JPH02141595A - Sn or sn alloy plating solution and its plating method - Google Patents
Sn or sn alloy plating solution and its plating methodInfo
- Publication number
- JPH02141595A JPH02141595A JP29691488A JP29691488A JPH02141595A JP H02141595 A JPH02141595 A JP H02141595A JP 29691488 A JP29691488 A JP 29691488A JP 29691488 A JP29691488 A JP 29691488A JP H02141595 A JPH02141595 A JP H02141595A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- alloy
- plating solution
- oxidation
- masking agent
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims description 9
- 229910001128 Sn alloy Inorganic materials 0.000 title abstract description 11
- 230000000873 masking effect Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009713 electroplating Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、Ｓｎ又はＳｎ合金めっき液中の有効成分であ
る３ ｎ ｔｒｉの酸化抑制効果を付与したＳｎ又はＳ
ｎ合金めっき液及びめっき方法に関するもので特にＣｕ
、Ｃｕ合金材料のめつきに適合するものである。Detailed Description of the Invention [Industrial Application Field] The present invention provides Sn or
Regarding n-alloy plating solution and plating method, especially Cu
, which is suitable for plating Cu alloy materials.
［従来の技術］
一般にＳｎ又はＳｎ合金めっきは、めっき液中の５ｎ２
ｆかめっきの有効成分であるか、Ｓｎ ２１は酸化して
Ｓ ｎ ”となり易い。５ｎ２Ｉの酸化による濃度低下
は、めっきの焼けや、Ｓｎ合金めつきてはめっき膜のＳ
ｎ含有率の低下等、めっき膜質の変動を招く。又生成し
た５ｎ４（はめっきの析出に寄与しないだけでなくメタ
スズ酸となってめっき槽に沈殿し、めっき液粘度上昇に
よる攪拌能力の低下、ひいては濾過機の目詰まりの原因
となる。[Prior art] Generally, Sn or Sn alloy plating is performed using 5n2 in the plating solution.
Sn 21 is easily oxidized and becomes Sn '', possibly because it is an active ingredient in plating.The decrease in concentration due to oxidation of 5n2I may cause burns in the plating, or if Sn alloy plating is applied, the S of the plating film.
This causes changes in the quality of the plating film, such as a decrease in the n content. In addition, the generated 5n4 (5n4) not only does not contribute to the precipitation of the plating, but also becomes metastannic acid and precipitates in the plating tank, which increases the viscosity of the plating solution, reduces the stirring ability, and causes clogging of the filter.
そこで従来よりＳｎ ｔ （の酸化抑制のため次ぎのよ
うな対策か提案されている。Therefore, the following measures have been proposed to suppress the oxidation of Sn t (.
（１）めっき液面をＮ２．Ａｒ、Ｃｏ２などの不活性ガ
スて覆い、液面でのＳｎ２′の酸化を抑制する。(1) Set the plating solution level to N2. Cover with an inert gas such as Ar or Co2 to suppress oxidation of Sn2' at the liquid surface.
（２）めっき液中にＮ ２ 、 Ａ ｒ 、 ＣＯ３な
どの不活性ガスを吹き込み、溶存酸素量を減らし、酸化
を抑制する。(2) Inert gas such as N2, Ar, or CO3 is blown into the plating solution to reduce the amount of dissolved oxygen and suppress oxidation.
（３）めっき槽からめっき液タンクへ戻る液を樋を用い
るなどして高低差を少なくして巻き込む気泡を減らして
酸化を抑制する。(3) The liquid returning from the plating tank to the plating solution tank is reduced by using a gutter to reduce the difference in height, thereby reducing air bubbles and suppressing oxidation.
（４）めっき液中に酸化防止剤を添加する。(4) Add an antioxidant to the plating solution.
［発萌が解決しようとする課題］
しかしながら、上記の何れの方法も充分な５ｎ２ｆの酸
化抑制効果が得られていない。本発明者らは、実験検討
の結果、めっき液にＣｕイオンが微量でも混入すると
３ｎ２Ｆの酸化が著しく促進され前記従来法では、酸化
抑制が不充分となることを見出した。[Problems to be solved by Homoe] However, none of the above-mentioned methods has been able to obtain a sufficient effect of inhibiting 5n2f oxidation. As a result of experimental studies, the present inventors found that if even a trace amount of Cu ions were mixed into the plating solution,
It has been found that the oxidation of 3n2F is significantly promoted and the conventional method is insufficient to suppress the oxidation.
Ｃｕイオンの混入原因としては、被めっき材料がＣｕ、
又はＣｕ合金の場合、前処理工程からＣｕイオンの持ち
こみ、或はめっき液中での被め９き材料の溶出等が考え
られる。このＣｕイオンに対する対策が酸化防止効果を
得る重要な鍵である。The cause of Cu ion contamination is that the material to be plated is Cu,
Alternatively, in the case of a Cu alloy, it is possible that Cu ions are brought in from the pretreatment process or that the plating material is eluted in the plating solution. Countermeasures against Cu ions are an important key to obtaining the antioxidant effect.
［課題を解決するための手段］
Ｓｎ又はＳｎ合金めっき液にエチレンジアミン四酢酸（
以下ＥＤＴＡという）、ニトリロ三酢酸（以下ＮＴＡと
いう）、トリエタノールアミンなる群より選ばれた少な
くとも１種類のマスク剤を添加することにあり、それに
よってＣｕイオンをマスクし、ｓ ｎ２ ［’の酸化を
大幅に抑制するものである。[Means for solving the problem] Adding ethylenediaminetetraacetic acid (
The method is to add at least one masking agent selected from the group consisting of EDTA (hereinafter referred to as EDTA), nitrilotriacetic acid (hereinafter referred to as NTA), and triethanolamine, thereby masking Cu ions and reducing the oxidation of s n2 ['. This will significantly suppress the
［作用］
Ｓｎ又はＳｎ合金めっき液中に添加するマスク剤として
は、ＥＤＴＡ、ＮＴＡ、トリエタノールアミン等の内の
一種である。これらのマスク剤を添加することにより、
めっき液中の２価のＳｎか４価のＳｎになることを抑制
することができる。[Function] The masking agent added to the Sn or Sn alloy plating solution is one of EDTA, NTA, triethanolamine, and the like. By adding these masking agents,
It is possible to suppress the formation of divalent Sn or tetravalent Sn in the plating solution.
上記マスク剤の添加量は、０．５・１Ｏ−３以上５．０
・１０３ｍｏｌ／ｕ以下が望ましい、その理由は１通常
めっき液に混入するＣｕイオンは、１１００ＰＰ程度で
あるがマスク剤量が０．５・１０−３ｍ ｏ １７文部
丁の場合、Ｓ ｎ ”の酸化抑制作用が不足し、５．０
・１０−３ｍｏｌ／ｉを超えるとめっき膜の焼けや変色
の原因となるからである。The amount of the above masking agent added is 0.5.1O-3 or more 5.0
- 103 mol/u or less is desirable; the reason is 1. Cu ions mixed in the plating solution are usually about 1100 PP, but when the amount of masking agent is 0.5 10-3 m o Insufficient inhibitory effect, 5.0
- If it exceeds 10-3 mol/i, it may cause burning or discoloration of the plating film.
尚、本発明の適用対象となるめっき液は。The plating solution to which the present invention is applicable is as follows.
Ｓｎめっき液の他Ｊ ５ｎ−Ｃｏ、５ｎ−Ｎ ｉ、５ｎ
−Ｐｂ等のＳｎ合金めっき液も含む。又被めっき物とし
ては、Ｃｕ、Ｃｕ合金が対象であり、その形状は板材１
条材、等特にこだわらない。In addition to Sn plating solution J 5n-Co, 5n-N i, 5n
- Also includes Sn alloy plating solution such as Pb. In addition, the objects to be plated are Cu and Cu alloys, and the shape is similar to that of the plate material 1.
I don't particularly care about the strips, etc.
［実施例］
めっき装置は、図示しないかバッチ式によるラック掛け
めっき装置を使用し、めっき液は、第１表の５ｎ−Ｎｉ
合金めっき液を用い、第２表に示すめっき条件で銅合金
よりなるリードフレーム材に１ケ月間めっき作業を行い
、１ケ月間めっき作業後の液中のＳｎ”／ （Ｓｎ”＋
Ｓｎ”）の割合を調査検討した。次ぎに同じ条件でＥＤ
ＴＡ。[Example] The plating apparatus used was a batch-type rack plating apparatus (not shown), and the plating solution was 5n-Ni as shown in Table 1.
Using an alloy plating solution, plating was performed on a lead frame material made of copper alloy for one month under the plating conditions shown in Table 2.
We investigated and considered the ratio of ED
T.A.
ＮＴＡ、トリエタノールアミンを添加して調査した。ま
た、調査時のめっき液を用いて、ハルセル試験を行いめ
っき外観を観察した。The investigation was conducted by adding NTA and triethanolamine. Furthermore, using the plating solution used during the investigation, a Hull cell test was conducted to observe the appearance of the plating.
第 １
表
第 ２
表
以上の結果を第３表へ示す。本発明のマスク剤を添加し
ない比較例は、１７月間のめっき作業で液中のＳｎ”／
（Ｓｎ”＋Ｓｎ”）の比が５％から４０％に大きく増
加しているのに対し、Ｃｕイオンをマスクするマスク材
を添加した実施例は、何れもＳｎ ２ ｆの酸化か大幅
に抑制されていることか判かる。The results from Table 1 and Table 2 are shown in Table 3. In a comparative example in which the masking agent of the present invention was not added, Sn''/
While the ratio of (Sn"+Sn") increased significantly from 5% to 40%, the oxidation of Sn 2 f was significantly suppressed in all of the examples in which a masking material was added to mask Cu ions. I can see that it is.
その効果は、 ０．５−１０−”ｍ ｏ １ ／ ｌ以
り添加した場合顕著であるか、５・１０−’ｍ ｏ ｌ
７文を超えて添加した場合は、建浴初期において高電
流密度ての焼けか発生し、実用上問題となることか判か
る。The effect is remarkable when more than 0.5-10-'mol/l is added, or 5-10-'mol/l
It can be seen that if more than 7 parts are added, burning occurs due to the high current density at the early stage of bath preparation, which may pose a practical problem.
以上の実施例においては、単にめっき液へのマスク剤添
加の効果について述べたが、不活性ガスによる酸素遮断
等、従来からの酸化防止方法を本発明方法と併用するこ
とは何等差支えなく、更に長期間のめっき液安窯化を図
ることも可能である。In the above examples, the effect of adding a masking agent to the plating solution was simply described, but there is no problem in using conventional oxidation prevention methods such as blocking oxygen with an inert gas in combination with the method of the present invention. It is also possible to store the plating solution in a stable kiln for a long period of time.
［発明の効果］
本発明は、以上説明したように構成されているので、以
下に記載されるような効果を奏す−る。[Effects of the Invention] Since the present invention is configured as described above, it produces the effects described below.
本発明のＳｎ又はＳｎ合金めっき液及びめフき方法によ
ればめっき液に所定のマスク剤を添加することにより、
めっき液中の５ｎ２１の５ｎ４ｆへの酸化を大幅に抑制
することができ、安定したメツキ作業か確立できる。According to the Sn or Sn alloy plating solution and cleaning method of the present invention, by adding a predetermined masking agent to the plating solution,
Oxidation of 5n21 to 5n4f in the plating solution can be significantly suppressed, and stable plating work can be established.
その結果、めっき液更新の頻度が大幅に減少しコストの
低減と相俟って、Ｓｎ又はＳｎ合金めっき膜質の品質が
向上する。As a result, the frequency of renewing the plating solution is significantly reduced, which, together with cost reduction, improves the quality of the Sn or Sn alloy plating film.
Claims (2)
リエタノールアミンなる群より選ばれた、少なくとも１
種類のマスク剤を添加することを特徴とするＳｎ又はＳ
ｎ合金めっき液。(1) At least one selected from the group consisting of ethylenediaminetetraacetic acid, nitrolilotriacetic acid, and triethanolamine.
Sn or S characterized by adding a type of masking agent
n-alloy plating solution.
するめっき方法。(2) A plating method characterized by plating a material to be plated made of Cu or a Cu alloy with the plating solution described in item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29691488A JPH02141595A (en) | 1988-11-24 | 1988-11-24 | Sn or sn alloy plating solution and its plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29691488A JPH02141595A (en) | 1988-11-24 | 1988-11-24 | Sn or sn alloy plating solution and its plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02141595A true JPH02141595A (en) | 1990-05-30 |
Family
ID=17839803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29691488A Pending JPH02141595A (en) | 1988-11-24 | 1988-11-24 | Sn or sn alloy plating solution and its plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02141595A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997023664A1 (en) * | 1995-12-22 | 1997-07-03 | Toyo Kohan Co., Ltd. | Tinning bath and tinning method |
| KR100554147B1 (en) * | 2001-08-29 | 2006-02-20 | 주식회사 포스코 | Ni-flash Plating solution for the cold-rolling strip |
| CN105463523A (en) * | 2015-12-23 | 2016-04-06 | 苏州市金星工艺镀饰有限公司 | Electroplate liquid capable of suppressing growth of tin whiskers of coating and application thereof |
| CN105506680A (en) * | 2015-12-23 | 2016-04-20 | 苏州市金星工艺镀饰有限公司 | Preparation method of electroplating liquid for reducing growth of plating layer tin whisker |
| CN109609980A (en) * | 2018-12-11 | 2019-04-12 | 湖北工程学院 | The method of acid tin plating liquid and preparation method thereof and copper-based material surface tinning |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516237A (en) * | 1978-07-20 | 1980-02-04 | Seiko Instr & Electronics Ltd | Electronic watch |
| JPS57161080A (en) * | 1981-02-25 | 1982-10-04 | Hooker Chemicals Plastics Corp | Metal plating composition and method |
| JPS5832237A (en) * | 1981-08-20 | 1983-02-25 | Matsushita Electric Ind Co Ltd | Optical pickup device |
| JPS5838519A (en) * | 1981-09-01 | 1983-03-07 | 松下電器産業株式会社 | Pressure jar rice cooker |
-
1988
- 1988-11-24 JP JP29691488A patent/JPH02141595A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5516237A (en) * | 1978-07-20 | 1980-02-04 | Seiko Instr & Electronics Ltd | Electronic watch |
| JPS57161080A (en) * | 1981-02-25 | 1982-10-04 | Hooker Chemicals Plastics Corp | Metal plating composition and method |
| JPS5832237A (en) * | 1981-08-20 | 1983-02-25 | Matsushita Electric Ind Co Ltd | Optical pickup device |
| JPS5838519A (en) * | 1981-09-01 | 1983-03-07 | 松下電器産業株式会社 | Pressure jar rice cooker |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997023664A1 (en) * | 1995-12-22 | 1997-07-03 | Toyo Kohan Co., Ltd. | Tinning bath and tinning method |
| KR100554147B1 (en) * | 2001-08-29 | 2006-02-20 | 주식회사 포스코 | Ni-flash Plating solution for the cold-rolling strip |
| CN105463523A (en) * | 2015-12-23 | 2016-04-06 | 苏州市金星工艺镀饰有限公司 | Electroplate liquid capable of suppressing growth of tin whiskers of coating and application thereof |
| CN105506680A (en) * | 2015-12-23 | 2016-04-20 | 苏州市金星工艺镀饰有限公司 | Preparation method of electroplating liquid for reducing growth of plating layer tin whisker |
| CN109609980A (en) * | 2018-12-11 | 2019-04-12 | 湖北工程学院 | The method of acid tin plating liquid and preparation method thereof and copper-based material surface tinning |
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