JPH052746B2 - - Google Patents
Info
- Publication number
- JPH052746B2 JPH052746B2 JP5220084A JP5220084A JPH052746B2 JP H052746 B2 JPH052746 B2 JP H052746B2 JP 5220084 A JP5220084 A JP 5220084A JP 5220084 A JP5220084 A JP 5220084A JP H052746 B2 JPH052746 B2 JP H052746B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- aluminum
- aluminum substrate
- copper
- hydrochloric acid
- 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 36
- 238000007747 plating Methods 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims description 11
- 239000011775 sodium fluoride Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000000052 comparative effect Effects 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 4
- 239000007788 liquid Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- -1 lack of magnetism Chemical compound 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
本発明はアルミニウム基板に直接メツキを行な
う際のメツキ前処理液に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a plating pretreatment liquid used when directly plating an aluminum substrate.
従来アルミニウムに直接電気メツキを行なう場
合他の金属に比べ、
表面酸化皮膜ができやすい。 Conventionally, when electroplating is performed directly on aluminum, a surface oxide film is more likely to form than on other metals.
電気化学的に活性で電解液におかされやす
い。 Electrochemically active and susceptible to electrolyte.
電気メツキ層にピンホールができ易い。 Pinholes are likely to form in the electroplated layer.
アルミニウムと電気メツキ金属層との熱膨張
係数が異なる。 The thermal expansion coefficients of aluminum and electroplated metal layers are different.
という事から密着の良いメツキを得るのは非常に
難かしかつた。しかしながら、アルミニウムにメ
ツキを施すことでアルミニウムの短所、例えば磁
性がない、硬度が低い、溶接性が良くない、など
のようなことを補なうことができ従来のアルミニ
ウムとは異なる特徴が得られるために、現在アル
ミニウム上へのメツキを行なう時は、ジンケート
法、ボンダル法などの亜鉛置換を行なつた後にメ
ツキする方法を取つている。しかしこの方法は多
くのプロセスを必要とするため、簡便な直接メツ
キ法が望まれている。Because of this, it was extremely difficult to obtain good adhesion. However, plating aluminum can compensate for the disadvantages of aluminum, such as lack of magnetism, low hardness, poor weldability, etc., and provides characteristics different from conventional aluminum. Therefore, when plating aluminum, a method such as zincate method or bondal method is used in which plating is performed after zinc substitution. However, since this method requires many processes, a simple direct plating method is desired.
本発明者らは、上記の方法に代わる直接メツキ
法に関し、種々の検討を行なう過程で、酸性弗化
ソーダと塩酸を含有すた水溶液を前処理液として
使用した場合に製造されるメツキ被覆品の表面性
及びメツキ金属のアルミニウムの密着性が改善さ
れることを見出し本発明を完成した。 In the process of conducting various studies regarding the direct plating method as an alternative to the above-mentioned method, the present inventors discovered that the plating-coated products produced when an aqueous solution containing acidic sodium fluoride and hydrochloric acid was used as a pretreatment liquid. The present invention was completed based on the discovery that the surface properties of aluminum and the adhesion of plating metal to aluminum can be improved.
即ち、本発明は、酸性弗化ソーダと塩酸の水溶
液（濃度化：酸性弗化ソーダ／塩酸＝0.003〜15）
とからなるアルミニウム基板のメツキ前処理液で
ある。 That is, the present invention provides an aqueous solution of acidic sodium fluoride and hydrochloric acid (concentration: acidic sodium fluoride/hydrochloric acid = 0.003 to 15).
This is a pre-treatment solution for plating aluminum substrates.
本発明の処理液を用いてアルミニウム基板の前
処理を行つた場合、メツキ表面の平面物性及びメ
ツキ金属とアルミニウム基板との密着性が向上
し、また、亜鉛置換法の如く多くのプロセスを必
要としない方法でアルミニウム基板への金属メツ
キができる等の効果を有する。 When an aluminum substrate is pretreated using the treatment solution of the present invention, the planar physical properties of the plated surface and the adhesion between the plated metal and the aluminum substrate are improved, and many processes such as the zinc substitution method are not required. It has the advantage of being able to plate metal on aluminum substrates using a method that would otherwise be impossible.
以下、本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明のメツキ前処理液は、塩酸水溶液に酸性
弗化ソーダを塩酸との濃度比が0.003〜15の範囲
（濃度比＝0.02〜２が特に好ましい）で添加し、
混合撹拌することにより調整される。濃度比が
0.003以下ではメツキ後の表面にむらがあり凹凸
ができ、濃度比が15以上ではエツチング速度が低
下し満足できる密着性が得られなくなつてしま
う。また、塩酸水溶液は36重量パーセント以下で
あれば良い。酸性弗化ソーダは0.01〜50ｇ／の
割合で添加するのが好ましく、特に0.5〜20ｇ／
が好ましい。 The plating pretreatment liquid of the present invention is prepared by adding acidic sodium fluoride to an aqueous hydrochloric acid solution at a concentration ratio of 0.003 to 15 (particularly preferably a concentration ratio of 0.02 to 2),
It is adjusted by mixing and stirring. The concentration ratio
If the concentration ratio is less than 0.003, the surface after plating will be uneven and uneven, and if the concentration ratio is more than 15, the etching rate will decrease and satisfactory adhesion will not be obtained. Further, the hydrochloric acid aqueous solution may be 36% by weight or less. Acidic sodium fluoride is preferably added at a rate of 0.01 to 50g/, particularly 0.5 to 20g/
is preferred.
本発明のメツキ前処理液が対象とするアルミニ
ウム基板は、JIS規格に記載されている規格品で
あれば何れでも使用できるが、アルミニウムの純
度が高い方が、含有される不純物の部分が選択的
にエツチングされることなく、緻密にエツチング
され、密着性が向上するために好ましい。 The aluminum substrate targeted by the plating pretreatment solution of the present invention can be any standard product listed in the JIS standard, but the higher the purity of the aluminum, the more selective the impurities it contains. This is preferable because it can be etched finely without being etched, and the adhesion can be improved.
本発明のメツキ処理液を用いてアルミニウム基
板を前処理する時間は、該処理液の酸度及び浴温
に左右されるので一概に決められないが、前処理
に際してアルミニウム基板の浸漬全表面に均一に
気泡ができるまでの時間が好ましい。また、それ
より多少長い時間でよい。例えば塩酸0.36重量％
水溶液に酸性弗化ソーダ20ｇ／を溶かした前処
理液の場合、アルミニウム基板の浸漬された全表
面に均一に気泡ができる時間は液温15℃で約20秒
である。また、処理温度は、特に制限されない
が、15〜30℃が好ましい。 The time for pre-treating an aluminum substrate using the plating treatment solution of the present invention cannot be determined unconditionally as it depends on the acidity of the treatment solution and the bath temperature, but during the pre-treatment, the entire immersed surface of the aluminum substrate should be uniformly coated. The time required to form bubbles is preferred. Also, a slightly longer time may be sufficient. For example, hydrochloric acid 0.36% by weight
In the case of a pretreatment solution in which 20 g of acidic sodium fluoride is dissolved in an aqueous solution, it takes about 20 seconds to uniformly form bubbles on the entire immersed surface of the aluminum substrate at a solution temperature of 15°C. Further, the treatment temperature is not particularly limited, but is preferably 15 to 30°C.
本発明のメツキ前処理液で処理されたアルミニ
ウム基板の電気メツキは、アルミニウムが両性金
属で酸、アルカリ共に侵され易いので中性領域で
行なわれるのが好ましい。例えばニツケルメツキ
ならば硫酸ニツケル浴、銅メツキならばピロリン
酸銅浴が好ましい。またこれらの金属の多層メツ
キを行なうこともできる。メツキ条件は通常のや
り方で実施できるが、最初メツキ膜厚0.3〜10μｍ
までは電流密度0.05〜2A／ｄm2で実施し、その
後所定の膜厚まで３〜20A／ｄm2の電流密度で実
施する方法が好ましい。 Electroplating of aluminum substrates treated with the plating pretreatment liquid of the present invention is preferably carried out in a neutral region, since aluminum is an amphoteric metal and is easily attacked by both acids and alkalis. For example, a nickel sulfate bath is preferred for nickel plating, and a copper pyrophosphate bath is preferred for copper plating. It is also possible to perform multilayer plating of these metals. Plating conditions can be carried out in the usual way, but the initial plating film thickness is 0.3 to 10 μm.
It is preferable to carry out the process at a current density of 0.05 to 2 A/dm 2 up to this point, and then at a current density of 3 to 20 A/dm 2 until a predetermined film thickness is reached.
以下、本発明を実施例及び比較例により詳細に
説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples.
なお、実施例及び比較例における平面性及び密
着性は、下記方法により測定した。 Note that the flatness and adhesion in Examples and Comparative Examples were measured by the following methods.
平面性；表面粗さ測定器を使用した。Flatness: A surface roughness measuring device was used.
密着性；第１図に示す如き試験片のＴ字型（90°）
剥離強度を測定した。（試験片40mm）
実施例 １
厚み40μｍのアルミニウム基板（JIS規格IN−
30）を、塩酸3.6重量パーセントの水溶液に酸性
弗化ソーダを20ｇ／の割合で溶かした前処理液
に浴温15℃で５秒浸漬したのち、ハーシヨウ村田
製ピロリン酸銅メツキ液を用いて、アルミニウム
基板を陰極とし、初め電流密度0.5A／ｄm2で平
均膜厚2μｍの銅メツキをした後、電流密度を
3.5A／ｄm2に増加させ計50μｍ厚の銅をアルミニ
ウム基板上にメツキした。その結果、表面の凹凸
は5μｍ以下であり、アルミニウムと銅の密着力
は300ｇ／mm2であつた。Adhesion: T-shape (90°) of the test piece as shown in Figure 1
Peel strength was measured. (Test piece 40 mm) Example 1 Aluminum substrate with a thickness of 40 μm (JIS standard IN-
30) was immersed in a pretreatment solution prepared by dissolving 20 g of acidic sodium fluoride in an aqueous solution of 3.6% by weight of hydrochloric acid at a bath temperature of 15°C for 5 seconds, and then using a copper pyrophosphate plating solution manufactured by Hershyou Murata. Using an aluminum substrate as a cathode, copper was plated with an average thickness of 2 μm at a current density of 0.5 A/ dm2 , and then the current density was increased.
A total of 50 μm thick copper was plated on an aluminum substrate at a rate of 3.5 A/dm 2 . As a result, the surface unevenness was 5 μm or less, and the adhesion between aluminum and copper was 300 g/mm 2 .
実施例 ２
厚み40μｍのアルミニウム基板（JIS規格IN−
30）を塩酸3.6重量パーセントの水溶液に酸性弗
化ソーダを２ｇ／の割合で溶かした前処理液に
浴温15℃で20秒浸漬したのち、ハーシヨウ村田製
ピロリン酸銅メツキ液を用いて、アルミニウム基
板を陰極とし、初め電流密度0.5A／ｄm2で平均
膜厚2μｍの銅メツキをした後、電流密度を
3.5A／ｄm2に増加させ計50μｍ厚の銅をアルミニ
ウム基板上にメツキした。その結果、表面の凹凸
は5μｍ以下であり、アルミニウムと銅の密着力
は270ｇ／mm2であつた。Example 2 Aluminum substrate with a thickness of 40 μm (JIS standard IN-
30) was immersed in a pretreatment solution prepared by dissolving 2 g of acidic sodium fluoride in an aqueous solution of 3.6% by weight of hydrochloric acid at a bath temperature of 15°C for 20 seconds. Using the substrate as a cathode, copper plating with an average thickness of 2 μm was first performed at a current density of 0.5 A/ dm2 , and then the current density was increased.
A total of 50 μm thick copper was plated on an aluminum substrate at a rate of 3.5 A/dm 2 . As a result, the surface unevenness was 5 μm or less, and the adhesion between aluminum and copper was 270 g/mm 2 .
比較例 １
厚み40μｍのアルミニウム基板（JIS規格IN−
30）を3.6重量パーセントの塩酸水溶液に浴温15
℃で５秒浸漬したのち、ハーシヨウ村田製ピロリ
ン酸銅メツキ液を用いて、アルミニウム基板を陰
極とし、初め電流密度0.5A／ｄm2で平均膜厚2μ
ｍ銅メツキした後、電流密度を3.5A／ｄm2に増
加させ計50μｍ厚の銅をアルミニウム基板上にメ
ツキした。その結果、表面の凹凸は20〜30μｍで
あつた。Comparative example 1 Aluminum substrate with a thickness of 40 μm (JIS standard IN-
30) Add to a 3.6 weight percent hydrochloric acid aqueous solution at a bath temperature of 15
After dipping for 5 seconds at ℃, using a copper pyrophosphate plating solution manufactured by Hershyou Murata, using the aluminum substrate as a cathode, the average film thickness was 2 μ at an initial current density of 0.5 A/dm 2 .
After copper plating, the current density was increased to 3.5 A/dm 2 to plate a total of 50 μm thick copper on the aluminum substrate. As a result, the surface unevenness was 20 to 30 μm.
比較例 ２
厚み40μｍのアルミニウム基板（JIS規格IN−
30）を濃度が２ｇ／の酸性弗化ソーダ水溶液に
浴温15℃で60秒浸漬したのち、ハーシヨウ村田製
ピロリン酸銅メツキ液を用いて、アルミニウム基
板を陰極とし、初め電流密度0.5A／ｄm2で平均
膜厚2μｍの銅メツキをした後、電流密度を
3.5A／ｄm2に増加させ計50μｍ厚の銅をアルミニ
ウム基板上にメツキした。その結果、表面の凹凸
は5μｍ以下で、アルミニウムと銅の密着力は、
60ｇ／mm2であつた。Comparative example 2 Aluminum substrate with a thickness of 40 μm (JIS standard IN-
30) was immersed in an acidic sodium fluoride aqueous solution with a concentration of 2 g/dm for 60 seconds at a bath temperature of 15°C, and using a copper pyrophosphate plating solution manufactured by Hershiyo Murata, the aluminum substrate was used as a cathode, and the initial current density was 0.5 A/dm. After copper plating with an average thickness of 2 μm in step 2 , the current density was
A total of 50 μm thick copper was plated on an aluminum substrate at a rate of 3.5 A/dm 2 . As a result, the surface irregularities were less than 5 μm, and the adhesion between aluminum and copper was
It was 60g/ mm2 .
第１図は、実施例及び比較例における密着性測
定用試験片の断面図である。
図中；１はメツキ層、２はアルミニウム層、θ
は90°、矢印は引張方向を示す。
FIG. 1 is a cross-sectional view of a test piece for measuring adhesion in Examples and Comparative Examples. In the figure; 1 is the plating layer, 2 is the aluminum layer, θ
is 90°, and the arrow indicates the direction of tension.
Claims (1)
性弗化ソーダ／塩酸＝0.003〜15）とからなるア
ルミニウム基板のメツキ前処理液。1. A pre-plating solution for aluminum substrates consisting of an aqueous solution of acidic sodium fluoride and hydrochloric acid (concentration ratio: acidic sodium fluoride/hydrochloric acid = 0.003-15).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5220084A JPS60197895A (en) | 1984-03-21 | 1984-03-21 | Solution for pretreating aluminum substrate before plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5220084A JPS60197895A (en) | 1984-03-21 | 1984-03-21 | Solution for pretreating aluminum substrate before plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60197895A JPS60197895A (en) | 1985-10-07 |
| JPH052746B2 true JPH052746B2 (en) | 1993-01-13 |
Family
ID=12908139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5220084A Granted JPS60197895A (en) | 1984-03-21 | 1984-03-21 | Solution for pretreating aluminum substrate before plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60197895A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH075337U (en) * | 1993-06-21 | 1995-01-27 | 幸 常田 | Fan |
-
1984
- 1984-03-21 JP JP5220084A patent/JPS60197895A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH075337U (en) * | 1993-06-21 | 1995-01-27 | 幸 常田 | Fan |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60197895A (en) | 1985-10-07 |
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