JP3135699B2 - Concentrated storage solution for electroless gold plating solution - Google Patents
Concentrated storage solution for electroless gold plating solutionInfo
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- JP3135699B2 JP3135699B2 JP04254345A JP25434592A JP3135699B2 JP 3135699 B2 JP3135699 B2 JP 3135699B2 JP 04254345 A JP04254345 A JP 04254345A JP 25434592 A JP25434592 A JP 25434592A JP 3135699 B2 JP3135699 B2 JP 3135699B2
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- concentration
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- plating solution
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Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は無電解金めっき液に関わ
り、めっき液成分を分割濃縮することにより長期にわた
って保存が可能であり、かつ安定な無電解金めっき液に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless gold plating solution, and more particularly to a stable electroless gold plating solution which can be stored for a long period of time by dividing and concentrating plating solution components.
【０００２】[0002]
【従来の技術】従来の無電解金めっき液は、例えば塩化
金（III）酸カリウム塩を還元剤としてボラン系化合物
を主成分とするものが特公昭５６−２０３５３号に開示
され、またチオ硫酸金（I）ナトリウムと還元剤として
チオ尿素を主成分とするものが特開昭６２−８６１７１
号に開示されている。2. Description of the Related Art As a conventional electroless gold plating solution, for example, a solution containing a borane compound as a main component using potassium chloroaurate (III) as a reducing agent is disclosed in JP-B-56-20353. Japanese Unexamined Patent Publication (Kokai) No. 62-86171 discloses a composition mainly composed of sodium gold (I) and thiourea as a reducing agent.
Issue.
【０００３】[0003]
【発明が解決しようとする課題】上述した特公昭５６−
２０３５３号および特開昭６２−８６１７１号の無電解
金めっき液は、金錯塩、錯化剤、ｐＨ緩衝剤および還元
剤等のめっき成分を順次混合して建浴するため、イオン
濃度は過飽和に達しており、濃縮化ができない。よっ
て、大量にめっき液を建浴する場合、めっき建浴時間に
多大な時間を要するだけでなく、均質なめっき液が得ら
れない。さらに前記無電解金めっき液は、未使用のまま
室温にて保管しておくと、約１カ月ほどでめっき液に沈
殿が生じて、めっき液として使用できなくなるので長期
に渡って保管できないという問題がある。[Problems to be Solved by the Invention]
The electroless gold plating solution disclosed in Japanese Patent No. 20353 and Japanese Patent Application Laid-Open No. 62-86171 is constructed by sequentially mixing plating components such as a gold complex salt, a complexing agent, a pH buffering agent, and a reducing agent. Reached and cannot be concentrated. Therefore, when a large amount of plating solution is to be bathed, not only a large amount of time is required for bathing time but also a uniform plating solution cannot be obtained. Further, when the electroless gold plating solution is stored unused at room temperature, the plating solution precipitates in about one month and cannot be used as a plating solution, so that it cannot be stored for a long time. There is.
【０００４】本発明の目的は、めっき液の濃縮化が可能
であり、かつ長期保存性に優れた無電解金めっき液を提
供することである。[0004] An object of the present invention is to provide an electroless gold plating solution capable of concentrating a plating solution and having excellent long-term storage properties.
【０００５】[0005]
【課題を解決するための手段】上記目的は、金錯塩と他
のめっき成分とを分割して建浴することにより、達成さ
れる。このとき金錯塩としては、３価の金錯塩よりさら
に安定な１価の金錯塩を用いることが望ましい。そして
前記１価の金錯塩としては、亜硫酸金（I）塩、チオ硫
酸金（I）塩、あるいはこれらを混合した金錯塩が望ま
しい。またこれら金錯塩を形成する配位子である亜硫酸
イオン及びチオ硫酸イオンは、３価の金イオンを１価の
金イオンに還元する能力を有するので、塩化金（III）
酸塩を出発物質として建浴しても、何等差し支えない。The above object is achieved by dividing a gold complex salt and another plating component into a bath. At this time, it is desirable to use a monovalent gold complex salt that is more stable than a trivalent gold complex salt. The monovalent gold complex is preferably a gold (I) sulfite, a gold (I) thiosulfate, or a gold complex obtained by mixing these. In addition, since sulfite ions and thiosulfate ions, which are ligands forming these gold complex salts, have the ability to reduce trivalent gold ions to monovalent gold ions, gold (III) chloride
There is no problem if a bath is prepared using an acid salt as a starting material.
【０００６】さらにめっき液を分割することにより、分
割液の濃縮が可能となるため、めっき液の均質化及び建
浴時の作業低減も同時に達成される。[0006] Further, by dividing the plating solution, it is possible to concentrate the divided solution, so that the plating solution can be homogenized and the work during the bathing can be reduced at the same time.
【０００７】なお、上記濃縮液の好ましい濃縮倍率につ
いては、後の実施例で詳述するが、各成分の溶解度に依
存し、実用的に有効な濃縮範囲は、２倍〜４０倍であ
る。[0007] The preferable concentration ratio of the above-mentioned concentrated solution will be described in detail in Examples below, but depends on the solubility of each component, and the practically effective concentration range is 2 to 40 times.
【０００８】[0008]
【作用】無電解金めっき液の長期保存性は、金錯体の安
定性に依存する。３価の金イオンは、Ａｕ2Ｏ3やＡｕ
（ＯＨ）3等のコロイドを生成し易く、３価の金錯体は
これらのコロイドに変化して沈殿を生じ易い。一方、１
価の金イオンは、これら液の不安定要因になりうるコロ
イドを生成することなく、金錯体として安定に存在する
ことから無電解金めっき液の金錯塩として適している。
よって１価の金イオンと安定な錯体を形成する錯化剤を
添加し、金錯体として分割することが望ましい。そして
錯化剤としては、亜硫酸塩あるいはチオ硫酸塩が望まし
い。The long-term storage stability of the electroless gold plating solution depends on the stability of the gold complex. Trivalent gold ions include Au 2 O 3 and Au
Colloids such as (OH) 3 are easily formed, and the trivalent gold complex is easily changed to these colloids and precipitates easily. Meanwhile, 1
Valent gold ions are suitable as a gold complex salt of an electroless gold plating solution because they are stably present as a gold complex without forming a colloid which may be an instability factor of these solutions.
Therefore, it is desirable to add a complexing agent that forms a stable complex with a monovalent gold ion to divide the complex as a gold complex. As the complexing agent, a sulfite or a thiosulfate is desirable.
【０００９】また無電解金めっき液の原液には、本来金
錯塩、錯化剤、およびｐＨ緩衝剤が、過飽和近くまで含
まれており、濃縮すれば溶解度の小さい成分が結晶沈殿
することが予期される。しかしめっき液を分割して保管
することで、分割液中のイオン量が分散するので、過飽
和状態が緩和される。よって分割液は濃縮可能となり、
特に金錯塩と錯化剤の分割濃縮液においては、錯化剤濃
度が高濃度となるため、金錯体の安定性も一段と高ま
り、長期保管が可能となる。ただし、室温においても還
元剤と金イオンの酸化還元反応が、徐々に進行し金の沈
殿や濁りを生じる可能性があるため、還元剤のみ単独で
濃縮保管し、他のめっき成分とめっき直前に混合するこ
とが望ましい。Also, the stock solution of the electroless gold plating solution originally contains a gold complex salt, a complexing agent, and a pH buffer to near supersaturation, and it is expected that components having low solubility will precipitate out of crystals when concentrated. Is done. However, when the plating solution is divided and stored, the amount of ions in the divided solution is dispersed, so that the supersaturated state is alleviated. Therefore, the split solution can be concentrated,
In particular, in the concentrated concentrated solution of the gold complex salt and the complexing agent, the concentration of the complexing agent is high, so that the stability of the gold complex is further enhanced and long-term storage is possible. However, even at room temperature, since the oxidation-reduction reaction between the reducing agent and the gold ions may proceed slowly and cause gold precipitation or turbidity, the reducing agent alone is concentrated and stored alone, and immediately before plating with other plating components. It is desirable to mix.
【００１０】なお分割の組み合わせは、 （１）２分割液： １液 金錯塩、錯化剤およびｐＨ緩衝剤（〜２倍） ２液 還元剤（〜４０倍） （２）３分割液： １液 金錯塩と錯化剤（〜４倍） ２液 ｐＨ緩衝剤 （〜２倍） ３液 還元剤 （〜４０倍） 次にこれらの各分割液について、以下（ａ）〜（ｇ）に
量的限定とその限定理由を述べる。 （１）２分割液： （ａ）金錯塩としての塩化金（III）酸ナトリウムの濃
縮量は５〜１５０ｇ／ｌが良く、好ましくは、１０〜５
０ｇ／ｌである。５ｇ／ｌより少ないと濃縮の意味がな
く、１５０ｇ／ｌより多いと、金の沈殿が生じる。The combination of the divisions is as follows: (1) Two-part liquid: One part Gold complex salt, complexing agent and pH buffer (up to twice) Two-part reducing agent (up to 40 times) (2) Three-part liquid: 1 Liquid Gold complex salt and complexing agent (up to 4 times) 2 liquids pH buffer (up to 2 times) 3 liquids Reducing agent (up to 40 times) Next, for each of these divided liquids, measure the following (a) to (g) State the limitations and the reasons for limitation. (1) Two-part liquid: (a) The concentration of sodium chloroaurate (III) as a gold complex salt is preferably 5 to 150 g / l, more preferably 10 to 5 g / l.
0 g / l. If it is less than 5 g / l, there is no meaning in concentration, and if it is more than 150 g / l, gold precipitates.
【００１１】（ｂ）金錯塩としての亜硫酸金（Ｉ）ナト
リウムの濃縮量は５〜１５０ｇ／ｌが良く、好ましく
は、１０〜５０ｇ／ｌである。５ｇ／ｌより少ないと濃
縮の意味がなく、１５０ｇ／ｌより多いと、金の沈殿が
生じる。(B) The concentration of sodium gold (I) sulfite as a gold complex salt is preferably 5 to 150 g / l, and more preferably 10 to 50 g / l. If it is less than 5 g / l, there is no meaning in concentration, and if it is more than 150 g / l, gold precipitates.
【００１２】（ｃ）金錯塩としての亜硫酸チオ硫酸金
（Ｉ）ナトリウムの濃縮量は５〜１５０ｇ／ｌが良く、
好ましくは、１０〜５０ｇ／ｌである。５ｇ／ｌより少
ないと濃縮の意味がなく、１５０ｇ／ｌより多いと、金
の沈殿が生じる。(C) The concentration of sodium gold (I) thiosulfate as a gold complex salt is preferably 5 to 150 g / l.
Preferably, it is 10 to 50 g / l. If it is less than 5 g / l, there is no meaning in concentration, and if it is more than 150 g / l, gold precipitates.
【００１３】（ｄ）錯化剤としてのチオ硫酸ナトリウム
の濃縮量は、１０〜３００ｇ／ｌが良く、好ましくは、
２０〜５０ｇ／ｌである。１０ｇ／ｌより少ないと濃縮
の意味がなく、３００ｇ／ｌより多いと、再結晶沈殿を
生じる。(D) The concentration of sodium thiosulfate as a complexing agent is preferably 10 to 300 g / l, preferably
20 to 50 g / l. If it is less than 10 g / l, there is no meaning in concentration, and if it is more than 300 g / l, recrystallization precipitation occurs.
【００１４】（ｅ）錯化剤としての亜硫酸ナトリウムの
濃縮量は、１０〜２００ｇ／ｌが良く、好ましくは、２
０〜１００ｇ／ｌである。１０ｇ／ｌより少ないと濃縮
の意味がなく、２００ｇ／ｌより多いと、再結晶沈殿を
生じる。(E) The concentration of sodium sulfite as a complexing agent is preferably 10 to 200 g / l, preferably 2 to 200 g / l.
0 to 100 g / l. If it is less than 10 g / l, there is no meaning in concentration, and if it is more than 200 g / l, recrystallization precipitation occurs.
【００１５】（ｆ）ｐＨ緩衝剤としての四ほう酸カリウ
ムの濃縮量は、１０〜３００ｇ／ｌが良く、好ましく
は、２５〜１５０ｇ／ｌである。１０ｇ／ｌより少ない
と濃縮の意味がなく、３００ｇ／ｌより多いと、再結晶
沈殿を生じる。(F) The concentration of potassium tetraborate as a pH buffer is preferably 10 to 300 g / l, and more preferably 25 to 150 g / l. If it is less than 10 g / l, there is no meaning in concentration, and if it is more than 300 g / l, recrystallization precipitation occurs.
【００１６】（ｇ）還元剤としてのチオ尿素の濃縮量
は、１〜１００ｇ／ｌが良く、好ましくは、２〜５０ｇ
／ｌである。２ｇ／ｌより少ないと濃縮の意味がなく、
１００ｇ／ｌより多いと、再結晶沈殿を生じる。(G) The concentration of thiourea as a reducing agent is preferably 1 to 100 g / l, and more preferably 2 to 50 g.
/ L. If it is less than 2 g / l, there is no meaning of concentration,
If it exceeds 100 g / l, recrystallization precipitation occurs.
【００１７】（２）３分割液：（ａ）金錯塩としての塩
化金（III）酸ナトリウムの濃縮量は５〜３００ｇ／ｌ
が良く、好ましくは、１０〜２００ｇ／ｌである。５ｇ
／ｌより少ないと濃縮の意味がなく、３００ｇ／ｌより
多いと、金の沈殿が生じる。(2) Tripartite liquid: (a) The concentration of sodium chloroaurate (III) as a gold complex salt is 5 to 300 g / l.
And preferably 10 to 200 g / l. 5g
If it is less than / l, there is no meaning of concentration, and if it is more than 300 g / l, gold precipitates.
【００１８】（ｂ）金錯塩としての亜硫酸金（Ｉ）ナト
リウムの濃縮量は５〜３００ｇ／ｌが良く、好ましく
は、１０〜２００ｇ／ｌである。５ｇ／ｌより少ないと
濃縮の意味がなく、３００ｇ／ｌより多いと、金の沈殿
が生じる。(B) The concentration of sodium gold (I) sulfite as a gold complex is preferably 5 to 300 g / l, more preferably 10 to 200 g / l. If it is less than 5 g / l, there is no meaning of concentration, and if it is more than 300 g / l, gold precipitates.
【００１９】（ｃ）金錯塩としての亜硫酸チオ硫酸金
（Ｉ）ナトリウムの濃縮量は５〜３００ｇ／ｌが良く、
好ましくは、１０〜２００ｇ／ｌである。５ｇ／ｌより
少ないと濃縮の意味がなく、３００ｇ／ｌより多いと、
金の沈殿が生じる。(C) The concentration of sodium gold (I) thiosulfite as a gold complex salt is preferably 5 to 300 g / l,
Preferably, it is 10 to 200 g / l. When the amount is less than 5 g / l, there is no meaning of concentration, and when the amount is more than 300 g / l,
Gold precipitation occurs.
【００２０】（ｄ）錯化剤としてのチオ硫酸ナトリウム
の濃縮量は、１０〜４００ｇ／ｌが良く、好ましくは、
２５〜１００ｇ／ｌである。１０ｇ／ｌより少ないと濃
縮の意味がなく、４００ｇ／ｌより多いと、再結晶沈殿
を生じる。(D) The concentration of sodium thiosulfate as a complexing agent is preferably 10 to 400 g / l, preferably
25 to 100 g / l. If it is less than 10 g / l, there is no meaning in concentration, and if it is more than 400 g / l, recrystallization precipitation occurs.
【００２１】（ｅ）錯化剤としての亜硫酸ナトリウムの
濃縮量は、１０〜３００ｇ／ｌが良く、好ましくは、２
５〜２００ｇ／ｌである。１０ｇ／ｌより少ないと濃縮
の意味がなく、３００ｇ／ｌより多いと、再結晶沈殿を
生じる。(E) The concentration of sodium sulfite as a complexing agent is preferably 10 to 300 g / l, preferably 2 to 300 g / l.
5 to 200 g / l. If it is less than 10 g / l, there is no meaning in concentration, and if it is more than 300 g / l, recrystallization precipitation occurs.
【００２２】（ｆ）ｐＨ緩衝剤としての四ほう酸カリウ
ムの濃縮量は、１０〜３００ｇ／ｌが良く、好ましく
は、２５〜２００ｇ／ｌである。１０ｇ／ｌより少ない
と濃縮の意味がなく、３００ｇ／ｌより多いと、再結晶
沈殿を生じる。(F) The concentration of potassium tetraborate as a pH buffer is preferably 10 to 300 g / l, more preferably 25 to 200 g / l. If it is less than 10 g / l, there is no meaning in concentration, and if it is more than 300 g / l, recrystallization precipitation occurs.
【００２３】（ｇ）還元剤としてのチオ尿素の濃縮量
は、１〜１００ｇ／ｌが良く、好ましくは、２〜５０ｇ
／ｌである。２ｇ／ｌより少ないと濃縮の意味がなく、
１００ｇ／ｌより多いと、再結晶沈殿を生じる。(G) The concentration of thiourea as a reducing agent is preferably from 1 to 100 g / l, more preferably from 2 to 50 g / l.
/ L. If it is less than 2 g / l, there is no meaning of concentration,
If it exceeds 100 g / l, recrystallization precipitation occurs.
【００２４】[0024]
【実施例】以下に本発明を実施例により詳細に説明す
る。 実施例１ 本発明の濃縮化した無電解金めっき液の長期保存性を調
べるために、以下に示すめっき液組成において従来液と
の比較を行った。The present invention will be described below in detail with reference to examples. Example 1 In order to examine the long-term storage stability of the concentrated electroless gold plating solution of the present invention, a plating solution composition shown below was compared with a conventional solution.
【００２５】（１）本実施例：２分割液 １液（２倍濃縮） 亜硫酸金（Ｉ）ナトリウム １０ｇ／ｌ チオ硫酸ナトリウム ５０ｇ／ｌ 亜硫酸ナトリウム １００ｇ／ｌ 四ほう酸カリウム ５０ｇ／ｌ ｐＨ ９．０ 保管条件 室温 ２液（２０倍濃縮）チオ尿素 ４０ｇ／ｌ 保管条件 室温 （２）従来液 塩化金（III）酸ナトリウム ５ｇ／ｌ チオ硫酸ナトリウム ２５ｇ／ｌ 亜硫酸ナトリウム ５０ｇ／ｌ 四ほう酸ナトリウム ３０ｇ／ｌ チオ尿素 ２ｇ／ｌ ｐＨ ９．０ 保管条件 室温 上記（１），（２）液を０．２２umフィルターでろ過後
テフロン瓶に移して密栓し、室温にて保管した。その結
果（１）の本実施例液は、保管後２００日経過しても、
１液２液とも沈殿あるいは濁り等の外観変化はみられな
かった。しかし（２）の従来液は、３０日後に、金の沈
殿が生成し液に濁りが生じて使用不能となった。本実施
例液の保管５０日後、および２００日後のめっき速度及
び無負荷寿命を測定するために、１液５００ｍｌに水４
５０ｍｌを加えて撹はんし、さらに２液５０ｍｌょ添加
して１ｌの無電解金めっき液とした後、８０℃にてめっ
き速度を測った。無負荷寿命は、８０℃で加温したまま
液中に沈殿あるいは濁りが生じるまでの時間で評価し
た。その結果、５０日後及び２００日後ともめっき速度
０．９um/h、無負荷寿命１４時間であり、従来液の建浴
直後と差異はみられなかった。これより、従来液と本発
明液とを比較した場合、本発明液は、２００日保管後も
変化はなく、３０日で液分解した従来液よりはるかに安
定であるといえる。(1) This Example: Two-part liquid 1 part (2-fold concentration) Sodium gold (I) sulfite 10 g / l Sodium thiosulfate 50 g / l Sodium sulfite 100 g / l Potassium tetraborate 50 g / l pH 9.0 Storage conditions Room temperature 2 solutions (20-fold concentration) thiourea 40 g / l Storage conditions Room temperature (2) Conventional solution Sodium chloroaurate (III) 5 g / l Sodium thiosulfate 25 g / l Sodium sulfite 50 g / l Sodium tetraborate 30 g / l Thiourea 2 g / l pH 9.0 Storage conditions Room temperature The above solutions (1) and (2) were filtered through a 0.22 μm filter, transferred to a Teflon bottle, sealed, and stored at room temperature. As a result, the liquid of Example 1 of (1) was stored 200 days after storage.
No change in appearance such as precipitation or turbidity was observed in both the first liquid and the second liquid. However, the conventional solution (2) became unusable after 30 days because gold precipitates formed and the solution became turbid. In order to measure the plating rate and the no-load life after 50 days and 200 days of storage of the solution of this example, 500 ml of water was added to 500 ml of one solution.
After adding 50 ml and stirring, and further adding 50 ml of the two solutions to obtain 1 liter of electroless gold plating solution, the plating rate was measured at 80 ° C. The no-load life was evaluated by the time until precipitation or turbidity occurred in the liquid while heating at 80 ° C. As a result, the plating rate was 0.9 μm / h and the no-load life was 14 hours both after 50 days and after 200 days, and there was no difference between the conventional solution and the bath immediately after bathing. Thus, when the conventional solution and the present solution are compared, it can be said that the present solution does not change even after storage for 200 days, and is much more stable than the conventional solution decomposed in 30 days.
【００２６】実施例２：２分割液 １液（２倍濃縮） 塩化金（III）酸ナトリウム １０ｇ／ｌ 水酸化ナトリウム ８ｇ／ｌ チオ硫酸ナトリウム ５０ｇ／ｌ 亜硫酸ナトリウム １００ｇ／ｌ 四ホウ酸カリウム ５０ｇ／ｌ ｐＨ調整（２０％Ｈｃｌ） ９．０ ２液（２０倍濃縮）チオ尿素 ４０ｇ／ｌ ２００日室温保管後も沈殿濁り等の外観変化はなかっ
た。さらに２００日保管後の１液５００ｍｌを１ｌビー
カーに移し、水４５０ｍｌを加えた後、２液５０ｍｌを
添加して１ｌの無電解金めっき液を建浴しめっきを行っ
たところ、めっき速度０．８９um/h、無負荷寿命（８０
℃）１０時間であり、２００日室温保管後のめっき速度
及び無負荷寿命は、従来液の建浴直後と差異はなかっ
た。Example 2: Two-part liquid 1 part (2-fold concentration) Sodium chloroaurate (III) 10 g / l Sodium hydroxide 8 g / l Sodium thiosulfate 50 g / l Sodium sulfite 100 g / l Potassium tetraborate 50 g / l pH adjustment (20% Hcl) 9.0 2 liquid (20-fold concentration) Thiourea 40 g / l Even after storage at room temperature for 200 days, there was no change in appearance such as cloudiness of the precipitate. Further, 500 ml of the first solution after storage for 200 days was transferred to a 1-liter beaker, 450 ml of water was added, and then 50 ml of the second solution was added to form a 1-liter electroless gold plating solution to perform plating. 89um / h, no-load life (80
C) for 10 hours, and the plating rate and the no-load life after storage at room temperature for 200 days were not different from those immediately after the bath of the conventional solution.
【００２７】実施例３：２分割液 実施例２の建浴順序を替えたものであり、ＮａＯＨを必
要としない。Example 3: Two-split solution This is the same as Example 2 except that the order of the bath was changed, and NaOH was not required.
【００２８】 １液（２倍濃縮） 亜硫酸ナトリウム １００ｇ／ｌ 四ホウ酸カリウム ５０ｇ／ｌ 塩化金（III）酸ナトリウム １０ｇ／ｌ チオ硫酸ナトリウム ５０ｇ／ｌ ｐＨ（無調整） ９．０ ２液（２０倍濃縮）チオ尿素 ４０ｇ／ｌ ２００日室温保管後も沈殿濁り等の外観変化はなかっ
た。さらに２００日保管後の１液５００ｍｌを１ｌビー
カーに移し、水４５０ｍｌを加えた後、２液５０ｍｌを
添加して１ｌの無電解金めっき液を建浴しめっきを行っ
た。めっき速度０．８５um/h、無負荷寿命（８０℃）１
０時間であり、２００日室温保管後のめっき速度及び無
負荷寿命は、従来液の建浴直後と差異はなかった。One solution (double concentration) Sodium sulfite 100 g / l Potassium tetraborate 50 g / l Sodium chloroaurate (III) 10 g / l Sodium thiosulfate 50 g / l pH (unadjusted) 9.0 2 solution (20 Double concentration) Thiourea 40 g / l After storage at room temperature for 200 days, there was no change in appearance such as turbidity of the precipitate. Further, 500 ml of the first solution after storage for 200 days was transferred to a 1-liter beaker, 450 ml of water was added, and then 50 ml of the second solution was added to form a 1-liter electroless gold plating solution for plating. Plating rate 0.85um / h, no-load life (80 ℃) 1
It was 0 hours, and the plating rate and the no-load life after storage at room temperature for 200 days were not different from those of the conventional solution immediately after bathing.
【００２９】実施例４：２分割液 １液（２倍濃縮） 亜硫酸ナトリウム １００ｇ／ｌ 亜硫酸チオ硫酸金（Ｉ）ナトリウム １０ｇ／ｌ チオ硫酸ナトリウム ５０ｇ／ｌ 四ホウ酸カリウム ５０ｇ／ｌ ２液（２０倍濃縮）チオ尿素 ４０ｇ／ｌ ２００日室温保管後も沈殿濁り等の外観変化はなかっ
た。さらに２００日保管後の１液５００ｍｌを１ｌビー
カーに移し、水４５０ｍｌを加えた後、２液５０ｍｌを
添加して１ｌの無電解金めっき液を建浴しめっきを行っ
た。めっき速度０．８４um/h、無負荷寿命（８０℃）１
４時間であり、２００日室温保管後のめっき速度及び無
負荷寿命は、従来液の建浴直後と差異はなかった。Example 4: Two-part liquid 1 solution (2 times concentrated) Sodium sulfite 100 g / l Sodium thiosulfite gold (I) sodium 10 g / l Sodium thiosulfate 50 g / l Potassium tetraborate 50 g / l 2 solution (20 Double concentration) Thiourea 40 g / l After storage at room temperature for 200 days, there was no change in appearance such as turbidity of the precipitate. Further, 500 ml of the first solution after storage for 200 days was transferred to a 1-liter beaker, 450 ml of water was added, and then 50 ml of the second solution was added to form a 1-liter electroless gold plating solution for plating. Plating speed 0.84um / h, no-load life (80 ℃) 1
It was 4 hours, and the plating rate and the no-load life after storage at room temperature for 200 days were not different from those of the conventional solution immediately after bathing.
【００３０】実施例５：３分割液 １液（４倍濃縮） 塩化金（III）酸ナトリウム ２０ｇ／ｌ チオ硫酸ナトリウム １００ｇ／ｌ 亜硫酸ナトリウム ２００ｇ／ｌ ｐＨ調整（２０％Ｈｃｌ） ８．５ ２液（４倍濃縮） 四ほう酸カリウム １００ｇ／ｌ ３液（４０倍濃縮）チオ尿素 ８０ｇ／ｌ ２００日室温保管後も沈殿濁り等の外観変化はなかっ
た。さらに２００日保管後の１液２５０ｍｌを１ｌビー
カーに移し、水４７５ｍｌを加えた後、２液２５０ｍｌ
を添加して撹はんしながら、３液２５ｍｌを添加して１
ｌの無電解金めっき液としめっきを行った。めっき速度
０．８６um/h、無負荷寿命（８０℃）１３時間であり、
２００日室温保管後のめっき速度及び無負荷寿命は、従
来液の建浴直後と差異はなかった。Example 5: Three-part liquid 1 solution (4 times concentration) Sodium chloroaurate (III) 20 g / l Sodium thiosulfate 100 g / l Sodium sulfite 200 g / l pH adjustment (20% Hcl) 8.5 2 solution (4-fold concentration) Potassium tetraborate 100 g / l 3 liquid (40-fold concentration) Thiourea 80 g / l Even after storage at room temperature for 200 days, there was no appearance change such as cloudiness of the precipitate. Further, 250 ml of one solution after storage for 200 days was transferred to a 1 liter beaker, and 475 ml of water was added.
While adding and stirring, add 25 ml of the 3 solution and add 1
Then, plating was performed using 1 electroless gold plating solution. The plating rate is 0.86 um / h, the no-load life (80 ° C) is 13 hours,
The plating rate and the no-load life after storage at room temperature for 200 days were not different from those of the conventional solution immediately after bathing.
【００３１】実施例６：３分割液 １液（４倍濃縮） 亜硫酸金（Ｉ）ナトリウム ２０ｇ／ｌ チオ硫酸ナトリウム １００ｇ／ｌ 亜硫酸ナトリウム ２００ｇ／ｌ ｐＨ調整（２０％Ｈｃｌ） ８．５ ２液（４倍濃縮） 四ほう酸カリウム １００ｇ／ｌ ３液（２０倍濃縮）チオ尿素 ４０ｇ／ｌ ２００日室温保管後も沈殿濁り等の外観変化はなかっ
た。さらに２００日保管後の１液２５０ｍｌを１ｌビー
カーに移し、水４５０ｍｌを加えた後、２液２５０ｍｌ
を添加して撹はんしながら、３液５０ｍｌを添加して１
ｌの無電解金めっき液としめっきを行った。めっき速度
０．８８um/h、無負荷寿命（８０℃）１２時間であり、
２００日室温保管後のめっき速度及び無負荷寿命は、従
来液の建浴直後と差異はなかった。Example 6: 1 liquid in 3 divided solutions (4 times concentration) Sodium gold (I) sulfite 20 g / l Sodium thiosulfate 100 g / l Sodium sulfite 200 g / l pH adjustment (20% Hcl) 8.5 2 liquid ( (4 times concentration) Potassium tetraborate 100 g / l 3 solutions (20 times concentration) thiourea 40 g / l Even after storage at room temperature for 200 days, there was no change in appearance such as cloudiness of precipitation. Further, 250 ml of the first solution after storage for 200 days was transferred to a 1 liter beaker, and 450 ml of water was added.
While adding and stirring, add 50 ml of 3 solutions and add 1
Then, plating was performed using 1 electroless gold plating solution. The plating rate is 0.88 um / h, the no-load life (80 ° C) is 12 hours,
The plating rate and the no-load life after storage at room temperature for 200 days were not different from those immediately after the bath of the conventional solution.
【００３２】実施例７：３分割液 １液（４倍濃縮） 亜硫酸チオ硫酸金（Ｉ）ナトリウム ２０ｇ／ｌ チオ硫酸ナトリウム １００ｇ／ｌ 亜硫酸ナトリウム ２００ｇ／ｌ ｐＨ調整（２０％Ｈｃｌ） ８．５ ２液（４倍濃縮） 四ほう酸カリウム １００ｇ／ｌ ３液（４０倍濃縮）チオ尿素 ８０ｇ／ｌ ２００日室温保管後も沈殿濁り等の外観変化はなかっ
た。さらに２００日保管後の１液２５０ｍｌを１ｌビー
カーに移し、水４７５ｍｌを加えた後、２液２５０ｍｌ
を添加して撹はんしながら、３液２５ｍｌを添加して１
ｌの無電解金めっき液としめっきを行った。めっき速度
０．８２um/h、無負荷寿命（８０％）１２時間であり、
２００日室温保管後のめっき速度及び無負荷寿命は、従
来液の建浴直後と差異はなかった。Example 7: 1 liquid (three-fold concentration) in 3 divided solutions 20 g / l sodium gold thiosulfate 100 g / l sodium thiosulfate 200 g / l sodium sulfite 200 g / l pH adjustment (20% Hcl) 8.5 2 Liquid (concentrated 4 times) Potassium tetraborate 100 g / l 3 liquid (concentrated 40 times) Thiourea 80 g / l Even after storage at room temperature for 200 days, there was no appearance change such as cloudiness of the precipitate. Further, 250 ml of the first solution after storage for 200 days was transferred to a 1-liter beaker, and 475 ml of water was added.
While adding and stirring, add 25 ml of the 3 solution and add 1
Then, plating was performed using 1 electroless gold plating solution. The plating rate is 0.82 um / h, the no-load life (80%) is 12 hours,
The plating rate and the no-load life after storage at room temperature for 200 days were not different from those immediately after the bath of the conventional solution.
【００３３】[0033]
【発明の効果】以上のょうに本発明によれば、めっき液
を分割濃縮化することにより、錯化剤濃度も高濃度とな
るため、金錯体の安全性が向上し、長期にわたって液の
劣化を招くことなく保管することができる。As described above, according to the present invention, since the concentration of the complexing agent is increased by dividing and concentrating the plating solution, the safety of the gold complex is improved, and the solution is deteriorated over a long period of time. Can be stored without inviting.
【００３４】また、めっき液を分割濃縮液として保管で
きるので、使用の都度めっき液の建浴に多大の時間をか
ける必要がなく、めっき作業を低減する効果がある。Further, since the plating solution can be stored as a divided concentrated solution, it is not necessary to spend much time for bathing of the plating solution each time it is used, and there is an effect of reducing the plating work.
【００３５】さらに。めっき液を分割濃縮液として保管
できるので、保管容積が小さくなり、かつ大量建浴が可
能でありめっき品質のばらつきの少ないめっき液を提供
できる。Further. Since the plating solution can be stored as a divided concentrated solution, the storage volume can be reduced, a large amount of bath can be built, and a plating solution with little variation in plating quality can be provided.
【００３６】さらに、長期間の保管が可能な濃縮液であ
るので、めっき不良が発生した場合においても、即使用
可能なめっき液をストックしておくことができ、作業効
率の向上につながる。Further, since the concentrated solution can be stored for a long period of time, even if plating failure occurs, a plating solution that can be used immediately can be stocked, which leads to an improvement in working efficiency.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 樫村 隆司 神奈川県横浜市戸塚区吉田町292番地株 式会社 日立製作所生産技術研究所内 (72)発明者 嶋崎 威 茨城県下館市大字小川1500番地日立化成 工業株式会社電子部品事業部内 (56)参考文献 特開 平２−145771（ＪＰ，Ａ) 特公 昭54−26495（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 18/44 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Kashimura 292, Yoshida-cho, Totsuka-ku, Yokohama-shi, Kanagawa Prefecture Inside of Hitachi, Ltd. (56) References JP-A-2-145771 (JP, A) JP-B-54-26495 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 18/44
Claims (3)
錯塩及び錯化剤を含む溶液と還元剤を含む溶液とに分割
し、かつ濃縮保存することを特徴とする無電解金めっき
液の濃縮保存液。An electroless gold plating solution characterized in that the components of the electroless gold plating solution are divided into a solution containing at least a gold complex salt and a complexing agent and a solution containing a reducing agent, and are concentrated and stored. Concentrated stock solution.
Ι）酸塩、亜硫酸金（Ι）塩、亜硫酸チオ硫酸金（Ι）
塩、またはそれらの混合物から選ばれ、かつ前記錯化物
が、チオ硫酸塩または亜硫酸塩であって、前記還元剤が
チオ尿素であることを特徴とする請求項１に記載の無電
解金めっき液の濃縮保存液。2. The method according to claim 1, wherein the gold complex salt comprises at least gold chloride (ΙΙ
Ι) Salt, gold sulfite (Ι) salt, gold thiosulfite (Ι)
The electroless gold plating solution according to claim 1, wherein the complex is selected from a salt or a mixture thereof, and the complex is thiosulfate or sulfite, and the reducing agent is thiourea. Concentrated stock solution.
であることを特徴とする請求項１に記載の無電解金めっ
き液の濃縮保存液。3. The concentrated preservation solution of an electroless gold plating solution according to claim 1, wherein the concentration ratio of the solution is in the range of 2 to 40 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04254345A JP3135699B2 (en) | 1992-09-24 | 1992-09-24 | Concentrated storage solution for electroless gold plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04254345A JP3135699B2 (en) | 1992-09-24 | 1992-09-24 | Concentrated storage solution for electroless gold plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06101055A JPH06101055A (en) | 1994-04-12 |
| JP3135699B2 true JP3135699B2 (en) | 2001-02-19 |
Family
ID=17263708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04254345A Expired - Lifetime JP3135699B2 (en) | 1992-09-24 | 1992-09-24 | Concentrated storage solution for electroless gold plating solution |
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| Country | Link |
|---|---|
| JP (1) | JP3135699B2 (en) |
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|---|---|---|---|---|
| JP4524773B2 (en) * | 2003-03-14 | 2010-08-18 | 石原薬品株式会社 | Split storage method of electroless tin plating bath |
-
1992
- 1992-09-24 JP JP04254345A patent/JP3135699B2/en not_active Expired - Lifetime
Cited By (1)
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH06101055A (en) | 1994-04-12 |
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