JPH04157165A - Electroless metal plating method - Google Patents
Electroless metal plating methodInfo
- Publication number
- JPH04157165A JPH04157165A JP27801290A JP27801290A JPH04157165A JP H04157165 A JPH04157165 A JP H04157165A JP 27801290 A JP27801290 A JP 27801290A JP 27801290 A JP27801290 A JP 27801290A JP H04157165 A JPH04157165 A JP H04157165A
- Authority
- JP
- Japan
- Prior art keywords
- soln
- adhesion
- metal plating
- copper
- electroless
- 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 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002318 adhesion promoter Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229960003280 cupric chloride Drugs 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 3
- 238000007772 electroless plating Methods 0.000 abstract description 2
- 101150003085 Pdcl gene Proteins 0.000 abstract 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract 2
- 235000011150 stannous chloride Nutrition 0.000 abstract 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 abstract 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 230000001235 sensitizing effect Effects 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 23
- 229910052802 copper Inorganic materials 0.000 description 23
- 239000000243 solution Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910000976 Electrical steel Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- KOWWOODYPWDWOJ-LVBPXUMQSA-N elatine Chemical compound C([C@]12CN(C3[C@@]45OCO[C@]44[C@H]6[C@@H](OC)[C@@H]([C@H](C4)OC)C[C@H]6[C@@]3([C@@H]1[C@@H]5OC)[C@@H](OC)CC2)CC)OC(=O)C1=CC=CC=C1N1C(=O)CC(C)C1=O KOWWOODYPWDWOJ-LVBPXUMQSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は無電解金属めっき方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to an electroless metal plating method.
印刷配線板は、銅張り積層板に穴明けを施した後、無電
解金属めっきを行うことで製造される。Printed wiring boards are manufactured by drilling holes in a copper-clad laminate and then performing electroless metal plating.
無電解金属めっき前処理工程は次のような工程で行われ
る。銅張り積層板に穴明は後、脱脂・洗浄工程を行い、
次に銅表面を軽くエラチン！し、稀硫酸で洗い、塩化パ
ラジウム、塩化スズ等を含む増感剤に浸漬した後、密着
促進剤で基板表面に付着している金属不純物（Ｓｎ”″
→αスズ＃）を取り除くと共に、パラジウム化合物を金
属パラジウムに還元させ、無電解金属めっき液に投入し
て銅を析出させる。The electroless metal plating pretreatment process is performed in the following steps. After drilling holes in the copper-clad laminate, we perform a degreasing and cleaning process.
Next, lightly elatin the copper surface! After washing with dilute sulfuric acid and immersing in a sensitizer containing palladium chloride, tin chloride, etc., metal impurities (Sn'') attached to the substrate surface are removed using an adhesion promoter.
→αTin#) is removed, and the palladium compound is reduced to metal palladium, which is then introduced into an electroless metal plating solution to deposit copper.
従来、この密着促進剤処理には、特開昭５０−８１９２
７号、硫酸と塩酸の混酸や、このような混酸に酒石酸を
添加した処理液に浸漬する方法や、あるいは特開昭５１
−８１２７号公報に開示されているように、Ｎａ ＯＨ
とエチレンジアミン四酢酸を含む水溶液に浸漬する方法
がある。Conventionally, this adhesion promoter treatment has been described in Japanese Patent Application Laid-Open No. 50-8192.
No. 7, a method of immersing in a mixed acid of sulfuric acid and hydrochloric acid, a treatment solution in which tartaric acid is added to such a mixed acid, or JP-A-51
As disclosed in Publication No.-8127, NaOH
There is a method of immersing it in an aqueous solution containing ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid.
本発明は、無電解金属めっきの前処理工程である密着促
進剤の水溶液中をエアーを入れてバブリングすることで
、下地銅と析出銅との密着性に優れる無電解金属めっき
方法を提供しようとするものである。The present invention aims to provide an electroless metal plating method that achieves excellent adhesion between the base copper and deposited copper by bubbling air into an aqueous solution of an adhesion promoter, which is a pretreatment step for electroless metal plating. It is something to do.
（ｆｆｌ！！を解決するための手段〕
本発明の！！＃電解金属めっき方法は、被めっき物を塩
化パラジウム及び塩化スズを含む増感剤で処理した後、
エアーでバブリングされた密着促進剤の水溶液中で処理
することを特徴とする。(Means for solving ffl!!) In the!!# electrolytic metal plating method of the present invention, after treating the object to be plated with a sensitizer containing palladium chloride and tin chloride,
It is characterized by treatment in an aqueous solution of an adhesion promoter bubbled with air.
本発明のｖＪ！着促進剤は、ｆＬｆｌ＆・有機酸・塩化
第二銅を主成分とし、その水溶液中にエアーをｏ、。vJ of the present invention! The adhesion promoter is mainly composed of organic acid and cupric chloride, and air is added to the aqueous solution.
１１／ｓｉｎ〜１０．０１ ／ｓｉｎ入れてバブリング
する。さらに好ましくは、０．１〜１．０１ ／ｓｉｎ
の範囲である。このエアー量は、下地銅と析出銅との密
着力と密着促進剤の寿命に影響する。エアー量が０．０
１１７ｓｉｎより低いと、下地銅と析出銅との密着力が
低下し、１− Ｏｊ ／ｓｉｎより高いと密着促進剤の
液寿命が低下する。Add 11/sin to 10.01/sin and bubble. More preferably, 0.1 to 1.01/sin
is within the range of The amount of air affects the adhesion between the base copper and the deposited copper and the life of the adhesion promoter. Air amount is 0.0
When it is lower than 117 sin, the adhesion between the base copper and the deposited copper decreases, and when it is higher than 1-Oj/sin, the liquid life of the adhesion promoter decreases.
コノヨウニ、エアーを０．０１ ｍ！ ／ｗｉｎ 〜１
．０１／ｓｉｎの範囲で流すことで、下地鋼と析出銅の
密着性を向上させ、液の長寿命化が得られる無電解金属
めっき方法を見出した。Konoyouni, air 0.01 m! /win ~1
．． We have discovered an electroless metal plating method that improves the adhesion between the base steel and the deposited copper by flowing within the range of 0.01/sin, thereby extending the life of the solution.
前記密着促進剤の水溶液中に、エアーを入れバブリング
することで、下地銅と析出銅との密着力に優れ、かつ液
の長寿命に連がる無電解金属めっきを行うことができる
。By bubbling air into the aqueous solution of the adhesion promoter, it is possible to perform electroless metal plating that provides excellent adhesion between the copper base and the deposited copper and extends the life of the solution.
実施例１
板ｆｆ１．６１１１１１１．銅ｆ６厚３５μ層のガラス
・エポキシ銅張り積層板ＭＣＬ−Ｅ−６７（日立化成工
業株式会社製、商品名）を被めっき材とした。Example 1 Plate ff1.6111111. A glass/epoxy copper-clad laminate MCL-E-67 (manufactured by Hitachi Chemical Co., Ltd., trade name) having a copper f6 layer thickness of 35 μm was used as the plated material.
無電解金属めっきの工程は次の通りとした。The process of electroless metal plating was as follows.
クリーナーコンディショナーであるＣＬＣ−３０１（日
立化成工業株式会社製、商品名）に６０℃で４分間浸漬
し、水洗後、遇ｇ酸アンモニウムでソフトエツチングを
行い、１０％硫酸で洗い、ＰＤ−２０１（日立化成工業
株式会社製、商品名）で処理後、ＭＳ−２０２Ｂ （日
立化成工業株式会社製、商品名）無電解めっき用触媒液
に５分間浸漬後、５分間水洗した。It was immersed in cleaner conditioner CLC-301 (manufactured by Hitachi Chemical Co., Ltd., trade name) at 60°C for 4 minutes, washed with water, soft-etched with ammonium chloride, washed with 10% sulfuric acid, and then treated with PD-201 (trade name). After treatment with MS-202B (manufactured by Hitachi Chemical Co., Ltd., trade name) for 5 minutes in an electroless plating catalyst solution, the sample was washed with water for 5 minutes.
この基材を、硫酸とクエン酸、塩化第二銅を含む水溶液
に、エアーをいれバブリングしながら５分間浸漬し、２
分間水洗水に浸漬した後、Ｎ電解銅めっき液であるＣｕ
５ｔ−２０１（日立化成工業株式会社製、商品名）に１
５分間浸漬する。This base material was immersed in an aqueous solution containing sulfuric acid, citric acid, and cupric chloride for 5 minutes while bubbling air.
After being immersed in rinsing water for a minute, the Cu
1 to 5t-201 (manufactured by Hitachi Chemical Co., Ltd., product name)
Soak for 5 minutes.
実施例２
密着促進剤として硫酸と酒石酸、塩化第二銅を含む水溶
液に、エアー攪拌を用いた以外は実施例１と同様とした
。Example 2 The same procedure as Example 1 was carried out except that air stirring was used for an aqueous solution containing sulfuric acid, tartaric acid, and cupric chloride as adhesion promoters.
比較例１
実施例１と同じ被めっき材を用い、同じ工程で銅めっき
を行った。密着促進剤はＡＤＰ−２０１（日立化成工業
株式会社製、商品名）を用いた。Comparative Example 1 The same material to be plated as in Example 1 was used and copper plating was performed in the same process. ADP-201 (manufactured by Hitachi Chemical Co., Ltd., trade name) was used as the adhesion promoter.
比較例２
実施例１と同じ被めうき材を用い、同し工程で銅めっき
を行った。密着促進剤はＡＤＰ−３０１（日立化成工業
株式会社製、商品名）を用いた。Comparative Example 2 The same material to be plated as in Example 1 was used, and copper plating was performed in the same process. ADP-301 (manufactured by Hitachi Chemical Co., Ltd., trade name) was used as the adhesion promoter.
特性評価を下記方法で行った。Characteristic evaluation was performed using the following method.
（下地銅と析出銅の密着性）
実施例１に記しためうき工程においては密着性はすべて
良好となり、密着不良の発生はない。(Adhesion between base copper and deposited copper) In the plating process described in Example 1, the adhesion was good in all cases, and no adhesion failure occurred.
そこで、実施例１のめっき工程で過硫酸アンモニウムに
よるエツチングを行わないことにした。Therefore, it was decided not to perform etching using ammonium persulfate in the plating process of Example 1.
その後、電解銅めっきを行い、端部よりカッターナイフ
等で引刺しを行い、下地網と析出銅との間での判れを確
認する。After that, electrolytic copper plating is performed, and the edges are pricked with a cutter knife or the like to check the difference between the base mesh and the deposited copper.
密着性が悪い場合、引剥した後に下地銅が残存する。If the adhesion is poor, the underlying copper will remain after peeling off.
（ざらつき） 実施例１に記した密着促進剤の水溶液にＣｕ”。(Roughness) Cu” in the aqueous solution of the adhesion promoter described in Example 1.
イオンを添加し、処理することで下地銅表面が酸化し易
い状態でＣｕ５ｔ−２０１に投入し、電気鋼めっきまで
行い、表面のざらつきの有無を確認する０以上の結果に
ついて表１に示した。The base copper surface was easily oxidized by adding ions, and the copper surface was put into Cu5t-201 in a state where it was easily oxidized, and then subjected to electrical steel plating. Table 1 shows the results of 0 or more to confirm the presence or absence of roughness on the surface.
実施例から、過度な状況下においても、エアー攪拌する
ことで下地銅と析出銅との密着性は良好である。又、被
めっき板表面のザラツキの発生はなく、液の長寿命に連
がる。From the examples, even under extreme conditions, the adhesion between the base copper and the deposited copper is good by air stirring. In addition, there is no occurrence of roughness on the surface of the plated plate, which leads to a long life of the liquid.
比較例１．２は、過度な状況でざらつきの発生が見られ
た。以上の結果から、本発明の無電解金属めっき方法が
優れた特性であることが判った。In Comparative Example 1.2, roughness was observed under excessive conditions. From the above results, it was found that the electroless metal plating method of the present invention has excellent characteristics.
Claims (2)
感剤で処理した後、エアー量を０．１ｌ／ｍｉｎ以上で
バブリングしている密着促進剤の水溶液で処理すること
を特徴とする無電解金属めっき方法。1. Electroless metal plating characterized in that the object to be plated is treated with a sensitizer containing palladium chloride and tin chloride, and then treated with an aqueous solution of an adhesion promoter in which air is bubbled at a rate of 0.1 l/min or more. Method.
銅を含む水溶液であることを特徴とする請求項１に記載
の無電解金属めっき方法。2. 2. The electroless metal plating method according to claim 1, wherein the main component of the adhesion promoter is an aqueous solution containing sulfuric acid, an organic acid, and cupric chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27801290A JPH04157165A (en) | 1990-10-17 | 1990-10-17 | Electroless metal plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27801290A JPH04157165A (en) | 1990-10-17 | 1990-10-17 | Electroless metal plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04157165A true JPH04157165A (en) | 1992-05-29 |
Family
ID=17591412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27801290A Pending JPH04157165A (en) | 1990-10-17 | 1990-10-17 | Electroless metal plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04157165A (en) |
-
1990
- 1990-10-17 JP JP27801290A patent/JPH04157165A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3009326B2 (en) | Method for applying metallization to non-conductive substrates | |
| US5250105A (en) | Selective process for printing circuit board manufacturing | |
| US4863758A (en) | Catalyst solutions for activating non-conductive substrates and electroless plating process | |
| EP0176736B1 (en) | Process for selective metallization | |
| US4639380A (en) | Process for preparing a substrate for subsequent electroless deposition of a metal | |
| JP2769954B2 (en) | Method for electrodepositing metal plating directly on plastic substrates | |
| US4999251A (en) | Method for treating polyetherimide substrates and articles obtained therefrom | |
| US4160050A (en) | Catalyzation processes for electroless metal deposition | |
| US5474798A (en) | Method for the manufacture of printed circuit boards | |
| US3694250A (en) | Electroless copper plating | |
| US5238550A (en) | Electroplating process | |
| US5425873A (en) | Electroplating process | |
| US5770032A (en) | Metallizing process | |
| JPS61194183A (en) | Electroless plating method | |
| US5206052A (en) | Electroless plating process | |
| JPH0376599B2 (en) | ||
| US4222778A (en) | Liquid seeders for electroless metal deposition | |
| JPH04157165A (en) | Electroless metal plating method | |
| US4693907A (en) | Process or non-electrolytic copper plating for printed circuit board | |
| US4874635A (en) | Method for removing residual precious metal catalyst from the surface of metal-plated plastics | |
| US5108786A (en) | Method of making printed circuit boards | |
| US5547559A (en) | Process for plating metals onto various substrates in an adherent fashion | |
| US5419829A (en) | Electroplating process | |
| EP0109402A1 (en) | Catalyst solutions for activating non-conductive substrates and electroless plating process. | |
| JP2002060965A (en) | Treating solution and treating method for reducing copper oxide |