JPS6115983A - Catalyst for electroless plating - Google Patents
Catalyst for electroless platingInfo
- Publication number
- JPS6115983A JPS6115983A JP13604284A JP13604284A JPS6115983A JP S6115983 A JPS6115983 A JP S6115983A JP 13604284 A JP13604284 A JP 13604284A JP 13604284 A JP13604284 A JP 13604284A JP S6115983 A JPS6115983 A JP S6115983A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- plating
- soln
- electroless plating
- 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
-
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
-
- 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
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/42—Plated through-holes or plated via connections
- H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は無電解めっき用触媒に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a catalyst for electroless plating.
(従来の技術)
無電解銅めっき等の無電解めっきは、印桐配線板の分野
で積層板などの絶縁基板に回路を形成するため広く用い
られている。この場合無電解めっきが施される面は活性
化、すなわち無電解めっきのための触媒核が形成される
。この触媒核を中心にして無電解めっき液中の銅イオン
等が金属銅等として析出し成長して銅膜となり回路とな
る。絶縁基板を活性化するため無電解めっきのための触
媒となる金属パラジウム、金属銀、金属銅、金属ニッケ
ルの微粒子を絶縁板基板表面に形成させる。従来この金
属はたとえばPdについては
P d C1h +S ncl*”’> P d”’+
S ncl 4のような反応で得られており、このた
めSn、 CJなどの不純物を多く含むうえに、強酸性
液体を使用するため、機器の損傷や多層回路における内
層回路のハロー現象をひき起したりしていた。(Prior Art) Electroless plating such as electroless copper plating is widely used in the field of Indo wiring boards to form circuits on insulating substrates such as laminates. In this case, the surface to which electroless plating is applied is activated, that is, catalyst nuclei for electroless plating are formed. Copper ions and the like in the electroless plating solution precipitate and grow as metallic copper etc. around this catalyst nucleus, forming a copper film and forming a circuit. In order to activate the insulating substrate, fine particles of metallic palladium, metallic silver, metallic copper, and metallic nickel, which serve as catalysts for electroless plating, are formed on the surface of the insulating substrate. Conventionally, this metal, for example, for Pd, P d C1h +S ncl*”'> P d”'+
It is obtained through a reaction similar to Sncl 4, and therefore contains many impurities such as Sn and CJ. In addition, it uses a strongly acidic liquid, which can cause damage to equipment and halo phenomena in the inner layer circuits of multilayer circuits. I was doing things like that.
(発明の目的)
本発明の目的は活性化処理工程で装置の損傷が少なく、
へ四−現象の起らない無電解めっき用触媒を提供するK
ある。(Objective of the Invention) The object of the present invention is to minimize damage to the equipment during the activation process.
K provides a catalyst for electroless plating that does not cause the 4-phenomenon.
be.
(発明の構成)
本発明は、アミドにパラジウム(II)、銀(I)、銅
(T)、銅(II)、ニッケル(I[)の化合物の少な
くとも一種を溶解し得られた錯体を含む無電解めっき用
触媒である。(Structure of the Invention) The present invention includes a complex obtained by dissolving at least one compound of palladium (II), silver (I), copper (T), copper (II), and nickel (I[) in an amide. This is a catalyst for electroless plating.
アミドは、ホルムアミド、ジメチルホルムアミド、ジエ
チルホルムアミド、ジメチルアセトアミド、ジメチルア
クリルアミド等及びそれらの混合物が使用される。As the amide, formamide, dimethylformamide, diethylformamide, dimethylacetamide, dimethylacrylamide, etc., and mixtures thereof are used.
パラジウム(If)、銀(I)、銅(I)、銅(II)
、ニッケル(II)と化合物としては、塩化物、フッ化
物、臭化物、ヨウ化物、硝酸塩、硫酸塩、酸化物、硫化
物等及びそれらの混合物が使用される。この中で塩化物
が特に好ましい。Palladium (If), silver (I), copper (I), copper (II)
As nickel (II) and compounds, chlorides, fluorides, bromides, iodides, nitrates, sulfates, oxides, sulfides, etc. and mixtures thereof are used. Among these, chlorides are particularly preferred.
アミドVc増化パラジウム等を溶解させ、アミド/パラ
ジウム等の錯体な得、これらの錯体は水、アルコールで
稀釈され濃度0.01〜1.0%、PH3〜14、好ま
しくはPH11,5〜12.5の溶液とされ無電解めっ
き用触媒となる。Amide Vc-enhanced palladium, etc. is dissolved to form a complex of amide/palladium, etc., and these complexes are diluted with water or alcohol to a concentration of 0.01 to 1.0%, pH 3 to 14, preferably PH 11.5 to 12. It is made into a solution of .5 and becomes a catalyst for electroless plating.
上記無電解めっき用触媒に、積層板セラミック等の絶縁
基板、プラスチック成形品、プラスチックフィルム等の
被めつ、き物を浸漬した後、還元性溶液に浸漬すると、
被めっき物表面にパラジウム、銀、銅、ニッケルのぐ属
粒子が生成する。還元性溶液としては、ホルムアルデヒ
ド、塩化第1スズ、水素化ホウ素ナトリウム(NaBH
4’)ブドウ糖等の還元性物質の水、アルコール等の溶
液が使用される。濃度は0,01〜10%好ましくはα
1〜1%で、出′!6〜14が好ましい。When an insulating substrate such as a ceramic laminate, a plastic molded product, a cover such as a plastic film, or a kimono is immersed in the above catalyst for electroless plating, and then immersed in a reducing solution,
Palladium, silver, copper, and nickel metal particles are generated on the surface of the plated object. Reducing solutions include formaldehyde, stannous chloride, and sodium borohydride (NaBH).
4') A solution of a reducing substance such as glucose in water, alcohol, etc. is used. The concentration is 0.01-10% preferably α
At 1-1%, it's out! 6 to 14 are preferred.
これらの還元剤は単独または併用も可能であり、あるい
は安定剤、増感剤など適宜添加してよい。These reducing agents may be used alone or in combination, or stabilizers, sensitizers, etc. may be added as appropriate.
このようKしてパラジウム等の金属粒子が生成した被め
っき物を無電解めっき液に浸漬すると無電解めっきが行
なわれる。無電解めっき液としては、銅、ニッケル等の
通常の無電解めっき液が使用される。Electroless plating is performed by immersing the object to be plated, on which metal particles such as palladium have been produced in this way, in an electroless plating solution. As the electroless plating solution, a normal electroless plating solution for copper, nickel, etc. is used.
アミド/パラジウム錯体等を含む本発明の無電解銅めっ
き用触媒に、被めっき物を浸漬する前に、前処理を行う
と、めっき活性化の効果が向上する。If the object to be plated is pretreated before being immersed in the electroless copper plating catalyst of the present invention containing an amide/palladium complex or the like, the plating activation effect will be improved.
このような前処理としては、過酸化水素水又硫酸でF4
13〜6にした濃度0.1〜10%の過酸化水素水、1
1(3〜6の塩酸、…3〜6の硫酸、ビスフェノールA
型のエポキシ樹脂を、水、アルコール、メチルエチルケ
トン等圧溶解した濃度[L1〜10%のエポキシ樹脂溶
液、更には、前記の還元性溶液が使用される。Such pre-treatment includes removing F4 with hydrogen peroxide or sulfuric acid.
13-6 hydrogen peroxide solution with a concentration of 0.1-10%, 1
1 (3-6 hydrochloric acid, 3-6 sulfuric acid, bisphenol A
An epoxy resin solution prepared by dissolving a type of epoxy resin in water, alcohol, or methyl ethyl ketone at a concentration [L1 to 10%] or the above-mentioned reducing solution is used.
実施例1
両面銅張りガラス・エポキシ積層板(厚さ1゜6ff1
m)を穴あけし洗浄処理後、ジメチルホルムアミドに2
.0%(重量%、以下同じ)のPdC6zを溶解した液
を水で希釈しP dcl 2を0.1%した液に5分間
処理を行い液切りを行ったあと、1%の水酸化ナトリウ
ム水洗液に水素化ホウ素ナトリウム(NaBH4)を1
%溶解した液に5分間基板を揺動しながら浸漬し、次に
無電解銅めっき液CUST−201(日立化成工業■製
部品名)中に20分間浸漬を行い水洗処理を行った。無
電解鋼めっきはガラスポキシ印刷回路配線基板の穴に均
一に銅が析出しており、ハロー現象はみられなかった。Example 1 Double-sided copper-clad glass/epoxy laminate (thickness 1°6ff1
m) After drilling and cleaning, soak in dimethylformamide for 2 hours.
.. A solution containing 0% PdC6z (wt%, same hereinafter) was diluted with water, and the solution containing 0.1% PdCl 2 was treated for 5 minutes, drained, and then washed with 1% sodium hydroxide. Add 1 part of sodium borohydride (NaBH4) to the solution.
The substrate was immersed for 5 minutes while rocking in a solution in which the substrate was dissolved, and then immersed for 20 minutes in an electroless copper plating solution CUST-201 (manufactured by Hitachi Chemical Co., Ltd., part name) for rinsing. With electroless steel plating, copper was deposited uniformly in the holes of the glass poxy printed circuit board, and no halo phenomenon was observed.
実施例2
両面銅張り紙・エポキシ積層板(厚さ1.6m111)
を穴あけ洗浄を行った。Example 2 Double-sided copper clad paper/epoxy laminate (thickness 1.6m111)
Drilled and cleaned.
次に1.0%の水素化ホウ素ナトリウム(NaBH4)
のα1%水酸化ナトリウム水溶液に30秒間処理を行う
。Then 1.0% sodium borohydride (NaBH4)
1% sodium hydroxide aqueous solution for 30 seconds.
次にホルムアミドに1%のPbCl2を溶解した液を0
.3%の水酸化ナトリウム水溶液に溶解し[105%の
Pb(Jz液とする。その建浴液に5分間基板を浸漬し
よく揺動を行う。次に液切りを行ってα1%の水酸化ナ
トリウム水溶液に1.0%の水素化ホウ素ナトリウム(
NaBHL )を溶解した還元性溶液に3分間基板を処
理し、無電解銅めっき液CUST−201(日立化成工
業■製部品名に20分を浸漬な行い水洗処理を行った。Next, a solution of 1% PbCl2 in formamide was added to 0.
.. Dissolved in 3% sodium hydroxide aqueous solution [105% Pb (referred to as Jz solution). Immerse the substrate in the bath preparation solution for 5 minutes and shake well. Next, drain the liquid and add α1% hydroxide. 1.0% sodium borohydride (
The substrate was treated for 3 minutes in a reducing solution containing NaBHL), immersed in an electroless copper plating solution CUST-201 (manufactured by Hitachi Chemical Co., Ltd.) for 20 minutes, and then rinsed with water.
無電解鋼めっきは基板の穴に均一に銅が析出しハロー現
象はなかった
(発明の効果)
本発明に於又は、次の効果が達成される。In electroless steel plating, copper was deposited uniformly in the holes of the substrate, and there was no halo phenomenon (effects of the invention).The following effects are achieved in the present invention.
(I)無電解めっき用触媒の田が6〜14であるので、
めりき装置の損傷が少ない。(I) Since the field of electroless plating catalyst is 6 to 14,
There is little damage to the plating device.
(2)均一なめっきが得られる。(2) Uniform plating can be obtained.
Claims (1)
、銅(II)、ニッケル(II)の化合物の少なくとも一種
を溶解し得られた錯体を含む無電解めっき用触媒。1. Palladium (II), silver (I), copper (I) in amide
A catalyst for electroless plating comprising a complex obtained by dissolving at least one of a compound of copper (II), copper (II), and nickel (II).
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13604284A JPS6115983A (en) | 1984-06-29 | 1984-06-29 | Catalyst for electroless plating |
EP85304381A EP0167326B1 (en) | 1984-06-29 | 1985-06-19 | Sensitizing agent for electroless plating and method for sensitizing substrate with the agent |
DE8585304381T DE3574270D1 (en) | 1984-06-29 | 1985-06-19 | Sensitizing agent for electroless plating and method for sensitizing substrate with the agent |
US06/750,779 US4734299A (en) | 1984-06-29 | 1985-07-01 | Sensitizing agent for electroless plating and method for sensitizing substrate with the agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13604284A JPS6115983A (en) | 1984-06-29 | 1984-06-29 | Catalyst for electroless plating |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6115983A true JPS6115983A (en) | 1986-01-24 |
JPH049874B2 JPH049874B2 (en) | 1992-02-21 |
Family
ID=15165814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13604284A Granted JPS6115983A (en) | 1984-06-29 | 1984-06-29 | Catalyst for electroless plating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6115983A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63159410A (en) * | 1986-11-07 | 1988-07-02 | モンサント カンパニー | Selective catalytic activation of polymer film |
WO2012046615A1 (en) * | 2010-10-08 | 2012-04-12 | 富士フイルム株式会社 | Laminate production process |
EP2868771A1 (en) | 2013-10-30 | 2015-05-06 | Rohm and Haas Electronic Materials LLC | Catalyst solution for electroless plating and method for electroless plating |
JP2019515138A (en) * | 2016-05-04 | 2019-06-06 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングAtotech Deutschland GmbH | Method for depositing a metal or metal alloy on a substrate surface comprising activation of the substrate surface |
-
1984
- 1984-06-29 JP JP13604284A patent/JPS6115983A/en active Granted
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63159410A (en) * | 1986-11-07 | 1988-07-02 | モンサント カンパニー | Selective catalytic activation of polymer film |
WO2012046615A1 (en) * | 2010-10-08 | 2012-04-12 | 富士フイルム株式会社 | Laminate production process |
EP2868771A1 (en) | 2013-10-30 | 2015-05-06 | Rohm and Haas Electronic Materials LLC | Catalyst solution for electroless plating and method for electroless plating |
JP2019515138A (en) * | 2016-05-04 | 2019-06-06 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングAtotech Deutschland GmbH | Method for depositing a metal or metal alloy on a substrate surface comprising activation of the substrate surface |
Also Published As
Publication number | Publication date |
---|---|
JPH049874B2 (en) | 1992-02-21 |
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