JPH0521993B2 - - Google Patents
Info
- Publication number
- JPH0521993B2 JPH0521993B2 JP19737188A JP19737188A JPH0521993B2 JP H0521993 B2 JPH0521993 B2 JP H0521993B2 JP 19737188 A JP19737188 A JP 19737188A JP 19737188 A JP19737188 A JP 19737188A JP H0521993 B2 JPH0521993 B2 JP H0521993B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- copper
- copper sulfate
- iron material
- strike
- 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.)
- Expired - Lifetime
Links
- 238000007747 plating Methods 0.000 claims description 77
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 35
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 35
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は鉄素材に密着のよい硫酸銅めつき皮膜
を形成することができる硫酸銅めつき方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a copper sulfate plating method capable of forming a copper sulfate plating film with good adhesion to an iron material.
鉄素材を酸性硫酸銅めつき液中に浸漬して硫酸
銅めつきを行なう場合、鉄素材をそのまま酸性硫
酸銅めつき液中に浸漬すると、イオン化傾向のた
め鉄素材から鉄イオンが硫酸鉄としてめつき液中
に溶解すると共に、めつき液中の銅イオンが鉄素
材表面に金属銅として析出する置換反応が生じ
る。そして、このように置換反応により銅が析出
した鉄素材に硫酸銅めつきを行なつても、鉄素材
に対する硫酸銅めつき皮膜の密着が悪いものにな
る。
When performing copper sulfate plating by immersing an iron material in an acidic copper sulfate plating solution, if the iron material is directly immersed in the acidic copper sulfate plating solution, iron ions from the iron material will be released as iron sulfate due to its tendency to ionize. While dissolving in the plating solution, a substitution reaction occurs in which copper ions in the plating solution precipitate as metallic copper on the surface of the iron material. Even if copper sulfate plating is performed on an iron material on which copper has been precipitated by the substitution reaction, the adhesion of the copper sulfate plating film to the iron material will be poor.
このために従来、鉄素材に硫酸銅めつきを行な
う場合は、青化銅めつき浴やピロリン酸銅めつき
浴をストライク浴として用い、青化銅ストライク
めつき、ピロリン酸銅ストライクめつきを行なつ
て鉄素材表面にこれらのめつきによる皮膜を形成
した後、硫酸銅めつきを行なう方法が採用されて
いる。 For this reason, conventionally, when copper sulfate plating is performed on iron materials, a bronze plating bath or a copper pyrophosphate plating bath is used as the strike bath, and copper bronze strike plating or copper pyrophosphate strike plating is performed. A method is adopted in which a film is formed by these platings on the surface of the iron material, and then copper sulfate plating is performed.
しかし、青化銅ストライクめつきを行なう方法
は、使用するストライクめつき浴が猛毒の青化物
を含むものであるため、その取り扱いに注意を要
する問題がある。一方、ピロリン酸銅ストライク
めつきは、その浴が赤潮発生の原因となるリン分
を多量に含むため廃液上の問題がある上、該ピロ
リン酸銅ストライクはその浴管理が面倒であり、
また浴が高価である。
However, the method of copper cronide strike plating has a problem in that the strike plating bath used contains a highly toxic cyanide, which requires careful handling. On the other hand, copper pyrophosphate strike plating has problems with waste liquid because the bath contains a large amount of phosphorus that causes red tide, and the copper pyrophosphate strike is troublesome to manage.
Also, baths are expensive.
本発明は上記欠点を除去するためになされたも
ので、鉄素材に酸性硫酸銅めつきを施す場合に、
密着性よく硫酸銅めつき皮膜を鉄素材に形成し得
ると共に、毒性、廃液上の問題が少なく、ストラ
イクめつき浴管理も比較的容易な硫酸銅めつき方
法を提供することを目的とする。 The present invention was made to eliminate the above-mentioned drawbacks, and when applying acidic copper sulfate plating to iron materials,
To provide a copper sulfate plating method which can form a copper sulfate plating film with good adhesion on an iron material, has few problems with toxicity and waste liquid, and is relatively easy to manage in a strike plating bath.
本発明者は上記目的を達成するために種々検討
を行なつた結果、アルカリ性無電解銅めつき浴を
ストライクめつき浴として用い、鉄素材にまずこ
のアルカリ性無電解銅めつき浴にてストライクめ
つきを施し、その表面に無電解銅めつき皮膜を形
成した後、これを酸性硫酸銅めつき液に浸漬し、
硫酸銅めつきを行なえば、最早置換めつき反応は
起らず、密着の良い硫酸銅めつきが可能になるこ
と、そしてこのようにアルカリ性無電解銅めつき
浴をストライクめつき浴として使用するので、青
化銅，ピロリン酸銅ストライクめつき浴を用いた
場合のような毒性、廃液上の問題が少なく、その
管理も容易であることを見い出し、本発明をなす
に至つた。
As a result of various studies in order to achieve the above object, the present inventor used an alkaline electroless copper plating bath as a strike plating bath, and first applied a strike plate to an iron material using this alkaline electroless copper plating bath. After plating and forming an electroless copper plating film on the surface, this is immersed in an acidic copper sulfate plating solution,
If copper sulfate plating is performed, the displacement plating reaction will no longer occur, and copper sulfate plating with good adhesion will be possible, and in this way, an alkaline electroless copper plating bath can be used as a strike plating bath. Therefore, the present inventors have discovered that there are fewer problems of toxicity and waste liquid that occur when copper bronze or copper pyrophosphate strike plating baths are used, and that the management thereof is easy, and the present invention has been completed.
従つて、本発明は、鉄素材を酸性硫酸銅電気め
つき液中に浸漬して硫酸銅めつきを行なうに際
し、鉄素材にアルカリ性無電解銅めつきを施して
該鉄素材表面を無電解銅めつき皮膜で被覆した
後、上記酸性硫酸銅電気めつき液中に浸漬するこ
とを特徴とする硫酸銅めつき方法を提供する。 Therefore, in the present invention, when performing copper sulfate plating by immersing the iron material in an acidic copper sulfate electroplating solution, the iron material is subjected to alkaline electroless copper plating to coat the surface of the iron material with electroless copper. A method for plating copper sulfate is provided, which comprises coating the material with a plating film and then immersing it in the acidic copper sulfate electroplating solution.
以下、本発明につき更に詳しく説明する。 The present invention will be explained in more detail below.
本発明は、鉄素材に硫酸銅めつきを施す方法に
係わるものであるが、ここで鉄素材としては純鉄
以外に通常のスチールや鉄鋳物を含むものであ
る。 The present invention relates to a method of plating iron material with copper sulfate, and the iron material here includes ordinary steel and cast iron in addition to pure iron.
而して、かかる鉄素材に硫酸銅めつきを施す場
合は、該鉄素材の表面状態に応じ、脱スケール、
脱脂、酸洗活性化といつた適宜な前処理を行なつ
た後、まずアルカリ性無電解銅ストライクめつき
を行なう。 When applying copper sulfate plating to such iron materials, descaling,
After appropriate pretreatment such as degreasing and pickling activation, alkaline electroless copper strike plating is first performed.
この場合、アルカリ無電解銅ストライクめつき
浴としては、プラスチツク上に無電解銅めつきを
施す場合に通常用いられるいずれの浴も使用でき
る。典型的には、アルカリ性無電解銅めつきスト
ライクめつき浴としては、硫酸銅等の水溶性銅
塩、ホルマリンやほう素系還元剤等の還元剤、錯
化剤、苛性アルカリ、安定剤などを含有するもの
が用いられる。ここで、水溶性銅塩の濃度は１
ｇ／〜20ｇ／、特に２ｇ／〜５ｇ／、還
元剤の濃度は１ｇ／〜20ｇ／、特に２ｇ／
〜５ｇ／が好ましい。また、錯化剤としては酒
石酸カリ、ロツセル塩、エチレンジアミン、
EDTA、クワドロールなどが挙げられ、その濃
度は0.05mol／〜0.5mol／、特に0.1mol／
〜0.2mol／とすることが好ましい。更に、苛
性アルカリとしては、苛性ソーダ、苛性カリ等が
使用でき、その濃度は２ｇ／〜20ｇ／、特に
３ｇ／〜６ｇ／とすることができる。また更
に、安定剤としてはシアン化ナトリウム、シアン
化カリウム、ジピリジンフエロシアン、フエナン
トロリンなどを使用することができ、その濃度は
１mg／〜２ｇ／、特に５mg／〜50mg／と
することが好ましい。 In this case, as the alkaline electroless copper strike plating bath, any bath commonly used for electroless copper plating on plastic can be used. Typically, a strike plating bath for alkaline electroless copper plating contains a water-soluble copper salt such as copper sulfate, a reducing agent such as formalin or a boron-based reducing agent, a complexing agent, a caustic alkali, a stabilizer, etc. The one containing is used. Here, the concentration of water-soluble copper salt is 1
g/~20g/, especially 2g/~5g/, the concentration of the reducing agent is 1g/~20g/, especially 2g/
~5g/ is preferred. In addition, as a complexing agent, potassium tartrate, Lotusel salt, ethylenediamine,
Examples include EDTA, Quadrol, etc., and the concentration is 0.05mol/~0.5mol/, especially 0.1mol/
It is preferable to set it to 0.2 mol/. Further, as the caustic alkali, caustic soda, caustic potash, etc. can be used, and the concentration thereof can be 2 g/~20 g/, particularly 3 g/~6 g/. Further, as a stabilizer, sodium cyanide, potassium cyanide, dipyridine ferocyanide, phenanthroline, etc. can be used, and the concentration thereof is preferably 1 mg/~2 g/, particularly 5 mg/~50 mg/.
なお、このアルカリ性無電解銅ストライクめつ
き浴のPHは12〜13、特に12.3〜12.8が好ましい。 The pH of this alkaline electroless copper strike plating bath is preferably 12 to 13, particularly preferably 12.3 to 12.8.
かかるめつき浴を用いてストライクめつきを行
なう場合の条件としては、めつき温度は15〜70
℃、特に25〜60℃とすることが好ましく、めつき
時間は通常１〜20分、より好適には３〜５分であ
る。 When performing strike plating using such a plating bath, the plating temperature is 15 to 70°C.
The temperature is preferably 25 to 60°C, and the plating time is usually 1 to 20 minutes, more preferably 3 to 5 minutes.
上記ストライクめつき後は、水洗、酸洗を適宜
行なつた後、硫酸銅めつきを行なうが、この場合
に使用するめつき液組成、めつき条件は通常の組
成、条件でよく、例えば硫酸銅50〜300ｇ／、
硫酸60〜250ｇ／、それに必要により光沢剤、
塩素イオン等を適宜添加した組成のめつき液を使
用し、陰極電流密度１〜30A／ｄm2、めつき温度
20〜60℃、空気攪拌という条件でめつきを行なう
ことができる。 After the strike plating described above, copper sulfate plating is performed after washing with water and pickling as appropriate. In this case, the composition of the plating solution used and the plating conditions may be the usual compositions and conditions, such as copper sulfate. 50~300g/,
60-250g of sulfuric acid, plus brightener if necessary,
Use a plating solution with a composition appropriately added with chlorine ions, etc., at a cathode current density of 1 to 30 A/dm 2 and at a plating temperature.
Plating can be performed under the conditions of 20 to 60°C and air agitation.
本発明によれば、鉄素材に密着性よく硫酸銅め
つき皮膜を析出させることができ、またストライ
クめつき浴は毒性、廃液上の問題が少なく、取り
扱いが容易であると共に、ストライクめつき管理
も容易である。
According to the present invention, a copper sulfate plating film can be deposited on iron materials with good adhesion, and the strike plating bath has few problems with toxicity and waste liquid, is easy to handle, and can be used to manage strike plating. is also easy.
以下、本発明の実施例を示すが、本発明は下記
の実施例に限定されるものではない。 Examples of the present invention will be shown below, but the present invention is not limited to the following examples.
鉄素材として純鉄を用い、常法に従つてアルカ
リ脱脂、電解脱脂、酸洗した後、下記の無電解銅
めつき浴を用いて下記条件でストライクめつきを
施した。
Pure iron was used as the iron material, and after alkaline degreasing, electrolytic degreasing, and pickling according to conventional methods, strike plating was performed using the following electroless copper plating bath under the following conditions.
組 成
硫酸銅 0.04mol／
ホルムアルデヒド 0.08mol／
水酸化ナトリウム 0.10mol／
EDTA 0.05mol／
ジピリジン 30mg／
めつき条件
めつき温度 55℃
めつき時間 ２分
次に、酸洗後、下記組成の硫酸銅めつき液によ
り下記条件で硫酸銅めつきを行なつた。Composition Copper sulfate 0.04mol / Formaldehyde 0.08mol / Sodium hydroxide 0.10mol / EDTA 0.05mol / Dipyridine 30mg / Plating conditions Plating temperature 55℃ Plating time 2 minutes Next, after pickling, copper sulfate plate with the following composition Copper sulfate plating was carried out using a plating solution under the following conditions.
組 成
硫酸銅 75ｇ／
硫酸 190ｇ／
塩素 60ppm
スルカツプAC−90 ５ml／
（光沢剤−上村工業(株)社製）
めつき条件
陰極電流密度 3A／ｄm2
めつき温度 25℃
攪拌 空気攪拌
めつき時間 ５分
上記硫酸銅めつき後、引張試験、ゴバン目テス
トという方法で鉄素材と硫酸銅めつき皮膜との密
着性を調べた結果、優れた密着性を示すことが認
められた。Composition Copper sulfate 75g / Sulfuric acid 190g / Chlorine 60ppm Sulkatup AC-90 5ml / (Brightening agent - manufactured by Uemura Kogyo Co., Ltd.) Plating conditions Cathode current density 3A/dm 2 Plating temperature 25℃ Stirring Air stirring Plating time 5 minutes After the above-mentioned copper sulfate plating, the adhesion between the iron material and the copper sulfate plating film was examined using a tensile test and a burlap test, and it was found that the film had excellent adhesion.
Claims (1)
て硫酸銅めつきを行なうに際し、鉄素材にアルカ
リ性無電解銅めつきを施して該鉄素材表面を無電
解銅めつき皮膜で被覆した後、上記酸性硫酸銅電
気めつき液中に浸漬することを特徴とする硫酸銅
めつき方法。1 When performing copper sulfate plating by immersing the iron material in an acidic copper sulfate electroplating solution, alkaline electroless copper plating was applied to the iron material to cover the surface of the iron material with an electroless copper plating film. A method for plating copper sulfate, which is then immersed in the acidic copper sulfate electroplating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19737188A JPH0247289A (en) | 1988-08-08 | 1988-08-08 | Copper plating method with copper sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19737188A JPH0247289A (en) | 1988-08-08 | 1988-08-08 | Copper plating method with copper sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0247289A JPH0247289A (en) | 1990-02-16 |
| JPH0521993B2 true JPH0521993B2 (en) | 1993-03-26 |
Family
ID=16373387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19737188A Granted JPH0247289A (en) | 1988-08-08 | 1988-08-08 | Copper plating method with copper sulfate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0247289A (en) |
-
1988
- 1988-08-08 JP JP19737188A patent/JPH0247289A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0247289A (en) | 1990-02-16 |
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