JPS5920459A - Electroless copper plating solution - Google Patents
Electroless copper plating solutionInfo
- Publication number
- JPS5920459A JPS5920459A JP13098182A JP13098182A JPS5920459A JP S5920459 A JPS5920459 A JP S5920459A JP 13098182 A JP13098182 A JP 13098182A JP 13098182 A JP13098182 A JP 13098182A JP S5920459 A JPS5920459 A JP S5920459A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- copper
- deposited
- cyanide
- compound
- 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
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は無電解ないしは自己触媒作用による銅メッキ液
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electroless or autocatalytic copper plating solution.
一般に無電解ないしは、自己触媒作用による金属析出液
は電気メツキ液と異なシバイブの内面や小孔の内部にま
で均一にメッキできること、プラスチック等の半導体の
表面にもメッキができることから電気メッキの下地とし
て印刷配線板等に広く利用されている。最近、印刷配線
板の製造方法として、絶縁板に、無電解銅メッキのみで
導電回路を形成する方法、いわゆるアディティブプロセ
スが採用されるようになっている。アディティブプロセ
スに使用される無電解銅メッキ液の代表的な溶液は溶媒
としての水、析出させようとする金属イオン（銅イオン
）の供給源、析出させよう表する金属イオン（銅イオン
）を金属に還元剤、シアン化化合物のような安定剤およ
びＰＨ調整剤とから成っている。しかしこれら無電解銅
メッキ液から析出する金属銅の物性（拡張力、伸び率）
は電気銅メッキ液から析出する金属鋼と比較して劣シ、
アディティブプロセスによって製造された印刷配線板に
おいては、部品実装時の半田付は等の高温雰囲気にさら
されると、スルホールの金属銅にクラックが生ずる欠点
があった。In general, electroless or autocatalytic metal deposition solutions can be used as a base for electroplating because, unlike electroplating solutions, they can uniformly plate the inner surfaces of surfaces and small pores, and can also plate the surfaces of semiconductors such as plastics. Widely used for printed wiring boards, etc. Recently, as a method for manufacturing printed wiring boards, a so-called additive process, in which a conductive circuit is formed on an insulating board only by electroless copper plating, has been adopted. Typical electroless copper plating solutions used in additive processes include water as a solvent, a source of metal ions (copper ions) to be deposited, and a source of metal ions (copper ions) to be deposited. and a reducing agent, a stabilizer such as a cyanide compound, and a pH adjuster. However, the physical properties (expansion force, elongation rate) of metallic copper deposited from these electroless copper plating solutions
is inferior to metal steel deposited from electrolytic copper plating solution,
Printed wiring boards manufactured by the additive process have the disadvantage that cracks occur in the copper metal in the through holes when exposed to high temperature atmospheres such as during soldering during component mounting.
本発明の目的は、アディティブプロセスに使用される無
電解銅メッキ液の従来の欠点を改善した物性の優れた析
出銅を与える無電解銅メッキ液を提供することにある。An object of the present invention is to provide an electroless copper plating solution that improves the drawbacks of conventional electroless copper plating solutions used in additive processes and provides deposited copper with excellent physical properties.
本発明の無電解銅メッキ液は、水、析出されるべき銅イ
オン、銅イオンに対する錯化剤、銅イオンに対する還元
剤、シアン化化合物、タリウム化合物およびＰＨ調整剤
から成ることを特徴とする。The electroless copper plating solution of the present invention is characterized by comprising water, copper ions to be deposited, a complexing agent for copper ions, a reducing agent for copper ions, a cyanide compound, a thallium compound, and a pH adjuster.
以下、本発明を実施例により詳細に説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
本発明において、無電解銅メッキ液の銅イオン源として
は、硫酸銅あるいは塩化第二銅が使用され、その添加量
は５〜２０ ｇ／ｌが適当である。銅イオンの錯化剤と
してはエチレンジアミンテトラ酢酸のナトリウム塩、Ｎ
、Ｎ、Ｎ’、Ｎ’−テトラキシス−２（２−ヒドロキシ
プロピル）エチレンジアミン等が使用され、これら化合
物は単独または混合して使用される。その添加量は銅イ
オンを錯化するのに十分な量、通常銅イオンのダラム当
量の１〜３倍の量が適当である。還元剤としてはホルム
アルデヒドあるいは、ホルムアルデヒドの早期硬化物、
例えばパラホルムアルデヒド等が適当である。シアン化
化合物としてはシアン化ナトリウムあるいはシアン化カ
リウムが使用され、その添加量は１０〜５０ｍｇ／ｌが
適当である。タリウム化合物としては硝酸第一タリウム
が適当であシ、その添加１は１０〜１ｏ０ｍｇ／ｌが適
当である。硝酸第一タリウムを無電解銅メッキ液に添加
すると、シアンイオンとの相乗作用によシ析出銅の光沢
性が増加し、析出銅の物性も向上する効果がある。In the present invention, copper sulfate or cupric chloride is used as a copper ion source in the electroless copper plating solution, and the appropriate amount of addition is 5 to 20 g/l. As a complexing agent for copper ions, sodium salt of ethylenediaminetetraacetic acid, N
, N, N', N'-tetraxis-2(2-hydroxypropyl)ethylenediamine, etc., and these compounds may be used alone or in combination. The amount to be added is sufficient to complex copper ions, usually 1 to 3 times the Durham equivalent of copper ions. As a reducing agent, formaldehyde or an early cured product of formaldehyde,
For example, paraformaldehyde is suitable. Sodium cyanide or potassium cyanide is used as the cyanide compound, and the amount added is suitably 10 to 50 mg/l. As the thallium compound, thallous nitrate is suitable, and its addition amount 1 is suitably 10 to 100 mg/l. When thallous nitrate is added to the electroless copper plating solution, it has the effect of increasing the glossiness of the deposited copper due to a synergistic effect with cyanide ions and improving the physical properties of the deposited copper.
本発明の無電解銅メッキ液の試験結果を比較例（ＡＩ
、Ａ２ ）と共に第１表に示す。第１表において無電解
銅メッキ液は使用中を通して液温を約７０℃に絣持しＰ
Ｈは１２．０に維持した。析出銅の抗張力は、ステンレ
ス板に無電解銅メッキした後、ステンレス板よシ析出銅
を剥離し、抗張力試験機で測定した。印刷配線板のスル
ホール析出銅のクラック発生の有無については、印刷配
線板を温度約２６０℃の溶融半田に約１０秒間浸漬した
後、印刷配線板のスルホール断面を観察して調べた。The test results of the electroless copper plating solution of the present invention are shown as a comparative example (AI
, A2) are shown in Table 1. In Table 1, the electroless copper plating solution is maintained at a temperature of approximately 70°C throughout use.
H was maintained at 12.0. The tensile strength of the deposited copper was measured using a tensile strength tester after electroless copper plating was applied to a stainless steel plate, and the deposited copper was peeled off from the stainless steel plate. The presence or absence of cracks in the through-hole deposited copper on the printed wiring board was investigated by immersing the printed wiring board in molten solder at a temperature of about 260° C. for about 10 seconds, and then observing the through-hole cross section of the printed wiring board.
以上、本発明による無電解鋼メッキ液は第１表に示した
ように、本発明の硝酸タリウムおよびシアンイオンを含
有した無電解銅メッキ溶液から析出した銅の物性（抗張
力）は著しくすぐれており、印刷配線板のスルホール信
頼性も著しく大きいことが羅認され、本発明の実用性は
著しく大きいことが立証された。As mentioned above, as shown in Table 1, the electroless steel plating solution according to the present invention has extremely excellent physical properties (tensile strength) of copper deposited from the electroless copper plating solution containing thallium nitrate and cyanide ions according to the present invention. It was also confirmed that the through-hole reliability of the printed wiring board was extremely high, and the practicality of the present invention was proved to be extremely high.
第１表Table 1
Claims (1)
剤と還元剤およびＰＨ訓整剤とから成る無電解銅メッキ
液に１０〜５０ ｍ ｇ／ｌのシアン化カリウムまたは
シアン化ナトリウムのシアン化化合物と１０〜１００ｍ
ｇ／ｌ の硝酪第−タリウムのタリウム化合物を添加し
て構成され／こことを＊似とする無電１解銅メツキ液。A cyanide compound of 10 to 50 mg/l of potassium cyanide or sodium cyanide is added to an electroless copper plating solution consisting of water, pot ions to be precipitated, a complexing agent for copper ions, a reducing agent, and a PH adjustment agent. and 10-100m
An electroless copper plating solution made by adding a thallium compound of g/l of nitrate butyro-thallium and similar to this.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13098182A JPS5920459A (en) | 1982-07-27 | 1982-07-27 | Electroless copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13098182A JPS5920459A (en) | 1982-07-27 | 1982-07-27 | Electroless copper plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5920459A true JPS5920459A (en) | 1984-02-02 |
Family
ID=15047119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13098182A Pending JPS5920459A (en) | 1982-07-27 | 1982-07-27 | Electroless copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5920459A (en) |
-
1982
- 1982-07-27 JP JP13098182A patent/JPS5920459A/en active Pending
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