JPS61238993A - Additive for electroplating bath - Google Patents
Additive for electroplating bathInfo
- Publication number
- JPS61238993A JPS61238993A JP8201885A JP8201885A JPS61238993A JP S61238993 A JPS61238993 A JP S61238993A JP 8201885 A JP8201885 A JP 8201885A JP 8201885 A JP8201885 A JP 8201885A JP S61238993 A JPS61238993 A JP S61238993A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- ethylene oxide
- additive
- moles
- added
- 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
Links
- 239000000654 additive Substances 0.000 title claims abstract description 17
- 238000009713 electroplating Methods 0.000 title claims abstract description 9
- 230000000996 additive effect Effects 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 238000007747 plating Methods 0.000 abstract description 34
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 abstract description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 18
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 abstract description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 9
- 229950011260 betanaphthol Drugs 0.000 abstract 1
- 238000005187 foaming Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic sulfonic acids Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt 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
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 本発明は、電気メッキ浴用添加剤に関するものである。[Detailed description of the invention] The present invention relates to additives for electroplating baths.
電気メッキ浴に供するメッキ浴添加剤、すなわち光沢付
与剤には、従来より各種の添加剤が使用されている。Conventionally, various additives have been used as plating bath additives, that is, brightening agents, for electroplating baths.
例えば、ニッケルメッキにおいては、ナフタレンスルホ
ン酸のような芳香族スルホン酸やサッカリン、アセチル
アルコール誘導体などが、亜鉛及び亜鉛系メッキにおい
てはナフトールのエチレンオキサイド付加体、又はその
硫酸エステル、リン酸エステルのような芳香族エトキシ
レート又はそのエステルやアルデヒド化合物、四級化ア
ミン化合物などが、それぞれ使用検討されている。For example, in nickel plating, aromatic sulfonic acids such as naphthalenesulfonic acid, saccharin, acetyl alcohol derivatives, etc. are used, and in zinc and zinc-based plating, ethylene oxide adducts of naphthol, or their sulfuric esters, phosphoric esters, etc. Aromatic ethoxylates or their esters, aldehyde compounds, quaternized amine compounds, and the like are being considered for use.
しかしながら、上記添加剤は、有効光沢メッキ幅におい
て、比較的狭い線中でのみ実用に供し得、すなわち、表
面凸凹面がほぼ一定で、陰極に対し被メッキ板が比較的
面として等距離にある場合に実用的である。したがって
、板のメッキには有効であるが、物体すなわち三次元的
被メッキ体には実用に供し得ない。However, the above additives can be used in practice only in a relatively narrow line in the effective bright plating width, that is, the surface unevenness is approximately constant and the plated plate is relatively equidistant from the cathode. Practical in some cases. Therefore, although it is effective for plating plates, it cannot be used practically for objects, that is, three-dimensional objects to be plated.
さらに、錫及び錫系メッキにおいては、α−ナフトール
エトキシレートスルホン酸、α−ナフトールエトキシレ
ートのような芳香族エトキシレートやアルカノールスル
ホン酸などが使用検討されている。Furthermore, in tin and tin-based plating, aromatic ethoxylates such as α-naphthol ethoxylate sulfonic acid and α-naphthol ethoxylate, alkanol sulfonic acids, and the like are being considered for use.
特に、米国特許第２４５７１５２号公報及び特公昭５７
−８０４３５号公報には、α又はβナフトールエトキシ
レート（エチレンオキサイド３〜１５モル）、及びα又
はβナフトールエトキシレート（エチレンオキサイド６
〜７モル）スルホン酸が有用と記され、事実当該メッキ
においては必須と思えるほど特長が見られる。In particular, US Pat. No. 2,457,152 and Japanese Patent Publication No. 57
-80435 publication describes α or β naphthol ethoxylate (3 to 15 moles of ethylene oxide), and α or β naphthol ethoxylate (ethylene oxide 6 moles).
~7 mol) sulfonic acid is described as useful, and in fact has such characteristics that it seems essential in the plating concerned.
α又はβ−ナフトールエトキシレートのエチレンオキサ
イド付加モル数が３〜１５モルと記載されているが、エ
チレンオキサイド付加モル数において４モル以下の場合
１通常水に対し溶解性に劣る一方、 ８モル以上付加さ
れた場合、発泡性が著しく発現し実用に問題がある。す
なわち、α又はβナフトールエトキシレートにおいて、
実用に供し得るのは、エチレンオキサイド付加モル数５
モル以上７モル以下であるが、しかしながら、有効光沢
メッキ幅が狭い。It is stated that the number of moles of ethylene oxide added to α- or β-naphthol ethoxylate is 3 to 15 moles, but if the number of moles of ethylene oxide added is 4 moles or less, the solubility in normal water is poor, but it is 8 moles or more. If it is added, the foaming property will be significantly increased and there will be a problem in practical use. That is, in α or β naphthol ethoxylate,
For practical use, the number of moles of ethylene oxide added is 5.
The amount is between 7 moles and more, but the effective bright plating width is narrow.
さらに、α又はβナフトールエトキシレート（エチレン
オキサイド付加モル数６〜７モル）スルホン酸において
も、アニオン界面活性剤となり、前記非イオン界面活性
剤のα又はβナフトールエトキシレート（エチレンオキ
サイド付加モル数５〜７モル）に比べ著しく発泡する。Furthermore, α or β naphthol ethoxylate (number of moles of ethylene oxide added: 6 to 7 moles) also becomes an anionic surfactant, and the nonionic surfactant α or β naphthol ethoxylate (number of moles of ethylene oxide added: 5 to 7 moles) also becomes an anionic surfactant. ~7 mol).
このように、有効光沢メッキ幅が狭いため、三次元的被
メッキ体への実用に供し得る効果並びに発泡性などに問
題がある。As described above, since the effective bright plating width is narrow, there are problems with practical effects on three-dimensional objects to be plated, foamability, etc.
本発明者等は、これらの問題点を解消すべく鋭意研究を
重ねた結果、本発明を提供するに至ったものである。す
な消５゜
下記一般式（１） 、 （２）及び（３）で示される化
合物から成る群より選ばれた少なくとも１種又は２種以
上を主成分とする電気メッキ浴用添加剤ζ゛ア３゜Ｈ３
（ただし、式中、見は １〜１０． ｎは０〜９の数字
をそれぞれ示し、かつｌ＋ｎ＝１−１０である。The present inventors have conducted extensive research to solve these problems, and as a result, have provided the present invention. An additive for electroplating baths containing at least one or two or more compounds selected from the group consisting of compounds represented by the following general formulas (1), (2) and (3). 3°H3 (wherein, the number is 1 to 10. n represents a number from 0 to 9, and l+n=1-10.
ｍは １−１５、 Ｘは ０〜１４の数字をそれぞれ示
し、かつｒｓ＋ ｘ＝ ５〜１５である。）本発明の添
加剤は、例えばα又はβナフトールに対し、最初にプロ
ピレンオキサイドを付加し、次にエチレンオキサイド単
独、又はエチレンオキサイドとプロピレンオキサイドを
付加することによって得られる。m is 1-15, X is a number from 0 to 14, and rs+x=5 to 15. ) The additives of the invention are obtained, for example, by first adding propylene oxide to α or β naphthol and then adding ethylene oxide alone or ethylene oxide and propylene oxide.
かかるエチレンオキサイド及びプロピレンオキサイドの
付加モル数は、合計量でエチレンオキサイドの場合５〜
１５モルであり、プロピレンオキサイドの場合 １−１
０モルである。The total number of moles of ethylene oxide and propylene oxide added is 5 to 5 in the case of ethylene oxide.
15 mol, in the case of propylene oxide 1-1
It is 0 mole.
エチレンオキサイドが５モル未満の場合、メッキ浴に対
する溶解性が悪い、さらに１５モルを超えた場合、発泡
性が問題となる。When the amount of ethylene oxide is less than 5 moles, the solubility in the plating bath is poor, and when it exceeds 15 moles, foaming properties become a problem.
またプロピレンオキサイドが １モル未満の場合、有効
なメッキ幅が得られない、１０モルを超えた場合、ナフ
トール法度が稀釈される型となり、均質性メッキ及び光
沢性が悪くなる。Furthermore, if the amount of propylene oxide is less than 1 mole, an effective plating width cannot be obtained, and if it exceeds 10 moles, the naphthol strength is diluted, resulting in poor plating homogeneity and gloss.
本発明の添加剤をメッキ浴へ添加する方法及びメッキ条
件は、当業者が通常行う方法及び条件と同じである。The method and plating conditions for adding the additives of the present invention to the plating bath are the same as those commonly used by those skilled in the art.
なお、本発明の目的を阻害しない線中であれば、他の添
加剤を併用してもさしつかえない。Note that other additives may be used in combination as long as they do not impede the purpose of the present invention.
本発明に従って得られる添加剤を電気メッキ浴に添加し
た場合、均質メッキ性、光沢性を付与し、かつ広い有効
メッキ幅を有する、すなわち凸凹を有する三次元的被メ
ッキ体に均質ノー２キ性、光沢性を付与することが容易
に可能である。When the additive obtained according to the present invention is added to an electroplating bath, it imparts homogeneous plating properties and glossiness, and has a wide effective plating width, that is, it provides homogeneous no-two-kissing properties to three-dimensional plated objects having unevenness. , it is easily possible to impart glossiness.
次に実施例によって、本発明の詳細な説明する。（％は
重量基準である）
実施例
下記メッキ浴条件下で子種に美術工芸用錫板を用い、−
極に前処理を行った鋼板をセットし、錫メッキを行い、
水洗風乾後評価に供した。Next, the present invention will be explained in detail with reference to Examples. (% is based on weight) Example: Using a tin plate for arts and crafts as a seed under the following plating bath conditions, -
A pretreated steel plate is set on the pole, tin plated,
After washing with water and air drying, it was subjected to evaluation.
ただし、評価は被メッキ鋼板の下端より２５ｍ厘位の有
効メッキ幅で行った。結果を第１表に示す。However, the evaluation was performed with an effective plating width of approximately 25 m from the lower end of the steel plate to be plated. The results are shown in Table 1.
ａ、鋼板の前処理：
鋼板をアルカリ脱脂剤により電解脱脂を行い、水洗後硫
酸で表面調整し、水洗後メッキテストに供す。a. Pretreatment of steel plate: The steel plate is electrolytically degreased with an alkaline degreaser, washed with water, surface-conditioned with sulfuric acid, and subjected to a plating test after washing with water.
ｂ、メッキテスト（ハルセルテスト）；参メッキ浴
硫酸第一錫 ４５．２３３／ ｌ ゛フェノ
ールスルホン酸（′ｌ＆酸換算）１０ｇ／Ｊｌ
添加剤 ８ｇ／又
・メッキ条件
メッキ浴温度 ５０℃
電 流 ＤＧ ３Ａ時
間 ４０秒往−１；発泡
性
＋００−ネスラー管に電気錫メッキに供したメッキ浴を
３０−採取し、５０℃にセット後 １００回／３０秒間
はげしく振動させ、ネスラー管を静置後、発生した泡の
一敗について静置直後及び６０秒後側定した。b. Plating test (Hull Cell test); Plating bath Stannous sulfate 45.233/l phenol sulfonic acid ('l & acid equivalent) 10g/Jl Additive 8g/l Plating conditions Plating bath temperature 50℃ Current DG 3A hour
Time: 40 sec. The failure of the foam was determined immediately after the foam was allowed to stand still and after 60 seconds.
注−２；メッキ浴安定性
発泡性テストに供したメッキ浴を５０℃×２４時間放置
し、添加剤の溶解安定性を肉眼で判定した。゛
０ −−−−−−−−一均一安定
Ｘ −−−−−−−−一添加剤分離
第１表の結果より、本発明例はいずれも電気錫メッキテ
ストでみられるように、有効メッキ幅が広く、低泡性で
溶解安定性の良いことが認められる。Note-2: Plating bath stability The plating bath subjected to the foamability test was left at 50°C for 24 hours, and the dissolution stability of the additives was visually determined.゛0 - - - - - - - Uniform stability It is recognized that the plating width is wide, low foaming and good dissolution stability.
この有効メッキ幅が広いととは、等距離に被メッキ板が
ある場合においても、メッキ条件を厳密に管理しなくて
も商品価値を低下させない生産が可能になることはもと
より、三次元的被メッキ体にも均質、光沢メッキが学え
られることが可能である。This wide effective plating width means that even if there are plates equidistant from each other, it is possible to produce products without reducing the product value without strictly controlling the plating conditions, as well as to produce three-dimensional coatings. It is also possible to learn homogeneous and glossy plating on plated bodies.
さらに、低泡性レベルにあることから、電気メッキ工程
中における発泡トラブルを解消せしめ、溶解性に難の無
い点で被メッキ部に汚染を至らしめない。Furthermore, since it has a low foaming level, it eliminates the problem of foaming during the electroplating process, and since it has no problem in solubility, it does not cause contamination of the part to be plated.
一方の比較量ＮＯ６は、溶解性は良いが有効メッキ幅が
比較的低く、発泡も高い、Ｎｏ７は特に有効メッキ幅、
発泡に劣り、Ｎｏ８はＰＯのモル数が０．５モルと低い
ため有効メッキ幅に改善がみちれない、Ｎｏ９はプロピ
レンオキサイドモル数が１２モルと高いレベルにあるた
め、溶解性に劣り被メッキ体の汚染が懸念される。！１
ｋ）１０はエチレンオキサイド付加モル数が高いため発
泡が著しい、Ｎｏ１ｌはエチレンオキサイド付加モル数
が低いため、溶解性が劣る。On the other hand, comparative amount No. 6 has good solubility, but the effective plating width is relatively low and foaming is also high. No. 7 has a particularly effective plating width,
No. 8 is inferior in foaming, and since the number of moles of PO is as low as 0.5 moles, there is no improvement in the effective plating width. No. 9 has a high mole number of propylene oxide at 12 moles, so it has poor solubility and is difficult to plate. There are concerns about body contamination. ! 1
k) No. 10 has a high number of added moles of ethylene oxide, resulting in significant foaming; No. 11 has a low number of added moles of ethylene oxide, so it has poor solubility.
陥１２は初めがＥＯ付加体のため有効メッキ幅の点が劣
る。Since the recess 12 is initially an EO adduct, the effective plating width is inferior.
Claims (1)
から成る群より選ばれた少なくとも１種又は２種以上を
主成分とする電気メッキ浴用添加剤。 （１）▲数式、化学式、表等があります▼・・（１） （２）▲数式、化学式、表等があります▼・・（２） （３）▲数式、化学式、表等があります▼・・（３） （ただし、式中、ｌは１〜１０、ｎは０〜９の数字をそ
れぞれ示し、かつｌ＋ｎ＝１〜１０である、ｍは１〜１
５、ｘは０〜１４の数字をそれぞれ示し、かつｍ＋ｘ＝
５〜１５である。）[Scope of Claims] An additive for electroplating baths, the main component of which is at least one or more selected from the group consisting of compounds represented by the following general formulas (1), (2) and (3). (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (1) (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (2) (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・(3) (In the formula, l represents a number from 1 to 10, n represents a number from 0 to 9, and l+n = 1 to 10, and m represents a number from 1 to 1.
5, x represents a number from 0 to 14, and m+x=
5 to 15. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8201885A JPS61238993A (en) | 1985-04-16 | 1985-04-16 | Additive for electroplating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8201885A JPS61238993A (en) | 1985-04-16 | 1985-04-16 | Additive for electroplating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61238993A true JPS61238993A (en) | 1986-10-24 |
| JPH0343356B2 JPH0343356B2 (en) | 1991-07-02 |
Family
ID=13762780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8201885A Granted JPS61238993A (en) | 1985-04-16 | 1985-04-16 | Additive for electroplating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61238993A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62238388A (en) * | 1986-04-09 | 1987-10-19 | Toyo Kohan Co Ltd | Additive for tinning bath and tinning method |
| US5897763A (en) * | 1995-10-27 | 1999-04-27 | Lpw-Chemie Gmbh | Method of electroplating glare-free nickel deposits |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140095210A (en) * | 2013-01-24 | 2014-08-01 | 대동공업주식회사 | Engine speed control system and control methods of agriculture vehicle |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59182986A (en) * | 1983-04-01 | 1984-10-17 | Keigo Obata | Tin, lead and tin-lead alloy plating bath |
-
1985
- 1985-04-16 JP JP8201885A patent/JPS61238993A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59182986A (en) * | 1983-04-01 | 1984-10-17 | Keigo Obata | Tin, lead and tin-lead alloy plating bath |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62238388A (en) * | 1986-04-09 | 1987-10-19 | Toyo Kohan Co Ltd | Additive for tinning bath and tinning method |
| US5897763A (en) * | 1995-10-27 | 1999-04-27 | Lpw-Chemie Gmbh | Method of electroplating glare-free nickel deposits |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0343356B2 (en) | 1991-07-02 |
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