JPH04333590A - Method for suppressing sludging in tin electro-plating - Google Patents
Method for suppressing sludging in tin electro-platingInfo
- Publication number
- JPH04333590A JPH04333590A JP13361091A JP13361091A JPH04333590A JP H04333590 A JPH04333590 A JP H04333590A JP 13361091 A JP13361091 A JP 13361091A JP 13361091 A JP13361091 A JP 13361091A JP H04333590 A JPH04333590 A JP H04333590A
- Authority
- JP
- Japan
- Prior art keywords
- bath
- sludge
- tin
- plating
- sludge generation
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title abstract description 15
- 238000009713 electroplating Methods 0.000 title abstract 2
- 239000010802 sludge Substances 0.000 claims abstract description 35
- 238000007747 plating Methods 0.000 claims abstract description 23
- -1 iron ion Chemical class 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は鋼板の表面に優れた錫め
っき層を形成する方法に関し、特にフェロスタン浴を用
いた電気錫めっきのスラッジ発生抑制方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an excellent tin plating layer on the surface of a steel plate, and more particularly to a method for suppressing sludge generation in electrolytic tin plating using a ferrostane bath.
【０００２】0002
【従来の技術】錫めっき浴として従来用いられているフ
ェロスタン浴は、一般にフェノールスルホン酸を用いて
、第１錫イオンを安定化し、１００％の陽極効率、９０
〜９５％の陰極効率を保っている。しかしながら、高速
めっき化するにつれて、フェロスタン浴中の第１錫イオ
ンが、空気中の酸素との化合、電極反応あるいは鉄イオ
ンの触媒作用によって、第２錫イオンの酸化物を形成す
る。このような酸化物は浴中にわずかしか溶解せず、ス
ラッジとして浴中に沈澱する。これらのスラッジは操業
上、電極反応における錫効率の低下、めっき浴からのス
ラッジ処理等の問題を発生させる。このため、スラッジ
発生の抑制を目的としてフェノールスルホン酸の高濃度
化、めっき浴温度の低下または鉄イオン濃度低下等を実
施してきた。また、陽極にＩｒ酸化物被膜を有する導電
性基体を用いて錫イオンの酸化によるスラッジ発生を抑
制する方法（特開平２−１９４１９２公報）もあるが、
その効果には限界がある。[Prior Art] A ferrostane bath conventionally used as a tin plating bath generally uses phenolsulfonic acid to stabilize stannous ions, and has an anode efficiency of 100% and 90%
Maintains cathode efficiency of ~95%. However, with high-speed plating, the stannous ions in the ferrostane bath form oxides of stannous ions by combination with oxygen in the air, electrode reaction, or catalytic action of iron ions. Such oxides dissolve only sparingly in the bath and precipitate therein as sludge. These sludges cause operational problems such as a decrease in tin efficiency in electrode reactions and sludge treatment from the plating bath. For this reason, efforts have been made to increase the concentration of phenolsulfonic acid, lower the plating bath temperature, or lower the iron ion concentration in order to suppress sludge generation. There is also a method of suppressing sludge generation due to oxidation of tin ions by using a conductive substrate having an Ir oxide film on the anode (Japanese Patent Application Laid-Open No. 2-194192).
There are limits to its effectiveness.
【０００３】0003
【発明が解決しようとする課題】本発明は、上記の問題
点に鑑み、優れた錫めっき層を形成させるための電気錫
めっき浴における、スラッジ発生を顕著に抑制する方法
を提供することを目的とする。[Problems to be Solved by the Invention] In view of the above problems, an object of the present invention is to provide a method for significantly suppressing the generation of sludge in an electrolytic tin plating bath for forming an excellent tin plating layer. shall be.
【０００４】0004
【課題を解決するための手段】すなわち、本発明はオキ
シエチレンを有するフェニル化合物を含有した酸性フェ
ロスタン電気錫めっき浴において、α−オキシカルボン
酸０．１〜３０ｇ／ｌ添加することを特徴とするスラッ
ジ発生の抑制方法を提供する。[Means for Solving the Problems] That is, the present invention is characterized in that 0.1 to 30 g/l of α-oxycarboxylic acid is added to an acidic ferrostane electrotin plating bath containing a phenyl compound having oxyethylene. A method for suppressing sludge generation is provided.
【０００５】[0005]
【作用】以下、本発明を詳細に説明する。本発明に用い
るめっき浴は硫酸第１錫とフェノールスルホン酸を主成
分とするフェロスタン浴である。浴組成の１例をあげる
と以下のような組成である。
Ｓｎ２＋；３０ｇ／ｌ
遊離酸；２０ｇ／ｌ（Ｈ２ＳＯ４換算で）また、必要に
応じて光沢剤、安定剤等が用いられる場合もある。フェ
ロスタン浴中におけるスラッジ発生の機構は一般に次の
ように考えられる。
２Ｆｅ２＋＋１／２Ｏ２＋２Ｈ＋ → ２
Ｆｅ３＋＋Ｈ２Ｏ （１） Ｓｎ
２＋＋２Ｆｅ３＋ → Ｓｎ４＋＋２Ｆｅ２＋
（２）すなわち、上記
（１）式に示すようにＦｅ２＋は浴中に溶解している酸
素により酸化され、Ｆｅ３＋となる。このＦｅ３＋が（
２）式に示すように浴中において還元されてＦｅ２＋と
なる。しかしながら一方においてはＳｎ２＋はＳｎ４＋
と酸化されて錫のスラッジが発生すると考えられる。
本発明のα−オキシカルボン酸を添加することによるス
ラッジ発生の抑制機構は次のように考えられる。すなわ
ちα−オキシカルボン酸の中に含まれるＣＯＯＨ基ある
いはＯＨ基が、浴中で酸化された３価のＦｅイオンと化
合することによって上記（２）式右向きの反応抑制剤と
して働く。つまりα−オキシカルボン酸は浴中でマスキ
ング剤として働き、（２）式の右向きの反応を抑制する
ことによってスラッジ発生を減少させるものと考えられ
る。本発明におけるスラッジ発生量の評価方法は以下の
通りである。すなわち、錫めっき浴を採取後１日放置し
、上澄み液を濾過し、濾液に抗酸化剤を所定量添加した
ものを５０℃で５時間エアレーションした。その時発生
した錫スラッジの乾燥重量を求めた。[Operation] The present invention will be explained in detail below. The plating bath used in the present invention is a ferrostane bath containing stannous sulfate and phenolsulfonic acid as main components. An example of the bath composition is as follows. Sn2+: 30 g/l Free acid: 20 g/l (in terms of H2SO4) In addition, brighteners, stabilizers, etc. may be used as necessary. The mechanism of sludge generation in a ferrostane bath is generally considered as follows. 2Fe2++1/2O2+2H+ → 2
Fe3++H2O (1) Sn
2++2Fe3+ → Sn4++2Fe2+
(2) That is, as shown in the above formula (1), Fe2+ is oxidized by oxygen dissolved in the bath to become Fe3+. This Fe3+ is (
2) As shown in the formula, it is reduced to Fe2+ in the bath. However, on the other hand, Sn2+ is Sn4+
It is thought that tin sludge is generated by oxidation. The mechanism of suppressing sludge generation by adding the α-oxycarboxylic acid of the present invention is thought to be as follows. That is, the COOH group or OH group contained in the α-oxycarboxylic acid acts as a rightward reaction inhibitor of the above formula (2) by combining with trivalent Fe ions oxidized in the bath. In other words, it is considered that α-oxycarboxylic acid acts as a masking agent in the bath and suppresses the rightward reaction of equation (2), thereby reducing sludge generation. The method for evaluating the amount of sludge generated in the present invention is as follows. That is, the tin plating bath was left for one day after collection, the supernatant liquid was filtered, and the filtrate to which a predetermined amount of antioxidant was added was aerated at 50° C. for 5 hours. The dry weight of the tin sludge generated at that time was determined.
【０００６】[0006]
実施例１
めっき浴組成は、以下のとおりである。
Ｓｎ；２６．８ｇ／ｌ
酸度；２３．２ｇ／ｌ
Ｆｅ；８．４ｇ／ｌ
酒石酸；０．１ｇ／ｌ〜３０．０ｇ／ｌ光沢剤；６．１
ｇ／ｌ
まためっき条件は電流密度３Ａ／ｄｍ２で５秒間行った
。この結果、酒石酸無添加の場合のスラッジ発生率は約
６０％であったが、酒石酸を０．１％添加するとスラッ
ジ発生率は５２〜５３％に減少する。その後酒石酸の添
加量を増すに従ってスラッジ発生率は減少し、およそ３
０ｇ／ｌの添加量でスラッジ発生率はほぼ０％近くなる
。最終的には、スラッジ発生率は９５％以上減少する効
果があった。その結果を図１に示す。Example 1 The plating bath composition is as follows. Sn; 26.8 g/l Acidity; 23.2 g/l Fe; 8.4 g/l Tartaric acid; 0.1 g/l to 30.0 g/l Brightener; 6.1
g/l The plating conditions were a current density of 3 A/dm2 for 5 seconds. As a result, the sludge generation rate when no tartaric acid was added was about 60%, but when 0.1% tartaric acid was added, the sludge generation rate decreased to 52-53%. After that, as the amount of tartaric acid added increased, the sludge generation rate decreased to approximately 3
When the amount added is 0 g/l, the sludge generation rate is almost 0%. Ultimately, the sludge generation rate was reduced by more than 95%. The results are shown in Figure 1.
【０００７】実施例２
めっき浴組成は、以下のとおりである。
Ｓｎ；２６．８ｇ／ｌ
酸度；２３．２ｇ／ｌ
Ｆｅ；８．４ｇ／ｌ
クエン酸；０．１ｇ／ｌ〜３０．０ｇ／ｌ光沢剤；６．
１ｇ／ｌ
まためっき条件は電流密度３Ａ／ｄｍ２で５秒間行った
。この結果、クエン酸無添加の場合のスラッジ発生率は
約６０％であったが、クエン酸を０．１％添加するとス
ラッジ発生率は５３〜５５％に減少する。その後クエン
酸の添加量を増すに従ってスラッジ発生率は減少し、お
よそ３０ｇ／ｌの添加量でスラッジ発生率はほぼ２２〜
２５％近くに収束する。最終的には、スラッジ発生率は
６０％以上減少する効果があった。その結果を図１に示
す。Example 2 The composition of the plating bath is as follows. Sn; 26.8 g/l Acidity; 23.2 g/l Fe; 8.4 g/l citric acid; 0.1 g/l to 30.0 g/l brightener; 6.
1 g/l The plating conditions were a current density of 3 A/dm2 for 5 seconds. As a result, the sludge generation rate was approximately 60% without the addition of citric acid, but when 0.1% citric acid was added, the sludge generation rate decreased to 53-55%. After that, as the amount of citric acid added increases, the sludge generation rate decreases, and when the amount of citric acid added is approximately 30g/l, the sludge generation rate is approximately 22 ~
It converges to nearly 25%. Ultimately, the sludge generation rate was reduced by more than 60%. The results are shown in Figure 1.
【０００８】実施例３
めっき浴組成は、以下のとおりである。
Ｓｎ；２６．８ｇ／ｌ
酸度；２３．２ｇ／ｌ
Ｆｅ；８．４ｇ／ｌ
乳酸；０．１ｇ／ｌ〜３０．０ｇ／ｌ
光沢剤；６．１ｇ／ｌ
まためっき条件は電流密度３Ａ／ｄｍ２で５秒間行った
。この結果、乳酸無添加の場合のスラッジ発生率は約６
０％であったが、乳酸を０．１％添加するとスラッジ発
生率は５５〜５７％に減少する。その後乳酸の添加量を
増すに従ってスラッジ発生率は減少し、およそ３０ｇ／
ｌの添加量でスラッジ発生率はほぼ２４〜２８％近くに
収束する。最終的には、スラッジ発生率は５０％以上減
少する効果があった。その結果を図１に示す。Example 3 The composition of the plating bath is as follows. Sn; 26.8 g/l Acidity; 23.2 g/l Fe; 8.4 g/l Lactic acid; 0.1 g/l to 30.0 g/l Brightener; 6.1 g/l The plating conditions are current density 3A/l dm2 for 5 seconds. As a result, the sludge generation rate when no lactic acid is added is approximately 6
However, when lactic acid is added at 0.1%, the sludge generation rate decreases to 55-57%. After that, as the amount of lactic acid added increased, the sludge generation rate decreased to approximately 30g/
The sludge generation rate converges to approximately 24 to 28% with an addition amount of 1. Ultimately, the sludge generation rate was reduced by more than 50%. The results are shown in Figure 1.
【０００９】[0009]
【発明の効果】本発明によれば、第１錫イオンの第２錫
イオンへの酸化が抑制され、めっき性を阻害することな
くスラッジ発生率を抑制する効果が大であり、可溶性ま
たは不溶性アノードを用いた錫めっきライン操業におい
て錫効率のアップが図られる。このためスラッジ除去処
理費用等の削減の効果もある。また、めっき浴装置の配
管詰まりを減少させる効果もある。Effects of the Invention According to the present invention, the oxidation of stannous ions to stannic ions is suppressed, and the sludge generation rate is greatly suppressed without impeding plating properties. The tin efficiency can be improved in tin plating line operations using this method. This also has the effect of reducing sludge removal processing costs. It also has the effect of reducing clogging of piping in plating bath equipment.
【００１０】0010
【図１】スラッジ発生率の変化を示したグラフである。FIG. 1 is a graph showing changes in sludge generation rate.
Claims (1)
物を含有した酸性フェロスタン電気錫めっき浴において
、α−オキシカルボン酸０．１〜３０ｇ／ｌ添加するこ
とを特徴とするスラッジ発生の抑制方法1. A method for suppressing sludge generation, which comprises adding 0.1 to 30 g/l of α-oxycarboxylic acid to an acidic ferrostane electrotin plating bath containing a phenyl compound having oxyethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13361091A JPH04333590A (en) | 1991-05-08 | 1991-05-08 | Method for suppressing sludging in tin electro-plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13361091A JPH04333590A (en) | 1991-05-08 | 1991-05-08 | Method for suppressing sludging in tin electro-plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04333590A true JPH04333590A (en) | 1992-11-20 |
Family
ID=15108834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13361091A Withdrawn JPH04333590A (en) | 1991-05-08 | 1991-05-08 | Method for suppressing sludging in tin electro-plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04333590A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9666547B2 (en) | 2002-10-08 | 2017-05-30 | Honeywell International Inc. | Method of refining solder materials |
| KR20180092999A (en) | 2015-12-11 | 2018-08-20 | 히타치 긴조쿠 가부시키가이샤 | Electrode device and method of manufacturing metal foil using the same |
-
1991
- 1991-05-08 JP JP13361091A patent/JPH04333590A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9666547B2 (en) | 2002-10-08 | 2017-05-30 | Honeywell International Inc. | Method of refining solder materials |
| KR20180092999A (en) | 2015-12-11 | 2018-08-20 | 히타치 긴조쿠 가부시키가이샤 | Electrode device and method of manufacturing metal foil using the same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Application deemed to be withdrawn because no request for examination was validly filed |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19980806 |