JPS59193261A - Electroless copper plating bath - Google Patents
Electroless copper plating bathInfo
- Publication number
- JPS59193261A JPS59193261A JP6662383A JP6662383A JPS59193261A JP S59193261 A JPS59193261 A JP S59193261A JP 6662383 A JP6662383 A JP 6662383A JP 6662383 A JP6662383 A JP 6662383A JP S59193261 A JPS59193261 A JP S59193261A
- Authority
- JP
- Japan
- Prior art keywords
- copper plating
- plating solution
- electroless copper
- plating bath
- copper
- 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
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/187—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating means therefor, e.g. baths, apparatus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Abstract
Description
【発明の詳細な説明】 本発明は無電解鋼めっき液に関Ｊるものである。[Detailed description of the invention] The present invention relates to an electroless steel plating solution.
基板に銅箔が設けられた印刷配線板は、その製造のとき
や部品取り付けなどの半田付けのとき、使用のとぎ等に
各種の熱が加えられ膨張や収縮が繰り返されるので、例
えばスルボールコーナの銅箔部分に細いクラックを生じ
たりする。このような不良は銅箔の伸びや引張り強さが
小さいためであり、伸びの大きな銅箔を形成しつる無電
解銅めっき液が要求されている。Printed wiring boards with copper foil on the board undergo repeated expansion and contraction due to the application of various types of heat during manufacturing and during soldering to attach parts. Thin cracks may occur in the copper foil part of the product. Such defects are due to the low elongation and tensile strength of the copper foil, and there is a need for an electroless copper plating solution that can form copper foil with high elongation.
また、めっき析出速度を上げて＠造時間を短縮するため
に、めっき液の温度やＰＨを高くしたりすることもある
が、この方法を採ると、必要とする回路以外の部分にま
で銅めっきが析出しく以下銅ふり現象という）、短絡不
良が生じる欠点がある。この欠点を防止するために析出
した余分な銅めっきを除去する作業をする方法もあるが
、工数が増加し、しかもこの作業によっても完全には除
去し難い欠点がある。また、めっき液の温度を低くする
ことによって銅ふり現象を防止する方法もあるが、析出
した銅箔の伸びが低下するという欠点がある。In addition, in order to increase the plating deposition rate and shorten the manufacturing time, the temperature and pH of the plating solution may be raised, but if this method is adopted, the copper plating will be applied to parts other than the necessary circuits. (hereinafter referred to as the "copper splatter phenomenon"), which causes short-circuit failure. In order to prevent this drawback, there is a method of removing the excess copper plating that has precipitated, but this method increases the number of man-hours and has the disadvantage that it is difficult to completely remove the deposited copper plating. There is also a method of preventing the copper flaking phenomenon by lowering the temperature of the plating solution, but this method has the disadvantage that the elongation of the deposited copper foil decreases.
本発明は、以上の欠点を改良し、銅箔の伸びや引張り強
さを増大でき、銅ふり現象を防止しつる無電解銅めっき
液の提供を目的とする。The object of the present invention is to provide an electroless copper plating solution that can improve the above-mentioned drawbacks, increase the elongation and tensile strength of copper foil, and prevent copper flaking.
本発明は、上記の目的を達成するために、（ａ）第２銅
塩、錯化剤、還元剤及び水酸化アルカリ並びに（ｂ ）
２．２’−ジピリジル、２−（２−ピリジル〉ベンズイ
ミダゾール、２．２’ −ジキノリル及び１．１０−フ
ェナンスロリン類の少なくとも１種を含む無電解銅めっ
き液において、オキシエチレンオキシプロピレン１０ツ
クポリマーを添加することを特徴とづる無電解銅めっき
液を提供するものである。In order to achieve the above object, the present invention provides (a) a cupric salt, a complexing agent, a reducing agent, and an alkali hydroxide;
In an electroless copper plating solution containing at least one of 2.2'-dipyridyl, 2-(2-pyridyl>benzimidazole, 2.2'-diquinolyl and 1.10-phenanthroline), oxyethylene oxypropylene 10 The present invention provides an electroless copper plating solution characterized by the addition of a plating polymer.
また、本発明は、上記の目的を達成するために、（ａ）
第２銅塩、錯化剤、還元剤及び水酸化アルカリ並びに（
ｂ ）２．２’−ジピリジル、２−（２−ピリジル）ベ
ンズイミダゾール、２．２’−ジキノリル及び１．１０
−フェナンスロリン類の少なくとも１種を含む無電解銅
めっき液において、オキシエチレンオキシプロピレンブ
ロックポリマーとアルキル型リン酸エステルとを添加す
ることを特徴とづる無電解銅めっき液を提供するもので
ある。Moreover, in order to achieve the above object, the present invention provides (a)
Cupric salts, complexing agents, reducing agents and alkali hydroxides and (
b) 2.2'-dipyridyl, 2-(2-pyridyl)benzimidazole, 2.2'-diquinolyl and 1.10
- Provides an electroless copper plating solution containing at least one kind of phenanthroline, characterized in that an oxyethylene oxypropylene block polymer and an alkyl type phosphate ester are added. .
さらに、本発明は、上記の目的を達成するために、（ａ
）第２銅塩、錯化剤、還元剤及び水酸化アルカリ並びに
（ｂ ）２．２’−ジピリジル、２−（２−ピリジル）
ベンズイミダゾール、２゜２′−ジキノリル及び１．１
０−７エナンスロリン類の少なくとも１種を含む無電解
銅めっき液において、オキシエチレンオキシプロピレン
ブロックポリマー、アルキル型リン酸エステル及びポリ
アルキレングリコール又はその誘導体を添加することを
特徴とする無電解銅めっき液を提供するものである。Furthermore, in order to achieve the above object, the present invention provides (a
) cupric salts, complexing agents, reducing agents and alkali hydroxides and (b) 2,2'-dipyridyl, 2-(2-pyridyl)
Benzimidazole, 2°2'-diquinolyl and 1.1
An electroless copper plating solution containing at least one kind of 0-7 enanthrolines, characterized in that an oxyethylene oxypropylene block polymer, an alkyl phosphate ester, and a polyalkylene glycol or a derivative thereof are added. It provides:
以下、本発明を実施例に基づいて説明する。Hereinafter, the present invention will be explained based on examples.
第２銅塩としては硫酸銅や硝酸銅、塩化第２銅等を７〜
１３Ｑ／λ用いる。錯化剤としてはエチレンジアミン四
酢酸やＮ、Ｎ、Ｎ’ 、Ｎ’ −テトラキス−２−ヒド
ロキシプロピルエチレンジアミン等を２０〜４０Ｑ／１
用いる。還元剤としてはホルマリン等を２〜１０ｍ、ｅ
＃！用いる。水酸化アルカリとしては水酸化ナトリウム
や水酸化カリウムをＰＨが１２．３〜１３となるように
加える。また、２．２′−ジピリジルを２５〜５０ｍａ
／１用いる。オキシエチレンオキシブ０ピレンブロツク
ポリマーを０．０３〜３ｍｆ！、／１用いる。アルキル
型リン酸エステルとしてはＧＡＦＡＣＲ，Ｅ−６５０（
東邦化学工業株式会社商品名）を０．０２〜０．２ＩＩ
ｌｆ／１用いる。ポリアルキレングリコールの誘導体と
しては分子量が５００〜３０００のポリエチレングリコ
ールのメチルエーテルやエチルエーテルを５〜５０ ｇ
／Ｒ用いる。Examples of cupric salts include copper sulfate, copper nitrate, cupric chloride, etc.
13Q/λ is used. As a complexing agent, ethylenediaminetetraacetic acid, N,N,N',N'-tetrakis-2-hydroxypropylethylenediamine, etc. are used at 20 to 40Q/1.
use As a reducing agent, formalin etc. is used at 2 to 10 m, e
#! use As the alkali hydroxide, sodium hydroxide or potassium hydroxide is added so that the pH becomes 12.3 to 13. In addition, 25-50 ma of 2,2'-dipyridyl
/1 is used. 0.03~3mf of oxyethylene oxybutylene block polymer! , /1 is used. As the alkyl type phosphate ester, GAFACR, E-650 (
Toho Chemical Industry Co., Ltd. (product name) 0.02-0.2II
Use lf/1. As a polyalkylene glycol derivative, 5 to 50 g of polyethylene glycol methyl ether or ethyl ether with a molecular weight of 500 to 3000 is used.
/R is used.
そして、表面を滑らかに研磨したステンレススチール板
の表面を脱脂し、めっき反応開始剤であるｐｄを付着さ
せた後、上記めっき液を用いて無電解銅めっき処理し、
厚さ３５μの銅箔を形成し、従来のめつき液により形成
された銅箔の伸びや銅ふり現象を測定したところ下記の
表の通りの結果が得られた。ＰＨはいづれのめつき液も
１２．７である。Then, after degreasing the surface of the stainless steel plate whose surface has been polished smoothly and adhering PD, which is a plating reaction initiator, electroless copper plating is performed using the above plating solution,
A copper foil with a thickness of 35 μm was formed, and the elongation and copper flaking phenomenon of the copper foil formed using a conventional plating solution were measured, and the results shown in the table below were obtained. The pH of both plating solutions is 12.7.
この表から明らかな通り、本発明によれば伸びは約２．
７〜５．３％、引張り強さは約２０〜２９％、各々増大
し、また、銅ふり現象は完全に無くなる。As is clear from this table, according to the present invention, the elongation is approximately 2.
The tensile strength increases by about 7 to 5.3%, and the tensile strength increases by about 20 to 29%, respectively, and the copper flaking phenomenon is completely eliminated.
以上の通り、本発明によれば、銅箔の伸びや引張り強さ
を増大できるので製造のときや部品取り付は等の半田付
けのとき等の断線不良を防止でき、また、銅ふり現象を
防止できるので製造時間を短縮できかつ短絡不良を防止
できまた液温の低いものを用いうる無電解銅めっき液が
得られる。As described above, according to the present invention, it is possible to increase the elongation and tensile strength of the copper foil, so it is possible to prevent wire breakage during manufacturing or when soldering parts, etc., and also to prevent copper flaking. Since this can be prevented, an electroless copper plating solution can be obtained which can shorten manufacturing time, prevent short circuit defects, and use a solution with a low temperature.
特許出願人 日立コンデンサ株式会社 ＝３２５−Patent applicant: Hitachi Capacitor Co., Ltd. =325-
Claims (1)
並びに（ｂ ）２．２’ −ジピリジル、２−（２−ピ
リジル）ベンズイミダゾール、２，２′−ジキノリル及
び１．１０−フェナンスロリン類の少なくとも１種を含
む無電解銅めっき液において、オキシエチレンオキシプ
ロピレン７０ツクポリマーを添加づ゛ることを特徴とす
る無電解銅めっき液。 （２）（ａ）第２銅塩、錯化剤、還元剤及び水酸化アル
カリ並びに（ｂ）２．２’ −ジピリジル、２−（２−
ピリジル）ベンズイミダゾール、２，２′−ジキノリル
及び１．１０−フェナンスロリン類の少なくとも１種を
含む無電解鋼めっき液において、オキシエチレンオキシ
プロピレン７０ツクポリマーとアルキル型リン酸エステ
ルとを添加することを特徴とする無電解銅めっき液。 （３）（ａ）第２銅塩、錯化剤、還元剤及び水酸化アル
カリ並びに（ｂ）２．２’ −ジピリジル、２−（２−
ピリジル）ベンズイミダゾール、２．２′−ジキノリル
及び１．１０−フェナンスロリン類の少な（とも１種を
含む無電解銅めっき液において、オキシエチレンオキシ
プロピレン７０ツクポリマー、アルキル型リン酸エステ
ル及びポリアルキレングリコール又はその誘導体を添加
することを特徴とする無電解銅めっき液。[Claims] m(a) cupric salt, complexing agent, reducing agent and alkali hydroxide; and (b) 2,2'-dipyridyl, 2-(2-pyridyl)benzimidazole, 2,2' - An electroless copper plating solution containing at least one of diquinolyl and 1.10-phenanthrolines, characterized in that an oxyethylene oxypropylene 70% polymer is added thereto. (2) (a) Cupric salts, complexing agents, reducing agents and alkali hydroxides and (b) 2,2'-dipyridyl, 2-(2-
In an electroless steel plating solution containing at least one of pyridyl)benzimidazole, 2,2'-diquinolyl, and 1,10-phenanthroline, an oxyethylene oxypropylene 70% polymer and an alkyl-type phosphate ester are added. An electroless copper plating solution characterized by: (3) (a) cupric salts, complexing agents, reducing agents and alkali hydroxides and (b) 2,2'-dipyridyl, 2-(2-
In an electroless copper plating solution containing a small amount (all one kind) of pyridyl)benzimidazole, 2,2'-diquinolyl, and 1,10-phenanthroline, oxyethylene oxypropylene 70% polymer, alkyl-type phosphate ester, and An electroless copper plating solution characterized by adding alkylene glycol or a derivative thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6662383A JPS59193261A (en) | 1983-04-15 | 1983-04-15 | Electroless copper plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6662383A JPS59193261A (en) | 1983-04-15 | 1983-04-15 | Electroless copper plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59193261A true JPS59193261A (en) | 1984-11-01 |
| JPH0214429B2 JPH0214429B2 (en) | 1990-04-09 |
Family
ID=13321193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6662383A Granted JPS59193261A (en) | 1983-04-15 | 1983-04-15 | Electroless copper plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59193261A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355645A (en) * | 2018-11-05 | 2019-02-19 | 常州大学 | A kind of method of weakly acidic pH chemical plating high W content Ni-W-P alloy layer |
-
1983
- 1983-04-15 JP JP6662383A patent/JPS59193261A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109355645A (en) * | 2018-11-05 | 2019-02-19 | 常州大学 | A kind of method of weakly acidic pH chemical plating high W content Ni-W-P alloy layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0214429B2 (en) | 1990-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6813582B2 (en) | Etching solution for copper and copper alloy surfaces | |
| US4725504A (en) | Metal coated laminate products made from textured polyimide film | |
| US4868071A (en) | Thermally stable dual metal coated laminate products made from textured polyimide film | |
| JP3400558B2 (en) | Copper and copper alloy etchant | |
| EP0797909B1 (en) | Copper coating | |
| KR100394315B1 (en) | Aqueous radio plating solution | |
| US6923919B2 (en) | Liquid crystal polymers for flexible circuits | |
| US8142840B2 (en) | Adhesion promotion in printed circuit boards | |
| US4832799A (en) | Process for coating at least one surface of a polyimide sheet with copper | |
| EP0300463A2 (en) | A remover solution for photoresist | |
| US4806395A (en) | Textured polyimide film | |
| JP3930885B2 (en) | Microetching agents for copper and copper alloys | |
| US4894124A (en) | Thermally stable dual metal coated laminate products made from textured polyimide film | |
| JP6109339B2 (en) | Aqueous composition for etching copper and copper alloys | |
| TWI568776B (en) | Copolymers of diglycidyl ether terminated polysiloxane compounds and non-aromatic polyamines | |
| JP2012214872A (en) | Method for manufacturing laminate with metallic film | |
| JPS59193261A (en) | Electroless copper plating bath | |
| JP3930732B2 (en) | MICRO ETCHING AGENT FOR COPPER AND COPPER ALLOY AND METHOD OF FINE Roughening of COPPER OR COPPER ALLOY USING THE SAME | |
| JP4418916B2 (en) | Etching composition | |
| JPS59193260A (en) | Electroless copper plating bath | |
| JP3932193B2 (en) | MICRO ETCHING AGENT FOR COPPER AND COPPER ALLOY AND METHOD OF FINE Roughening of COPPER OR COPPER ALLOY USING THE SAME | |
| JPS61227176A (en) | Electroless copper plating solution | |
| KR20240009210A (en) | Coating solution for adhesion improving and coating method using same | |
| JPH03235395A (en) | Manufacture of copper through hole printed wiring board | |
| EP0562187A1 (en) | Process for production of copper through-hole printed wiring boards |