JPH05112877A - Electroless tin-lead alloy plating solution - Google Patents
Electroless tin-lead alloy plating solutionInfo
- Publication number
- JPH05112877A JPH05112877A JP29982791A JP29982791A JPH05112877A JP H05112877 A JPH05112877 A JP H05112877A JP 29982791 A JP29982791 A JP 29982791A JP 29982791 A JP29982791 A JP 29982791A JP H05112877 A JPH05112877 A JP H05112877A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- plating solution
- lead alloy
- sulfonic acid
- mol
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、銅系基材面に密着性
の優れた錫−鉛合金皮膜を作業性良く十分な厚さで形成
することができる無電解はんだめっき液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless solder plating solution capable of forming a tin-lead alloy film having excellent adhesion on a copper-based substrate surface with good workability and a sufficient thickness.
【０００２】[0002]
【従来技術とその課題】電気機器或いは電子機器部品等
として使用される銅又は銅合金材面の酸化を防止し良好
なはんだ付け性を確保する手段の１つに、錫イオン及び
鉛イオンを含む処理液中に前記銅系基材面を浸漬し、そ
の際の置換反応によって該基材面に錫−鉛合金（はん
だ）皮膜を析出させる「無電解錫−鉛合金めっき」があ
る。2. Description of the Related Art Tin and lead ions are included as one of means for preventing oxidation of a copper or copper alloy material surface used for electric equipment or electronic equipment parts and ensuring good solderability. There is "electroless tin-lead alloy plating" in which the surface of the copper-based substrate is immersed in a treatment liquid and a tin-lead alloy (solder) film is deposited on the substrate surface by a substitution reaction at that time.
【０００３】そして、このような「無電解錫−鉛合金め
っき」に適用されるめっき液としては、塩酸をベ−スと
したもの（特開昭４９−６４５２７号公報，特開昭５０
−５７９２７号公報等を参照）、硼フッ化水素酸をベ−
スとしたもの（特公昭６２−２６３０号公報等を参照）
並びに有機スルホン酸をベ−スとしたもの（特開平１−
１８４２７９号公報，特開平１−２９０７７４号公報，
特開平２−１９７５８０号公報，特開平３−６３５７号
公報，特開平３−２８３６０号公報等を参照）が知られ
ている。As a plating solution applied to such "electroless tin-lead alloy plating", hydrochloric acid-based plating solution is used (JP-A-49-64527 and JP-A-50).
-57927, etc.), borohydrofluoric acid
Those that have been made (see Japanese Patent Publication No. 62-2630, etc.)
And those based on organic sulfonic acid (JP-A-1-
184279, Japanese Patent Laid-Open No. 1-290774,
JP-A-2-197580, JP-A-3-6357, JP-A-3-28360, etc.) are known.
【０００４】ところが、このうち、塩酸をベ−スとした
無電解錫−鉛合金めっき液には「塩酸のミストが発生し
て使用時に周りの環境悪化や設備の腐食を招く」という
問題のあることが、また、硼フッ化水素酸をベ−スとし
た無電解錫−鉛合金めっき液に対しては「排水中に有害
なフッ素が含まれるのを防止するのが非常に困難であ
る」との問題を有していることが指摘されていた。その
上、これらの無電解錫−鉛合金めっき液から得られるめ
っき皮膜は何れも銅系基材との密着性が悪く、剥がれを
生じ易いという欠点もあった。However, among them, the electroless tin-lead alloy plating solution using hydrochloric acid as a base has a problem that "mist of hydrochloric acid is generated to cause deterioration of surrounding environment and corrosion of equipment during use". In addition, it is "it is very difficult to prevent harmful fluorine from being contained in the waste water" for the electroless tin-lead alloy plating solution based on borofluoric acid. It was pointed out that there is a problem with. In addition, all of the plating films obtained from these electroless tin-lead alloy plating solutions have the drawback that they have poor adhesion to the copper-based substrate and are liable to peel off.
【０００５】一方、有機スルホン酸をベ−スとした無電
解錫−鉛合金めっき液には上記のような問題はないもの
の、このめっき液を使用した場合には形成される無電解
錫−鉛合金めっき皮膜の厚さが精々２〜３μｍ程度にし
か達せず、塩酸浴や硼フッ化水素酸浴を使用した場合と
同等の十分な膜厚を確保することができなかった。On the other hand, although the electroless tin-lead alloy plating solution based on organic sulfonic acid does not have the above-mentioned problems, the electroless tin-lead formed when this plating solution is used is formed. The thickness of the alloy plating film reached at most about 2 to 3 μm, and it was not possible to secure a sufficient film thickness equivalent to the case where a hydrochloric acid bath or a borofluoric acid bath was used.
【０００６】このようなことから、本発明が目的とした
のは、銅系基材面に密着性の良い錫−鉛合金皮膜を環境
上の問題少なく十分な膜厚で形成させ得る“置換型の無
電解錫−鉛合金めっき液”を提供することであった。In view of the above, the object of the present invention is to provide a "substitution type" capable of forming a tin-lead alloy film having good adhesion on the surface of a copper-based substrate with a sufficient film thickness without environmental problems. "Electroless tin-lead alloy plating solution".
【０００７】[0007]
【課題を解決するための手段】本発明は、上記目的を達
成すべく、特に“有機スルホン酸浴”の「環境上の問題
が比較的少ない上に密着性の良好な錫−鉛合金めっき皮
膜が得られる」という利点に着目し、それらを生かしつ
つ析出膜厚の増大が図れる手立てを求めて重ねられた研
究の結果等を基に完成されたものであり、「無電解錫−
鉛合金めっき液を、 有機スルホン酸： 0.01〜 1 mol/L(リッ
トル) ， 有機スルホン酸の２価の錫塩： 0.01〜0.5 mol/L ， 有機スルホン酸の２価の鉛塩： 0.01〜0.5 mol/L ， チオ尿素及び／又はその誘導体： 0.05〜 2 mol/L ， 硝酸イオン： 0.01 mol/L以上 を含有して成る組成とすることにより、 銅系基材面に密
着性の良い錫−鉛合金皮膜を十分な膜厚で形成させ得る
ようにした点」に大きな特徴を有している。In order to achieve the above-mentioned object, the present invention provides a tin-lead alloy plating film which has a particularly small "environmental problem and good adhesion" of "organic sulfonic acid bath". It was completed on the basis of the results of research conducted in order to find a way to increase the deposited film thickness while taking advantage of the advantages of "electroless tin-
Lead alloy plating solution, organic sulfonic acid: 0.01 to 1 mol / L (liter), divalent tin salt of organic sulfonic acid: 0.01 to 0.5 mol / L, divalent lead salt of organic sulfonic acid: 0.01 to 0.5 mol / L, thiourea and / or its derivative: 0.05 to 2 mol / L, nitrate ion: 0.01 mol / L or more is included, so that tin- The point is that the lead alloy film can be formed with a sufficient film thickness. "
【０００８】このように、本発明は、「有機スルホン
酸，２価の錫イオン，２価の鉛イオン並びにチオ尿素及
び／又はその誘導体をベ−スとする溶液に硝酸イオンを
添加して成る液組成」を無電解錫−鉛合金めっき液の基
本組成としたことを骨子としているが、これら主成分の
ほか、この種の置換型無電解めっき液の助剤として一般
に用いられている還元剤や界面活性剤等も加えて良いこ
とは言うまでもない。As described above, according to the present invention, "a nitrate ion is added to a solution containing organic sulfonic acid, divalent tin ion, divalent lead ion and thiourea and / or its derivative as a base. The main idea is to have "liquid composition" as the basic composition of the electroless tin-lead alloy plating solution. In addition to these main components, a reducing agent that is commonly used as an auxiliary agent for this type of substitutional electroless plating solution. It goes without saying that a surfactant or the like may be added.
【０００９】なお、本発明に係わる上記無電解錫−鉛合
金めっき液のｐＨは、錫イオン，鉛イオンの溶解度の観
点から２以下とするのが好ましい。また、この無電解錫
−鉛合金めっき液は５０℃以上の温度で使用するのが良
いが、液成分の蒸発，揮発等の兼ね合いからすると加温
は９０℃までとするのが望ましい。更に、めっき処理に
際して液の攪拌を均一に行うことは、得られるめっき皮
膜の均一性のために重要である。そして、めっき液の攪
拌に“空気吹き込み”といった手段を採用することは液
中の錫イオンの酸化が起きるので避けねばならず、その
ため攪拌はスタ−ラや機械揺動によるべきである。The pH of the electroless tin-lead alloy plating solution according to the present invention is preferably 2 or less from the viewpoint of solubility of tin ions and lead ions. Also, this electroless tin-lead alloy plating solution is preferably used at a temperature of 50 ° C. or higher, but it is desirable to heat up to 90 ° C. in consideration of the evaporation and volatilization of the liquid components. Further, it is important to uniformly stir the solution during the plating treatment for the uniformity of the obtained plating film. The use of means such as "air blowing" for stirring the plating solution must be avoided because oxidation of tin ions in the solution occurs, and therefore stirring should be performed by a stirrer or mechanical shaking.
【００１０】以下、本発明に係わる無電解錫−鉛合金め
っき液の基本組成を前記の如くに限定した理由を、各構
成成分の作用と共に詳述する。Hereinafter, the reason why the basic composition of the electroless tin-lead alloy plating solution according to the present invention is limited as described above will be described in detail together with the action of each component.
a) 有機スルホン酸 有機スルホン酸は溶液中の２価の錫イオン（Sn2+）及び
鉛イオン（Pb2+）の安定化のために必要な成分である
が、その含有割合が 0.01mol/L未満であると前記イオン
が不安定となって酸化物，水酸化物として沈澱するよう
になり、一方、１mol/L を超えて含有されると、めっき
液の酸性度が強くなって被めっき材等の腐食が大きくな
りすぎるという不都合を生じる。従って、有機スルホン
酸の含有割合は0.01〜１mol/L と定めた。a) Organic sulfonic acid Organic sulfonic acid is a component necessary for stabilizing the divalent tin ion (Sn 2+ ) and lead ion (Pb 2+ ) in the solution, but its content is 0.01 mol / When it is less than L, the above-mentioned ions become unstable and precipitate as oxides and hydroxides, while when it is contained in excess of 1 mol / L, the acidity of the plating solution becomes strong and the plating target This causes an inconvenience that the corrosion of the material and the like becomes too large. Therefore, the content ratio of the organic sulfonic acid is set to 0.01 to 1 mol / L.
【００１１】なお、使用できる有機スルホン酸として
は、メタンスルホン酸，エタンスルホン酸，プロパンス
ルホン酸，2-プロパンスルホン酸，2-ヒドロキシエタン
スルホン酸，2-ヒドロキシプロパンスルホン酸，p-フェ
ノ−ルスルホン酸，p-アミノベンゼンスルホン酸，p-ト
ルエンスルホン酸等のアルカンスルホン酸，アルカノ−
ルスルホン酸，芳香族スルホン酸を挙げることができ
る。The organic sulfonic acids that can be used include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-propanesulfonic acid, 2-hydroxyethanesulfonic acid, 2-hydroxypropanesulfonic acid, p-phenol sulfone. Acids, alkane sulfonic acids such as p-aminobenzene sulfonic acid, p-toluene sulfonic acid, alkano-
Examples thereof include sulfonic acid and aromatic sulfonic acid.
【００１２】b) 有機スルホン酸の２価の錫塩及び鉛塩 前記有機スルホン酸の２価の錫塩並びに鉛塩は、めっき
液中に２価の錫イオン（Sn2+）及び鉛イオン（Pb2+）を
供給するために必要な成分であり、この錫イオン，鉛イ
オンの組成比を制御することで、得られる析出物（めっ
き皮膜）の錫／鉛の組成比を任意に変化させることがで
きる。これらのイオンは、前記有機スルホン酸の溶液に
酸化錫（２価）や酸化鉛（２価）を溶解させることによ
っても供給され得る。なお、有機スルホン酸の２価の錫
塩及び鉛塩の含有割合がそれぞれ 0.01mol/Lを下回ると
めっきの析出速度が実際作業上不都合な程に遅くなるこ
とから、各々の含有割合の下限は 0.01mol/Lと定めた。
一方、溶解度の関係から含有割合の上限を何れも0.5mol
/Lと定めた。B) Divalent tin salt and lead salt of organic sulfonic acid The divalent tin salt and lead salt of the organic sulfonic acid are divalent tin ion (Sn 2+ ) and lead ion (in the plating solution). Pb 2+ ) is a necessary component for supplying Pb 2+ ), and by controlling the composition ratio of tin ions and lead ions, the tin / lead composition ratio of the obtained precipitate (plating film) can be arbitrarily changed. be able to. These ions can also be supplied by dissolving tin oxide (divalent) or lead oxide (divalent) in the organic sulfonic acid solution. If the content ratio of divalent tin salt and lead salt of organic sulfonic acid is less than 0.01 mol / L, the deposition rate of plating will be slow enough to be practically inconvenient. Therefore, the lower limit of each content ratio is It was set at 0.01 mol / L.
On the other hand, the upper limit of the content ratio is 0.5 mol for both due to solubility.
/ L.
【００１３】c) チオ尿素及び／又はその誘導体 チオ尿素及び／又はその誘導体は置換反応の進行に伴い
めっき液中に溶出する銅イオン（Cu+ ）の錯化剤として
必要な成分であるが、その含有割合が 0.05mol/L未満で
あると置換反応が殆ど起こらなくなる。一方、該成分の
含有割合が多くなっても格別な不都合はないが、溶解度
の関係から２mol/L 以下に止めるのが好ましいと言え
る。従って、チオ尿素及び／又はその誘導体の含有割合
は0.05〜２mol/L と定めた。なお、チオ尿素の誘導体と
しては、ジメチルチオ尿素，ジエチルチオ尿素，アリル
チオ尿素等が挙げられる。C) Thiourea and / or its derivative Thiourea and / or its derivative are components necessary as a complexing agent for copper ions (Cu + ) which are eluted in the plating solution as the substitution reaction proceeds. If the content ratio is less than 0.05 mol / L, the substitution reaction hardly occurs. On the other hand, even if the content ratio of the component is increased, there is no particular inconvenience, but it can be said that it is preferably limited to 2 mol / L or less in view of solubility. Therefore, the content ratio of thiourea and / or its derivative was set to 0.05 to 2 mol / L. Examples of thiourea derivatives include dimethylthiourea, diethylthiourea, allylthiourea and the like.
【００１４】d) 硝酸イオン 本発明に係わる無電解錫−鉛合金めっき液において、硝
酸イオン析出物（めっき皮膜）の膜厚を増加させる重要
な作用を担っている。しかしながら、硝酸イオンの含有
割合が 0.01mol/Lを下回ると上記作用による所望の効果
が得られないことから、硝酸イオン含有割合の下限を
0.01mol/Lと定めた。一方、硝酸イオン量の上限は格別
に定める必要はないが、硝酸イオン源として硝酸を添加
した場合にその含有割合が多くなると基材（被めっき
材）の溶解が著しくなるといった問題を引き起こすこと
から、硝酸イオンは0.5mol/L程度までとするのが望まし
いと言える。D) Nitrate ion In the electroless tin-lead alloy plating solution according to the present invention, it plays an important role of increasing the film thickness of nitrate ion precipitate (plating film). However, if the content ratio of nitrate ions is less than 0.01 mol / L, the desired effect due to the above action cannot be obtained.
It was set at 0.01 mol / L. On the other hand, the upper limit of the amount of nitrate ions does not have to be specified in particular, but when nitric acid is added as a nitrate ion source, the problem is that if the content ratio increases, the base material (material to be plated) will significantly dissolve. It can be said that it is desirable that the nitrate ion is up to about 0.5 mol / L.
【００１５】なお、適用される硝酸イオン源としては、
硝酸，硝酸ナトリウム，硝酸カリウム，硝酸リチウム，
硝酸アンモニウム等、水可溶性の化合物を挙げることが
できる。しかし、陽イオンとして錫，鉛よりも析出電位
が貴な金属イオンを含むものは、めっき皮膜への不必要
な共析が起きるために好ましくない。The applicable nitrate ion source is
Nitric acid, sodium nitrate, potassium nitrate, lithium nitrate,
Water-soluble compounds such as ammonium nitrate can be mentioned. However, cations containing metal ions having a higher deposition potential than tin and lead are not preferable because unnecessary eutectoid to the plating film occurs.
【００１６】前述したように、本発明に係わる無電解錫
−鉛合金めっき液には還元剤，界面活性剤等の成分を加
えることができるが、錫イオン（Sn2+）の酸化防止のた
めに次亜リン酸ナトリウム，ヒドラジン等の還元剤の添
加は非常に効果的である。この場合、還元剤の濃度は０
〜0.5mol/Lの範囲に調整するのが良い。As described above, components such as a reducing agent and a surfactant can be added to the electroless tin-lead alloy plating solution according to the present invention, but in order to prevent oxidation of tin ions (Sn 2+ ). The addition of reducing agents such as sodium hypophosphite and hydrazine is very effective. In this case, the concentration of the reducing agent is 0
It is better to adjust to the range of ~ 0.5mol / L.
【００１７】界面活性剤としては特に非イオン界面活性
剤が好ましく、濃度は０〜10g/L 、望ましくは５g/L 以
下（より望ましくは 0.1〜１g/L ）の範囲に調整するの
が良い。なお、非イオン界面活性剤は基材面の液の濡れ
性を向上しめっきムラを無くするのに有効な成分であ
り、例えば「ノニポ−ル（商品名：三洋化成工業株式会
社）」，「ノイゲン（商品名：第一工業製薬株式会
社）」，「エマルゲン（商品名：花王石鹸株式会
社）」，「ノニオン（商品名：日本油脂株式会社）」等
が使用できる。As the surface active agent, a nonionic surface active agent is particularly preferable, and the concentration should be adjusted within the range of 0 to 10 g / L, preferably 5 g / L or less (more preferably 0.1 to 1 g / L). The nonionic surfactant is an effective component for improving the wettability of the liquid on the surface of the base material and eliminating the unevenness of plating. For example, "Nonipol (trade name: Sanyo Chemical Industry Co., Ltd.)", Neugen (trade name: Dai-ichi Kogyo Seiyaku Co., Ltd.), “Emulgen (trade name: Kao Soap Co., Ltd.)”, “Nonion (trade name: NOF Corporation)” and the like can be used.
【００１８】続いて、本発明を実施例によって更に具体
的に説明する。Next, the present invention will be described more specifically by way of examples.
〈実施例１〉まず、下記に示す組成の無電解錫−鉛合金
（はんだ）めっき液（水溶液）を調合した。 メタンスルホン酸 0.1 mol/L， メタンスルホン酸錫（２価） 0.1 mol/L， メタンスルホン酸鉛（２価） 0.05 mol/L， チオ尿素 1.0 mol/L， 硝酸 0.1 mol/L， 次亜リン酸ナトリウム 0.2 mol/L， 非イオン界面活性剤 0.5 g/L 。<Example 1> First, an electroless tin-lead alloy (solder) plating solution (aqueous solution) having the composition shown below was prepared. Methanesulfonic acid 0.1 mol / L, tin methanesulfonate (divalent) 0.1 mol / L, lead methanesulfonate (divalent) 0.05 mol / L, thiourea 1.0 mol / L, nitric acid 0.1 mol / L, hypophosphorus Sodium acid salt 0.2 mol / L, nonionic surfactant 0.5 g / L.
【００１９】次に、被めっき材たる銅製基板を酸性脱脂
剤「ＣＰ−１４０（商品名：日本鉱業株式会社）」を用
いて脱脂した後、エッチング剤「ＣＰ−２０３８（商品
名：日本鉱業株式会社）」でソフトエッチングを行い、
続いて１０％硫酸に浸漬してから上記無電解錫−鉛合金
めっき液に浸漬した。この際、めっき液の液温は７０℃
に保持し、マグネチックスタ−ラでゆるやかに攪拌し
た。Next, the copper substrate to be plated is degreased with an acidic degreasing agent "CP-140 (trade name: Nippon Mining Co., Ltd.)", and then an etching agent "CP-2038 (trade name: Nippon Mining Co., Ltd.) Company) "
Then, it was dipped in 10% sulfuric acid and then dipped in the above electroless tin-lead alloy plating solution. At this time, the temperature of the plating solution is 70 ° C.
The temperature was maintained at 0 ° C. and gently stirred with a magnetic stirrer.
【００２０】５分及び３０分の浸漬後、銅製基板は液よ
り引き上げられ、乾燥された。このように処理された銅
製基板上には灰白色の皮膜が析出しており、この膜厚を
測定したところ、５分の浸漬では 3.3μｍ，３０分の浸
漬では7.2μｍとなっていた。After dipping for 5 minutes and 30 minutes, the copper substrate was taken out of the liquid and dried. An off-white film was deposited on the copper substrate thus treated, and the film thickness was measured and found to be 3.3 μm after immersion for 5 minutes and 7.2 μm after immersion for 30 minutes.
【００２１】また、皮膜の組成を調査したところ「錫／
鉛＝38／62（重量比）」のはんだ組成となっていること
が確認された。そして、セロハンテ−プを用いて基材と
皮膜の密着性を評価したところ、従来の“有機スルホン
酸をベ−スとした無電解はんだめっき液”を用いたもの
に劣らない十分に優れた密着性を示した。Further, when the composition of the film was investigated, "tin /
It was confirmed that the solder composition was lead = 38/62 (weight ratio). Then, the adhesion between the base material and the film was evaluated using cellophane tape, and it was found that the adhesion was sufficiently superior to the one using the conventional "electroless solder plating solution based on organic sulfonic acid". Showed sex.
【００２２】〈比較例１〉実施例１に示した液から硝酸
成分を除いた組成の無電解錫−鉛合金めっき液を調合し
た。そして、実施例１の場合と同様の銅製基板を被めっ
き材とし、実施例１におけると同様の前処理の後、上記
めっき液によるめっき処理を行った。なお、めっき液の
液温，攪拌条件及び浸漬時間が実施例１と同様に設定さ
れたことは言うまでもない。Comparative Example 1 An electroless tin-lead alloy plating solution having a composition obtained by removing the nitric acid component from the solution shown in Example 1 was prepared. Then, a copper substrate similar to that in the case of Example 1 was used as a material to be plated, and after the same pretreatment as in Example 1, plating treatment with the above plating solution was performed. Needless to say, the temperature of the plating solution, the stirring conditions, and the immersion time were set as in Example 1.
【００２３】この結果、銅製基板上には灰白色の皮膜が
析出しており、皮膜の組成は「錫／鉛＝65／35（重量
比）」となっていて基材と皮膜の密着性は良好であった
が、皮膜の膜厚を測定したところ、５分の浸漬及び３０
分の浸漬とも 2.1μｍでしかなかった。As a result, an off-white film was deposited on the copper substrate, and the composition of the film was "tin / lead = 65/35 (weight ratio)", indicating good adhesion between the substrate and the film. However, when the film thickness of the film was measured, it was immersed for 5 minutes and was
The immersion time was only 2.1 μm.
【００２４】〈実施例２〉下記組成の無電解錫−鉛合金
（はんだ）めっき液（水溶液）を調合した。 p-フェノ−ルスルホン酸 0.05 mol/L， p-フェノ−ルスルホン酸錫（２価） 0.07 mol/L， p-フェノ−ルスルホン酸鉛（２価） 0.05 mol/L， チオ尿素 1.0 mol/L， 硝酸ナトリウム 0.2 mol/L， 非イオン界面活性剤 0.5 g/L 。Example 2 An electroless tin-lead alloy (solder) plating solution (aqueous solution) having the following composition was prepared. p-phenol sulfonic acid 0.05 mol / L, p-phenol sulfonic acid tin (divalent) 0.07 mol / L, p-phenol sulfonic acid lead (divalent) 0.05 mol / L, thiourea 1.0 mol / L, Sodium nitrate 0.2 mol / L, nonionic surfactant 0.5 g / L.
【００２５】そして、実施例１の場合と同様の銅製基板
を被めっき材とし、実施例１におけると同様の前処理の
後、上記めっき液によるめっき処理を行った。なお、こ
の際、めっき液の液温を８０℃としたほかは、攪拌条件
及び浸漬時間とも実施例１と同様に設定された。このよ
うに処理された銅製基板上には灰白色の皮膜が析出して
おり、この膜厚を測定したところ、５分の浸漬では 4.0
μｍ，３０分の浸漬では 8.2μｍとなっていた。Then, a copper substrate similar to that in Example 1 was used as a material to be plated, and after the same pretreatment as in Example 1, plating treatment with the above plating solution was performed. At this time, the stirring conditions and the immersion time were set in the same manner as in Example 1 except that the plating solution temperature was 80 ° C. An off-white film is deposited on the copper substrate treated in this way. The film thickness was measured to be 4.0
It was 8.2 μm after immersion for 30 minutes in μm.
【００２６】また、皮膜の組成を調査したところ「錫／
鉛＝７／３（重量比）」のはんだ組成となっていること
が確認された。そして、セロハンテ−プを用いて基材と
皮膜の密着性を評価したところ、従来の“有機スルホン
酸をベ−スとした無電解錫−鉛合金めっき液”を用いた
ものに劣らない十分に優れた密着性を示した。Further, when the composition of the film was investigated, "tin /
It was confirmed that the lead had a solder composition of 7/3 (weight ratio). Then, the adhesion between the base material and the film was evaluated using cellophane tape, and it was found that it was not inferior to the one using the conventional "electroless tin-lead alloy plating solution based on organic sulfonic acid". It showed excellent adhesion.
【００２７】〈比較例２〉実施例２に示した液から硝酸
ナトリウムを除いた組成の無電解錫−鉛合金めっき液を
調合した。そして、実施例２の場合と同様の銅製基板を
被めっき材とし、実施例２におけると同様の前処理の
後、上記めっき液によるめっき処理を行った。なお、め
っき液の液温，攪拌条件及び浸漬時間が実施例２と同様
に設定されたことは言うまでもない。Comparative Example 2 An electroless tin-lead alloy plating solution having a composition obtained by removing sodium nitrate from the solution shown in Example 2 was prepared. Then, a copper substrate similar to that in the case of Example 2 was used as a material to be plated, and after the same pretreatment as in Example 2, plating treatment with the above plating solution was performed. It goes without saying that the liquid temperature of the plating solution, the stirring conditions, and the immersion time were set as in Example 2.
【００２８】この結果、銅製基板上には灰白色の皮膜が
析出しており、皮膜の組成は「錫／鉛＝８／２（重量
比）」となっていて基材と皮膜の密着性は良好であった
が、皮膜の膜厚を測定したところ、５分の浸漬及び３０
分の浸漬とも 1.8μｍでしかなかった。As a result, an off-white film was deposited on the copper substrate, and the composition of the film was "tin / lead = 8/2 (weight ratio)", indicating good adhesion between the substrate and the film. However, when the film thickness of the film was measured, it was immersed for 5 minutes and was
The immersion time was only 1.8 μm.
【００２９】[0029]
【効果の総括】以上に説明した如く、この発明によれ
ば、銅系基材面に密着性の優れた錫−鉛合金皮膜を十分
な膜厚で形成させることができ、かつ環境悪化成分の含
有量も極力少ない置換型無電解錫−鉛合金めっき液が提
供されるなど、産業上非常に有用な効果がもたらされ
る。[Summary of Effects] As described above, according to the present invention, it is possible to form a tin-lead alloy film having excellent adhesion on the surface of a copper-based substrate in a sufficient thickness, and The substitution-type electroless tin-lead alloy plating solution whose content is as small as possible is provided, which brings very useful effects in industry.
Claims (1)
っき液。1. An organic sulfonic acid as a plating solution component: 0.01 to 1 mol / L, a divalent tin salt of an organic sulfonic acid: 0.01 to 0.5 mol / L, a divalent lead salt of an organic sulfonic acid: 0.01 to 0.5 An electroless tin-lead alloy plating solution containing mol / L, thiourea and / or its derivative: 0.05 to 2 mol / L, and nitrate ion: 0.01 mol / L or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29982791A JPH05112877A (en) | 1991-10-18 | 1991-10-18 | Electroless tin-lead alloy plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29982791A JPH05112877A (en) | 1991-10-18 | 1991-10-18 | Electroless tin-lead alloy plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05112877A true JPH05112877A (en) | 1993-05-07 |
Family
ID=17877405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29982791A Pending JPH05112877A (en) | 1991-10-18 | 1991-10-18 | Electroless tin-lead alloy plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05112877A (en) |
-
1991
- 1991-10-18 JP JP29982791A patent/JPH05112877A/en active Pending
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