google Patents

Electroless gold plating solution

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Publication number
JP2003277942A
JP2003277942A JP2002082882A JP2002082882A JP2003277942A JP 2003277942 A JP2003277942 A JP 2003277942A JP 2002082882 A JP2002082882 A JP 2002082882A JP 2002082882 A JP2002082882 A JP 2002082882A JP 2003277942 A JP2003277942 A JP 2003277942A
Authority
JP
Japan
Prior art keywords
plating solution
electroless
gold
gold plating
plating film
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
Application number
JP2002082882A
Other languages
Japanese (ja)
Other versions
JP3831842B2 (en
Inventor
Katsushige Iwamatsu
Kimiko Kudo
Naomi Murase
Kaoru Naito
Teruaki Shimoji
輝明 下地
薫 内藤
克茂 岩松
喜美子 工藤
直美 村瀬
Original Assignee
Okuno Chem Ind Co Ltd
奥野製薬工業株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Okuno Chem Ind Co Ltd, 奥野製薬工業株式会社 filed Critical Okuno Chem Ind Co Ltd
Priority to JP2002082882A priority Critical patent/JP3831842B2/en
Publication of JP2003277942A publication Critical patent/JP2003277942A/en
Application granted granted Critical
Publication of JP3831842B2 publication Critical patent/JP3831842B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroless gold plating solution which can form a good plating film on an electroless nickel plating film and can minimize the corrosion of the nickel plating film. <P>SOLUTION: The electroless gold plating film contains (i) a water-soluble gold compound, (ii) a complexing agent, (iii) at least one component selected from the group consisting of acids including chalcogen elements of an oxidation number 2 to 4 and their salts, (iv) at least one component selected from the group consisting of hydrazine and its derivative, and (v) a compound having an ethylene group including ≥2 imono groups within the molecule and having a substituent in some cases between the nitrogen atoms of the imino group. <P>COPYRIGHT: (C)2004,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention
【0001】[0001]
【発明の属する技術分野】本発明は、無電解金めっき液
に関する。
TECHNICAL FIELD The present invention relates to an electroless gold plating solution.
【0002】[0002]
【従来の技術】プリント配線板、電子部品等を製造する
際に、最終工程の一つとして、無電解金めっき処理が行
われている。これは、主として、プリント配線板の銅回
路表面の酸化防止や、電子部品の接続面のはんだ接合性
を向上させることを目的とするものであり、この処理に
よって、プリント配線板と実装される電子部品との間で
良好な半田接合強度が確保されている。
2. Description of the Related Art Electroless gold plating is used as one of the final steps in manufacturing printed wiring boards, electronic components and the like. This is mainly intended to prevent the oxidation of the copper circuit surface of the printed wiring board and to improve the solder bondability of the connection surface of the electronic component. Good solder joint strength with parts is secured.
【0003】近年、各種電子部品に対して高い信頼性が
要求されており、プリント配線板と電子部品との接合強
度に関しては、はんだの剪断強度と同程度以上の高い強
度が必要とされている。
In recent years, high reliability has been demanded for various electronic parts, and the bonding strength between the printed wiring board and the electronic parts is required to be as high as the shear strength of solder or higher. .
【0004】通常、プリント配線板、電子部品等に無電
解金めっき皮膜を形成する場合には、回路材料である銅
金属中への金めっき皮膜の拡散を防止すること等を目的
として、銅金属上に無電解ニッケルめっき皮膜を形成し
た後、無電解金めっきを行うことが一般的である。この
場合、無電解金めっき液としては、一般的に置換型のめ
っき液が用いられているが、置換型のめっき液を用いる
と、ニッケルめっき皮膜との置換反応によって金めっき
皮膜が形成されるために、ニッケルめっき皮膜に腐食が
生じて、ニッケル皮膜表面が、ポーラスな状態となるこ
とが避けられない。
Usually, when an electroless gold plating film is formed on a printed wiring board, electronic parts, etc., copper metal is used for the purpose of preventing diffusion of the gold plating film into copper metal which is a circuit material. It is common to perform electroless gold plating after forming an electroless nickel plating film on it. In this case, a substitution type plating solution is generally used as the electroless gold plating solution, but when the substitution type plating solution is used, a gold plating film is formed by a substitution reaction with the nickel plating film. Therefore, it is unavoidable that the nickel plating film is corroded and the surface of the nickel film becomes porous.
【0005】一般に、無電解金めっき上のハンダ接合強
度は、無電解ニッケルめっき皮膜の表面状態の影響を大
きく受け、ポーラスな状態の無電解ニッケル皮膜では、
ハンダと無電解ニッケル皮膜との間に良好な金属間結合
を形成することが難しく、その結果、ハンダ接続強度の
低下を招くという大きな問題点がある。
Generally, the solder joint strength on electroless gold plating is greatly affected by the surface condition of the electroless nickel plating film, and in the case of a porous electroless nickel film,
It is difficult to form a good intermetallic bond between the solder and the electroless nickel film, and as a result, there is a serious problem that the solder connection strength is lowered.
【0006】[0006]
【発明が解決しようとする課題】本発明は、上記した従
来技術の現状に鑑みてなされたものであり、その主な目
的は、無電解ニッケルめっき皮膜上に良好な金めっき皮
膜を形成し得る無電解金めっき液であって、ニッケルめ
っき皮膜の腐食を最小限に抑制することが可能な新規な
めっき液を提供することである。
SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and its main purpose is to form a good gold plating film on an electroless nickel plating film. It is an object of the present invention to provide a novel plating solution which is an electroless gold plating solution and which can suppress corrosion of a nickel plating film to a minimum.
【0007】[0007]
【課題を解決するための手段】本発明者は、上記した目
的を達成すべく研究を重ねた結果、特定の還元剤、腐食
抑制剤、安定剤等を配合した無電解金めっき液によれ
ば、無電解ニッケルめっき皮膜上に無電解金めっき皮膜
を形成する際に、ニッケルめっき皮膜の腐食を最小限に
抑制した上で、良好な金めっき皮膜を形成することが可
能となることを見出し、ここに本発明を完成するに至っ
た。
Means for Solving the Problems As a result of repeated studies to achieve the above object, the present inventor has found that an electroless gold plating solution containing a specific reducing agent, corrosion inhibitor, stabilizer, etc. When forming an electroless gold plating film on an electroless nickel plating film, it was found that it is possible to form a good gold plating film while suppressing the corrosion of the nickel plating film to a minimum, The present invention has been completed here.
【0008】即ち、本発明は、下記の無電解金めっき液
を提供するものである。 1.(i)水溶性金化合物、(ii)錯化剤、(iii)酸
化数2〜4のカルコゲン元素を含む酸及びその塩からな
る群から選ばれた少なくとも一種の成分、(iv)ヒドラ
ジン及びその誘導体からなる群から選ばれた少なくとも
一種の成分、並びに(v)分子内に2個以上のイミノ基
を含み、置換基を有することのあるエチレン基を該イミ
ノ基の窒素原子間に有する化合物、を含有することを特
徴とする無電解金めっき液。 2. 水溶性金化合物がシアン化金錯塩であり、錯化剤
が、エチレンジアミン誘導体である上記項1に記載の無
電解金めっき液。
That is, the present invention provides the following electroless gold plating solution. 1. (I) water-soluble gold compound, (ii) complexing agent, (iii) at least one component selected from the group consisting of acids containing chalcogen elements having an oxidation number of 2 to 4 and salts thereof, (iv) hydrazine and its At least one component selected from the group consisting of derivatives, and (v) a compound having two or more imino groups in the molecule and having an ethylene group which may have a substituent between the nitrogen atoms of the imino groups, An electroless gold plating solution comprising: 2. Item 2. The electroless gold plating solution according to Item 1, wherein the water-soluble gold compound is a gold cyanide complex salt, and the complexing agent is an ethylenediamine derivative.
【0009】[0009]
【発明の実施の形態】本発明の無電解金めっき液は、
(i)水溶性金化合物、(ii)錯化剤、(iii)酸化数
2〜4のカルコゲン元素を含む酸及びその塩からなる群
から選ばれた少なくとも一種の成分、(iv)ヒドラジン
及びその誘導体からなる群から選ばれた少なくとも一種
の成分、並びに(v)分子内に2個以上のイミノ基を含
み、置換基を有することのあるエチレン基を該イミノ基
の窒素原子間に有する化合物、を含有するものである。
以下、本発明の無電解金めっき液で用いられる各成分に
ついて説明する。 (i)水溶性金化合物:本発明の無電解金めっき液で
は、金化合物として、水溶性の金化合物であれば特に限
定なく使用できるが、特に、シアン化金錯塩を用いるこ
とが好ましい。
BEST MODE FOR CARRYING OUT THE INVENTION The electroless gold plating solution of the present invention is
(I) water-soluble gold compound, (ii) complexing agent, (iii) at least one component selected from the group consisting of acids containing chalcogen elements having an oxidation number of 2 to 4 and salts thereof, (iv) hydrazine and its At least one component selected from the group consisting of derivatives, and (v) a compound having two or more imino groups in the molecule and having an ethylene group which may have a substituent between the nitrogen atoms of the imino groups, Is included.
Hereinafter, each component used in the electroless gold plating solution of the present invention will be described. (I) Water-soluble gold compound: In the electroless gold plating solution of the present invention, as the gold compound, any water-soluble gold compound can be used without particular limitation, and it is particularly preferable to use a gold cyanide complex salt.
【0010】シアン化金錯塩の具体例としては、シアン
化金カリウム、シアン化金ナトリウム等を挙げることが
できる。水溶性金化合物は、一種単独又は二種以上混合
して用いることができる。
Specific examples of the gold cyanide complex salt include potassium gold cyanide, sodium gold cyanide and the like. The water-soluble gold compounds can be used alone or in combination of two or more.
【0011】本発明の無電解金めっき液中における水溶
性金化合物の濃度については、特に限定的ではないが、
金化合物の濃度が低すぎると、金めっきの析出速度が遅
くなって、所定の金めっき皮膜を形成するために長時間
を要することになる。一方、金化合物の濃度が高すぎる
場合には、めっき液からの金化合物の持ち出し量が多く
なってコスト高となるので好ましくない。この様な点か
ら、通常、無電解金めっき液中の水溶性金化合物の濃度
は、0.001〜0.1mol/l程度とすることが好
ましく、0.002〜0.05mol/l程度とするこ
とがより好ましい。 (ii)錯化剤:本発明の無電解金めっき液では、金の析
出は、下地金属との置換反応と還元剤による還元反応の
二種類の反応によるものと考えられる。このため、ニッ
ケルめっき皮膜上にめっき処理を行う際合には、反応の
初期においてニッケルめっき皮膜上に金皮膜の置換反応
が生じて、めっき液中にニッケルが溶解する。
The concentration of the water-soluble gold compound in the electroless gold plating solution of the present invention is not particularly limited,
If the concentration of the gold compound is too low, the deposition rate of gold plating will be slow and it will take a long time to form a predetermined gold plating film. On the other hand, if the concentration of the gold compound is too high, the amount of the gold compound carried out from the plating solution increases and the cost increases, which is not preferable. From such a point, usually, the concentration of the water-soluble gold compound in the electroless gold plating solution is preferably about 0.001 to 0.1 mol / l, and about 0.002 to 0.05 mol / l. More preferably. (Ii) Complexing agent: In the electroless gold plating solution of the present invention, gold deposition is considered to be caused by two types of reactions, a substitution reaction with a base metal and a reduction reaction with a reducing agent. Therefore, when the plating treatment is performed on the nickel plating film, a substitution reaction of the gold film occurs on the nickel plating film in the initial stage of the reaction, and nickel is dissolved in the plating solution.
【0012】本発明めっき液に配合する錯化剤は、この
ようなニッケルの溶解反応を円滑に進行させ、さらに、
溶解したニッケルイオンをめっき液中で可溶化させる働
きをするものである。
The complexing agent to be added to the plating solution of the present invention smoothly promotes such a nickel dissolution reaction.
It functions to solubilize the dissolved nickel ions in the plating solution.
【0013】本発明めっき液では、錯化剤としては、め
っき液中でニッケルイオンを安定に可溶化させることが
できるものであれば、特に限定なく使用できるが、特
に、エチレンジアミン誘導体を用いることが好ましい。
本発明において有効に使用できるエチレンジアミン誘導
体の具体例としては、エチレンジアミン四酢酸、N−ヒ
ドロキシエチルエチレンジアミン−N,N’,N’−三
酢酸(バーセノール)、ジエチレントリアミン五酢酸、
N,N,N’,N’−テトラヒドロキシエチルエチレン
ジアミン(クォードロール)、エチレンジアミンテトラ
メチレンホスホン酸等のエチレンジアミン又はジエチレ
ントリアミンの窒素原子上に、ヒドロキシアルキル基、
カルボキシアルキル基、スルホン酸基等から選ばれた置
換基を3〜5個程度有する誘導体、これらの誘導体のナ
トリウム塩、カリウム塩等のアルカリ金属塩、アンモニ
ウム塩等の塩を挙げることができる。
In the plating solution of the present invention, the complexing agent can be used without particular limitation as long as it is capable of stably solubilizing nickel ions in the plating solution. In particular, an ethylenediamine derivative is used. preferable.
Specific examples of the ethylenediamine derivative that can be effectively used in the present invention include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine-N, N ′, N′-triacetic acid (versenol), diethylenetriaminepentaacetic acid,
On the nitrogen atom of ethylenediamine or diethylenetriamine such as N, N, N ′, N′-tetrahydroxyethylethylenediamine (quadrol), ethylenediaminetetramethylenephosphonic acid, a hydroxyalkyl group,
Examples thereof include derivatives having about 3 to 5 substituents selected from a carboxyalkyl group, a sulfonic acid group and the like, alkali metal salts such as sodium salt and potassium salt of these derivatives, and salts such as ammonium salt.
【0014】本発明のめっき液では、錯化剤は、一種単
独又は二種以上混合して用いることができる。
In the plating solution of the present invention, the complexing agent may be used alone or in combination of two or more.
【0015】本発明めっき液における錯化剤の濃度につ
いては、特に限定的ではないが、錯化剤濃度が低すぎる
と、溶解したニッケルイオンを金めっき液中に安定に可
溶化させることが困難となって、水酸化ニッケル等の沈
殿を生じ易くなる。一方、錯化剤濃度が高すぎると、無
電解ニッケル皮膜からのニッケルの溶解が過剰となっ
て、無電解ニッケル皮膜の腐食を引き起こし易くなる。
これらの点から、錯化剤濃度は、0.001〜1mol
/l程度とすることが好ましく、0.002〜0.1m
ol/l程度とすることがより好ましい。 (iii)酸化数2〜4のカルコゲン元素を含む酸及びそ
の塩からなる群から選ばれた少なくとも一種の成分:こ
れらの成分は、めっき液中に含まれる水溶性金塩に対す
る還元剤として有効な成分である。この様な特定の還元
剤を用いることによって、適度な析出速度を有し、且つ
安定性に優れた無電解金めっき液が得られる。
The concentration of the complexing agent in the plating solution of the present invention is not particularly limited, but if the concentration of the complexing agent is too low, it will be difficult to stably solubilize the dissolved nickel ions in the gold plating solution. Therefore, precipitation of nickel hydroxide or the like is likely to occur. On the other hand, if the concentration of the complexing agent is too high, the dissolution of nickel from the electroless nickel coating becomes excessive, and corrosion of the electroless nickel coating is likely to occur.
From these points, the complexing agent concentration is 0.001 to 1 mol.
/ L is preferable, and 0.002 to 0.1 m
More preferably, it is about ol / l. (Iii) At least one component selected from the group consisting of an acid containing a chalcogen element having an oxidation number of 2 to 4 and a salt thereof: these components are effective as a reducing agent for the water-soluble gold salt contained in the plating solution. It is an ingredient. By using such a specific reducing agent, an electroless gold plating solution having an appropriate deposition rate and excellent stability can be obtained.
【0016】酸化数2〜4のカルコゲン元素を含む酸及
びその塩としては、本発明のめっき液に可溶な化合物で
あれば特に限定なく使用できる。その具体例としては、
スルホキシル酸、亜硫酸、チオ硫酸、二亜チオン酸、亜
セレン酸、亜テルル酸等の酸、これらの酸のナトリウム
塩、カリウム塩等のアルカリ金属塩、アンモニウム塩等
を挙げることができ、更に、ホルムアルデヒドナトリウ
ムスルホキシレート(ロンガリット)等の上記酸又は塩
の誘導体も用いることができる。上記還元剤は、一種単
独又は二種以上混合して用いることができる。
As the acid containing the chalcogen element having an oxidation number of 2 to 4 and its salt, any compound can be used without particular limitation as long as it is a compound soluble in the plating solution of the present invention. As a concrete example,
Acids such as sulfoxylic acid, sulfurous acid, thiosulfuric acid, dithionous acid, selenious acid, and telluric acid, sodium salts of these acids, alkali metal salts such as potassium salts, ammonium salts and the like, and further, Derivatives of the above acids or salts such as formaldehyde sodium sulfoxylate (Rongalit) can also be used. The reducing agents may be used alone or in combination of two or more.
【0017】本発明めっき液中における上記還元剤の濃
度は、特に限定的ではないが、0.001〜1mol/
l程度とすることが好ましく、0.002〜0.5mo
l/l程度とすることがより好ましい。還元剤濃度が低
すぎると、金イオンの還元速度が遅くなって所定の金め
っき皮膜を形成するために長時間を要することになり、
一方還元剤濃度が高すぎると、めっき液の分解が生じや
すくなるので、いずれも好ましくない。 (iv)ヒドラジン及びその誘導体からなる群から選ばれ
た少なくとも一種の成分:これらの成分は、ニッケルめ
っき皮膜の腐食を抑制するために有効な成分(以下「腐
食抑制剤」という)である。
The concentration of the reducing agent in the plating solution of the present invention is not particularly limited, but is 0.001-1 mol /
It is preferable to be about 1 and 0.002 to 0.5 mo
More preferably, it is about 1 / l. If the reducing agent concentration is too low, the reduction rate of gold ions will be slow and it will take a long time to form a predetermined gold plating film.
On the other hand, if the concentration of the reducing agent is too high, the plating solution is likely to be decomposed, which is not preferable. (Iv) At least one component selected from the group consisting of hydrazine and its derivatives: These components are effective components for suppressing the corrosion of the nickel plating film (hereinafter referred to as "corrosion inhibitors").
【0018】ヒドラジン誘導体としては、例えば、ピラ
ゾール類、トリアゾール類、チアジアゾール類、マレイ
ン酸ヒドラジド等を用いることができる。これらの内
で、ピラゾール類としては、ピラゾールの他に、5−ア
ミノ−3−メチルピラゾール等のピラゾール誘導体を用
いることができ、トリアゾール類としては、1,2,4
−トリアゾール等のトリアゾールの他に、3−アミノ−
1,2,4−トリアゾール等のトリアゾール誘導体等を
用いることができ、チアジアゾール類としては、2−ア
ミノ−5−エチル−1,3,4−チアジアゾール等のチ
アジアゾール誘導体を用いることができる。
As the hydrazine derivative, for example, pyrazoles, triazoles, thiadiazoles, maleic hydrazide and the like can be used. Among these, as pyrazoles, pyrazole derivatives such as 5-amino-3-methylpyrazole can be used in addition to pyrazole, and as triazoles, 1,2,4
-In addition to triazoles such as triazole, 3-amino-
Triazole derivatives such as 1,2,4-triazole can be used, and as thiadiazoles, thiadiazole derivatives such as 2-amino-5-ethyl-1,3,4-thiadiazole can be used.
【0019】本発明では、ヒドラジン及び上記したヒド
ラジン誘導体は、一種単独又は二種以上混合して用いる
ことができる。
In the present invention, the hydrazine and the above-mentioned hydrazine derivatives can be used alone or in combination of two or more.
【0020】本発明めっき液中における腐食抑制剤の濃
度については、特に限定的ではないが、腐食抑制剤の濃
度が低すぎると、ニッケルめっき皮膜の腐食を抑制する
効果が不足して、ニッケルめっき皮膜の腐食が発生しや
すくなり、一方、高すぎる場合には、無電解金めっき皮
膜の初期析出が阻害されて、十分な膜厚の金めっき皮膜
を形成することが困難になる。この様な点から、腐食抑
制剤の濃度は、0.001〜1mol/l程度とするこ
とが好ましく、0.002〜0.1mol/l程度とす
ることがより好ましい。 (v)分子内に2個以上のイミノ基を含み、置換基を有
することのあるエチレン基を該イミノ基の窒素原子間に
有する化合物:この化合物は、めっき液の安定化剤とし
て作用するものである。このような化合物(以下、「安
定化剤」という)の好ましい例としては、下記一般式
The concentration of the corrosion inhibitor in the plating solution of the present invention is not particularly limited, but if the concentration of the corrosion inhibitor is too low, the effect of suppressing the corrosion of the nickel plating film will be insufficient, resulting in nickel plating. Corrosion of the film is likely to occur, while if it is too high, the initial deposition of the electroless gold plating film is hindered, and it becomes difficult to form a gold plating film having a sufficient film thickness. From this point of view, the concentration of the corrosion inhibitor is preferably about 0.001 to 1 mol / l, more preferably about 0.002 to 0.1 mol / l. (V) Compound having two or more imino groups in the molecule and having an ethylene group which may have a substituent between nitrogen atoms of the imino group: This compound acts as a stabilizer of the plating solution Is. Preferred examples of such a compound (hereinafter referred to as “stabilizer”) include the following general formula
【0021】[0021]
【化1】 [Chemical 1]
【0022】(式中、R1及びR2は、同一または異なっ
て、低級アルキル基を示し、R3〜R6は、同一または異
なって、低級アルキル基または水素原子を示す。nは1
〜4の整数である。)で表される化合物を挙げることが
できる。
(In the formula, R 1 and R 2 are the same or different and represent a lower alkyl group, and R 3 to R 6 are the same or different and represent a lower alkyl group or a hydrogen atom. N is 1
Is an integer of ~ 4. The compound represented by these can be mentioned.
【0023】上記一般式において、低級アルキル基とし
ては、メチル、エチル、n−プロピル、イソプロピル、
n−ブチル、イソブチル、tert−ブチル等の炭素数
1〜4程度の直鎖状又は分岐鎖状のアルキル基を例示で
きる。
In the above general formula, examples of the lower alkyl group include methyl, ethyl, n-propyl, isopropyl,
Examples thereof include linear or branched alkyl groups having about 1 to 4 carbon atoms such as n-butyl, isobutyl, tert-butyl and the like.
【0024】この様な化合物の具体例としてはN,N’
−ジメチルエチレンジアミン、N,N’−ジエチルエチ
レンジアミン、N,N’’−ジメチルジエチレントリア
ミン、N,N’−ジメチル−1,2−ジアミノプロパン
等を挙げることができる。これらの化合物は、一種単独
または二種以上混合して用いることができる。
Specific examples of such compounds include N, N '.
-Dimethylethylenediamine, N, N'-diethylethylenediamine, N, N ''-dimethyldiethylenetriamine, N, N'-dimethyl-1,2-diaminopropane and the like can be mentioned. These compounds may be used alone or in combination of two or more.
【0025】安定化剤の濃度については、特に限定的で
はないが、低すぎる場合にはめっき液の安定性が不足し
て分解が生じやすくなり、一方、高すぎる場合には上記
した腐食抑制剤による腐食抑制効果が妨げられて、ニッ
ケルめっき皮膜の腐食が生じやすくなる。これらの点か
ら、安定化剤の濃度は、0.001〜10mmol/l
程度とするとが好ましく、0.002〜1mol/l程
度とすることがより好ましい。
The concentration of the stabilizer is not particularly limited, but if it is too low, the stability of the plating solution is insufficient and decomposition tends to occur, while if it is too high, the corrosion inhibitor described above is used. The corrosion inhibition effect due to is impeded, and corrosion of the nickel plating film is likely to occur. From these points, the concentration of the stabilizer is 0.001 to 10 mmol / l.
The amount is preferably about 0.002 to 1 mol / l, and more preferably about 0.002 to 1 mol / l.
【0026】本発明の無電解金めっき液には、さらに、
めっき液の特性に悪影響を及ぼさない限り、上記した成
分の他に、他の金属塩、有機化合物などが含まれていて
もよい。無電解めっき方法 :本発明の無電解金めっき液を用いる
めっき方法は、通常の無電解めっきの処理方法と同様で
よい。一般的には、該無電解金めっき液中に被めっき物
を浸漬し、めっき液の温度を所定の温度範囲とすること
によって、被めっき物の表面に無電解金めっき皮膜を形
成することができる。この場合、必要に応じて、めっき
液を攪拌してもよい。
The electroless gold plating solution of the present invention further comprises
In addition to the above components, other metal salts, organic compounds, etc. may be contained as long as the characteristics of the plating solution are not adversely affected. Electroless plating method : The plating method using the electroless gold plating solution of the present invention may be the same as the ordinary electroless plating treatment method. Generally, an electroless gold plating film can be formed on the surface of an object to be plated by immersing the object to be plated in the electroless gold plating solution and setting the temperature of the plating solution within a predetermined temperature range. it can. In this case, the plating solution may be stirred if necessary.
【0027】無電解金めっき液の液温については、低す
ぎると析出反応が緩慢となって金めっき皮膜の未析出や
外観不良等が発生し易くなるので、通常、40℃程度以
上とすればよいが、液温が高すぎるとめっき液の分解が
生じ易くなり、更に、水の蒸発が激しすぎるために、め
っき液中に含まれる成分の濃度維持が困難となる。この
ため、めっき液の液温は、60〜100℃程度とするこ
とが好ましい。
If the temperature of the electroless gold plating solution is too low, the precipitation reaction slows down and the gold plating film may not be precipitated or the appearance may be poor. However, if the solution temperature is too high, the plating solution is likely to be decomposed, and further, the evaporation of water is too violent, which makes it difficult to maintain the concentration of the components contained in the plating solution. Therefore, the liquid temperature of the plating solution is preferably about 60 to 100 ° C.
【0028】めっき液のpHについては、低すぎるとめ
っき液中のシアンイオンが大気中に放出されてめっき液
の安定性が低下し、作業環境も悪化する。一方、pHが
高すぎると、還元剤の還元電位が高すぎてめっき液の安
定性が低下する。
If the pH of the plating solution is too low, the cyan ions in the plating solution are released into the atmosphere, the stability of the plating solution is lowered, and the working environment is deteriorated. On the other hand, if the pH is too high, the reduction potential of the reducing agent will be too high and the stability of the plating solution will decrease.
【0029】これらの点から、めっき液のpHは3〜1
2程度とすることが好ましく、5〜10程度とすること
がより好ましい。
From these points, the pH of the plating solution is 3 to 1
It is preferably about 2 and more preferably about 5 to 10.
【0030】被めっき物の種類については、特に限定は
なく、金属材料の他、プラスチック材料、セラミック材
料など各種の材質の材料を被めっき物とすることができ
る。この場合、被めっき物の種類に応じて、必要に応じ
て、公知の方法に従って、適宜、触媒付与などを行えば
よい。本発明の無電解金めっき液は、ニッケルめっき皮
膜上に金めっき皮膜を形成する際に、ニッケルめっき皮
膜の腐食を最小限に抑えることができるという特徴を有
するものである。従って、無電解ニッケルめっき皮膜が
形成された物品を被めっき物とする場合に、特に、本発
明の無電解金めっき液を有効に使用することができる。
この様な被めっき物の内で、形成された無電解金めっき
皮膜上にハンダ付けを行う物品、例えば、プリント配線
板、電子部品等を被めっき物とする場合には、下地とし
て形成するニッケル皮膜の腐食を抑制でき、ニッケル皮
膜の腐食に伴うハンダ接続強度の低下を防止できる点
で、本発明の無電解金めっき液の効果が特に有効に発揮
される。
The type of the object to be plated is not particularly limited, and various materials such as a plastic material and a ceramic material can be used as the object to be plated in addition to the metal material. In this case, depending on the type of the object to be plated, if necessary, a catalyst may be appropriately added according to a known method. The electroless gold plating solution of the present invention has a feature that corrosion of the nickel plating film can be suppressed to a minimum when the gold plating film is formed on the nickel plating film. Therefore, when the article on which the electroless nickel plating film is formed is used as the object to be plated, the electroless gold plating solution of the present invention can be effectively used.
In such an object to be plated, when an article to be soldered on the formed electroless gold plating film, for example, a printed wiring board, an electronic component or the like is used as the object to be plated, nickel formed as a base The effect of the electroless gold plating solution of the present invention is particularly effectively exhibited in that the corrosion of the coating can be suppressed and the decrease in solder connection strength due to the corrosion of the nickel coating can be prevented.
【0031】[0031]
【発明の効果】本発明の無電解金めっき液は、安定性が
良好であって、均一で良好な外観の金めっき皮膜を形成
することができ、さらに、ニッケル上に無電解金めっき
皮膜を形成する場合に、ニッケルの腐食が非常に少ない
という優れた特徴を有するものである。
EFFECTS OF THE INVENTION The electroless gold plating solution of the present invention has good stability and can form a gold plating film having a uniform and good appearance. Further, an electroless gold plating film is formed on nickel. When it is formed, it has an excellent feature that nickel corrosion is very small.
【0032】従って、本発明の無電解金めっき液を用い
ることにより、無電解ニッケルめっき皮膜が形成された
プリント配線板、電子部品等を被めっき物とする場合に
は、特に、ニッケルめっき皮膜の腐食を抑制して、ハン
ダ接合強度の低下を防止できるという優れた効果が発揮
される。
Therefore, when the electroless gold plating solution of the present invention is used to form a printed wiring board, an electronic component or the like on which an electroless nickel plating film has been formed, a nickel plating film It has an excellent effect of suppressing corrosion and preventing a decrease in solder joint strength.
【0033】[0033]
【実施例】以下、実施例を挙げて本発明をさらに詳細に
説明する。
EXAMPLES The present invention will be described in more detail with reference to examples.
【0034】実施例1 パッド径0.5mmのBGA搭載用の銅回路を有する5
×10cmの独立回路基板について、該銅回路上に厚さ約
5μmの無電解ニッケルめっき皮膜(含リン率5〜8
%)を形成した基板を被めっき物として用いた。
Example 1 5 having a copper circuit for mounting a BGA with a pad diameter of 0.5 mm
For an independent circuit board of × 10 cm, an electroless nickel plating film (phosphorus content of 5 to 8) having a thickness of about 5 μm was formed on the copper circuit.
%) Was used as the object to be plated.
【0035】この被めっき物を、下記表1に示す無電解
金めっき液中に10分間浸漬して無電解金めっき皮膜を
形成した。
This object to be plated was immersed in an electroless gold plating solution shown in Table 1 below for 10 minutes to form an electroless gold plating film.
【0036】形成された金めっき皮膜について、下記の
方法で析出速度、外観、ハンダ接合強、浴安定性及びニ
ッケル皮膜腐食状態を評価した。結果を下記表2に示
す。 *析出速度:蛍光X線膜厚測定装置を用いて膜厚を測定
し、10分間当たりの析出速度を求めた。 *外観:目視により色調および未析出の有無を調べた。 *ハンダ接合強度:パッド径0.5mmのBGA搭載用
パターンに、直径0.63mmの共晶はんだボールをリフ
ロー装置を用いて搭載し、常温はんだボールプル試験器
を用いて、ハンダボールを機械で挟んで垂直に引っ張り
上げる方法によってはんだの接続強度を測定した。 *浴安定性:金濃度及び各種成分の濃度を測定し、補給
操作を行いながら、繰り返し無電解金めっきを行い、2
ターン終了後、めっき液を0.2μmのメンブランフィ
ルターで濾過した。その後、フィルター上に残った濾過
物について、蛍光X線分析装置を用いて金の有無を調べ
た。濾過物中に金の存在が認められなかった場合には、
浴安定性を安定と評価し、濾過物中に金の存在が認めら
れた場合には、浴安定性を不安定と評価した。 *ニッケル皮膜腐食状態:無電解金めっきを行った後、
金剥離剤にて金めっき皮膜を剥離し、走査型電子顕微鏡
でニッケルめっき皮膜の表面状態を観察し、下記の基準
で評価した。
The gold plating film formed was evaluated for deposition rate, appearance, solder joint strength, bath stability and nickel film corrosion state by the following methods. The results are shown in Table 2 below. * Deposition rate: The film thickness was measured using a fluorescent X-ray film thickness measuring device, and the deposition rate per 10 minutes was determined. * Appearance: The color tone and the presence or absence of non-precipitation were visually examined. * Solder bond strength: A 0.63 mm diameter eutectic solder ball is mounted on a BGA mounting pattern with a pad diameter of 0.5 mm using a reflow device, and the solder ball is sandwiched by a machine using a normal temperature solder ball pull tester. The connection strength of the solder was measured by the method of pulling up vertically with. * Bath stability: The gold concentration and the concentration of various components are measured, and electroless gold plating is repeatedly performed while performing the replenishment operation.
After the end of the turn, the plating solution was filtered with a 0.2 μm membrane filter. Then, the filtered material remaining on the filter was examined for the presence of gold using a fluorescent X-ray analyzer. If no gold is found in the filtrate,
The bath stability was evaluated as stable, and when the presence of gold was found in the filtrate, the bath stability was evaluated as unstable. * Nickel film corrosion state: After performing electroless gold plating,
The gold plating film was peeled off with a gold peeling agent, the surface state of the nickel plating film was observed with a scanning electron microscope, and the following criteria were evaluated.
【0037】○:良好、△:一部腐食あり、×:腐食が
多数発生
◯: Good, Δ: Partially corroded, ×: Many corroded
【0038】[0038]
【表1】 [Table 1]
【0039】[0039]
【表2】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 下地 輝明 大阪府大阪市鶴見区放出東1丁目10番25号 奥野製薬工業株式会社表面技術研究所内 (72)発明者 工藤 喜美子 大阪府大阪市鶴見区放出東1丁目10番25号 奥野製薬工業株式会社表面技術研究所内 (72)発明者 村瀬 直美 大阪府大阪市鶴見区放出東1丁目10番25号 奥野製薬工業株式会社表面技術研究所内 Fターム(参考) 4K022 AA41 AA42 BA03 DA01 DB01 DB05 5E343 BB23 BB24 BB44 CC78 DD33   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Teruaki Shimoji             Osaka Prefecture Osaka City Tsurumi-ku Release 1-10-25 East               Okuno Pharmaceutical Industry Co., Ltd. (72) Inventor Kimiko Kudo             Osaka Prefecture Osaka City Tsurumi-ku Release 1-10-25 East               Okuno Pharmaceutical Industry Co., Ltd. (72) Inventor Naomi Murase             Osaka Prefecture Osaka City Tsurumi-ku Release 1-10-25 East               Okuno Pharmaceutical Industry Co., Ltd. F term (reference) 4K022 AA41 AA42 BA03 DA01 DB01                       DB05                 5E343 BB23 BB24 BB44 CC78 DD33

Claims (2)

    【特許請求の範囲】[Claims]
  1. 【請求項1】(i)水溶性金化合物、(ii)錯化剤、
    (iii)酸化数2〜4のカルコゲン元素を含む酸及びそ
    の塩からなる群から選ばれた少なくとも一種の成分、
    (iv)ヒドラジン及びその誘導体からなる群から選ばれ
    た少なくとも一種の成分、並びに(v)分子内に2個以
    上のイミノ基を含み、置換基を有することのあるエチレ
    ン基を該イミノ基の窒素原子間に有する化合物、を含有
    することを特徴とする無電解金めっき液。
    1. A water-soluble gold compound (i), a complexing agent (ii),
    (Iii) at least one component selected from the group consisting of acids containing chalcogen elements having an oxidation number of 2 to 4 and salts thereof,
    (Iv) at least one component selected from the group consisting of hydrazine and its derivatives, and (v) an ethylene group containing two or more imino groups in the molecule and optionally having a substituent, the nitrogen atom of the imino group An electroless gold plating solution comprising a compound having atoms.
  2. 【請求項2】水溶性金化合物がシアン化金錯塩であり、
    錯化剤が、エチレンジアミン誘導体である請求項1に記
    載の無電解金めっき液。
    2. The water-soluble gold compound is a gold cyanide complex salt,
    The electroless gold plating solution according to claim 1, wherein the complexing agent is an ethylenediamine derivative.
JP2002082882A 2002-03-25 2002-03-25 Electroless gold plating solution Active JP3831842B2 (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004038063A1 (en) * 2002-10-22 2004-05-06 Nihon Koujundo Kagaku Co., Ltd. Substitution type electroless gold plating bath
JP2008144187A (en) * 2006-12-06 2008-06-26 C Uyemura & Co Ltd Electroless gold plating bath, electroless gold plating method, and electronic component
JP2008144188A (en) * 2006-12-06 2008-06-26 C Uyemura & Co Ltd Electroless gold plating bath, electroless gold plating method, and electronic component
JP2008169425A (en) * 2007-01-11 2008-07-24 C Uyemura & Co Ltd Method for maintaining plating capability of electroless gold-plating bath
JP2008174774A (en) * 2007-01-17 2008-07-31 Okuno Chem Ind Co Ltd Reduction precipitation type electroless gold plating liquid for palladium film
JP2008214703A (en) * 2007-03-05 2008-09-18 Rohm & Haas Electronic Materials Llc Electroless gold plating liquid
JP2008266668A (en) * 2007-04-16 2008-11-06 C Uyemura & Co Ltd Electroless gold-plating method and electronic component
KR101483599B1 (en) 2008-07-04 2015-01-16 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 An electroless gold plating solution
CN108026642A (en) * 2015-09-21 2018-05-11 埃托特克德国有限公司 Method for bath compositions and deposition thereof without electric golden plating

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004038063A1 (en) * 2002-10-22 2004-05-06 Nihon Koujundo Kagaku Co., Ltd. Substitution type electroless gold plating bath
KR101393478B1 (en) 2006-12-06 2014-05-13 우에무라 고교 가부시키가이샤 Electroless gold plating bath, electroless gold plating method and electronic parts
JP2008144187A (en) * 2006-12-06 2008-06-26 C Uyemura & Co Ltd Electroless gold plating bath, electroless gold plating method, and electronic component
KR101393477B1 (en) 2006-12-06 2014-05-13 우에무라 고교 가부시키가이샤 Electroless gold plating bath, electroless gold plating method and electronic parts
TWI457462B (en) * 2006-12-06 2014-10-21 Uyemura C & Co Ltd Electroless gold plating bath, electroless gold plating method and electronic parts
JP2008144188A (en) * 2006-12-06 2008-06-26 C Uyemura & Co Ltd Electroless gold plating bath, electroless gold plating method, and electronic component
KR101488885B1 (en) 2007-01-11 2015-02-02 우에무라 고교 가부시키가이샤 Method for maintaining plating capacity in electroless gold plating bath
JP2008169425A (en) * 2007-01-11 2008-07-24 C Uyemura & Co Ltd Method for maintaining plating capability of electroless gold-plating bath
JP2008174774A (en) * 2007-01-17 2008-07-31 Okuno Chem Ind Co Ltd Reduction precipitation type electroless gold plating liquid for palladium film
JP2008214703A (en) * 2007-03-05 2008-09-18 Rohm & Haas Electronic Materials Llc Electroless gold plating liquid
TWI424085B (en) * 2007-04-16 2014-01-21 Uyemura C & Co Ltd Electroless gold plating method and electronic parts
US8124174B2 (en) * 2007-04-16 2012-02-28 C. Uyemura & Co., Ltd. Electroless gold plating method and electronic parts
JP2008266668A (en) * 2007-04-16 2008-11-06 C Uyemura & Co Ltd Electroless gold-plating method and electronic component
KR101483599B1 (en) 2008-07-04 2015-01-16 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 An electroless gold plating solution
CN108026642A (en) * 2015-09-21 2018-05-11 埃托特克德国有限公司 Method for bath compositions and deposition thereof without electric golden plating
TWI709663B (en) * 2015-09-21 2020-11-11 德商德國艾托特克公司 Plating bath composition for electroless plating of gold, method for depositing a gold layer and use of ethylenediamine derivative

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