JPS62149884A - Pretreatment for electroless copper plating - Google Patents
Pretreatment for electroless copper platingInfo
- Publication number
- JPS62149884A JPS62149884A JP28948485A JP28948485A JPS62149884A JP S62149884 A JPS62149884 A JP S62149884A JP 28948485 A JP28948485 A JP 28948485A JP 28948485 A JP28948485 A JP 28948485A JP S62149884 A JPS62149884 A JP S62149884A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- copper
- solution
- electroless
- dip
- 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
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/166—Process features with two steps starting with addition of reducing agent followed by metal deposition
-
- 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
- C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
- C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
- C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
- C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Abstract
Description
【発明の詳細な説明】
本発明は、銅基材の無電解銅めっきの前処理方法に関す
るものであり、特には銅張基板からプリント配線板を製
造するに当って用いられる銅の無電解めっきにおけるめ
っき付着不良を防止する為、無電解めっきの直前に銅基
板を特定の還元剤水溶液浴に浸漬する前処理方法に関す
る。本発明は、特に独立パターン部を有する基板の、無
電解銅めっきの前処理法として有効に適用しうる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a pretreatment method for electroless copper plating of a copper base material, and in particular to electroless plating of copper used in manufacturing printed wiring boards from copper-clad substrates. This invention relates to a pretreatment method in which a copper substrate is immersed in a specific reducing agent aqueous solution bath immediately before electroless plating in order to prevent poor plating adhesion. The present invention can be effectively applied as a pretreatment method for electroless copper plating, particularly for substrates having independent pattern parts.
プリント配線板の製造は基本的に、銅張り積層板にスル
ーホールを形成し、エツチングによって回路形成を行い
そして上記スルーホールに無電解めっきを施して回路を
接続することから成る。これを基本として多数の方法が
、工程の簡易化、低コスト化、精度の向上等をめざして
ジ・唱され実施されてきている。例えば、銅箔上に所定
の回路を選択的にエツチングすることにより形成し、回
路の所定位置にスルーホールを形成し、スルーホール壁
及び回路上に無電解銅めっき前処理層を形成し、回路上
の上記前処理層の機械的除去を行い、スルーホールとそ
れに繋る回路部以外にソルダーレジスト膜を形成し、そ
の後スルーホール及び必要回路に無電解鋼めっきを施す
方法；上記においてスルーホールの形成をソルダーレジ
スト膜形成後に行う方法；スルーホールを形成し、スル
ーホ−ルめつきを行った後、スルーホール壁及び銅箔面
上に電解法によって銅めっきを行い、スルーホール内に
インクをつめて必要回路上にエツチングレジスト膜を形
成し、その後鋼箔不必要部をエツチング除去する方法；
銅張り積層板にスルーホールを形成し、スルーホール内
を触媒で活性化し、銅箔の所定部分をエツチング除去し
、ランド部とスルーホール以外の所望部にソルダーレジ
スト膜を形成し、無電解銅めっきを行う方法等枚挙のい
とまがない。スルーホールの形成段階、パターンの形成
、触媒付着、レジスト形成、エツチング等を行う順序に
様々の観点から多数の変更が加えられている。The production of printed wiring boards basically consists of forming through holes in a copper-clad laminate, forming circuits by etching, and connecting the circuits by electroless plating the through holes. Based on this, many methods have been advocated and implemented with the aim of simplifying the process, reducing cost, improving accuracy, etc. For example, a predetermined circuit is formed by selectively etching a copper foil, a through hole is formed at a predetermined position of the circuit, an electroless copper plating pretreatment layer is formed on the through hole wall and the circuit, and the circuit is formed by selectively etching a predetermined circuit on a copper foil. A method in which the pretreatment layer above is mechanically removed, a solder resist film is formed on areas other than the through holes and the circuits connected to them, and then electroless steel plating is applied to the through holes and the necessary circuits; A method in which formation is performed after forming a solder resist film; After forming a through hole and plating the through hole, copper plating is performed on the through hole wall and copper foil surface by electrolytic method, and ink is filled in the through hole. A method of forming an etching resist film on the necessary circuit, and then etching away unnecessary parts of the steel foil;
A through-hole is formed in a copper-clad laminate, the inside of the through-hole is activated with a catalyst, a predetermined portion of the copper foil is etched away, a solder resist film is formed on the desired portion other than the land area and the through-hole, and electroless copper is formed. There are too many ways to perform plating. Many changes have been made to the order of through-hole formation, pattern formation, catalyst deposition, resist formation, etching, etc. from various viewpoints.
こうした状況において、最近、ＩＣ，抵抗等の塔載部品
のチップ化が進み、基板において、触媒付与処理したス
ルーホールと接続している部分と、当該スルーホールに
接続していない部分、即ち独立パターン部とが必要とな
ってきた。第１図はそうした状況の一例を示す。銅箔部
Ａ、Ｂは触媒付きスルーホール■、■とそれぞれ接続し
ているが、独立パターンｍｃ、Ｄ、Ｅ、Ｆはスルーホー
ルと接続していない。こうした場合、触媒付きスルーホ
ールと接続した鋼箔部Ａ、Ｂは該スルーホールと触媒に
対して電位的に等価であるが、独立パターン部はＣｕに
対する電位しか持たない。即ち、独立パターン部はスル
ーホールと接続した部位より電位が高い。Under these circumstances, recently, ICs, resistors, and other mounted components have been made into chips, and the parts of the board that are connected to the through-holes that have been treated with a catalyst and the parts that are not connected to the through-holes, that is, independent patterns. It has become necessary to have a department. Figure 1 shows an example of such a situation. Copper foil portions A and B are connected to catalyst-equipped through holes (2) and (2), respectively, but independent patterns mc, D, E, and F are not connected to any through holes. In such a case, the steel foil portions A and B connected to the through-hole with catalyst are equivalent in potential to the through-hole and the catalyst, but the independent pattern portion has a potential only to Cu. That is, the independent pattern portion has a higher potential than the portion connected to the through hole.
この理由のため、スルーホールに無電解銅めっきを行う
に際して、独立パターン部にめっきが付か々い状況がし
ばしば発生した。これは基板の外観を悪化するばかりで
なく、めっき後、第２図に示すようなランド部と独立パ
ターン部との間にめっき厚高低差を生ずる。従来この問
題はほとんど無視されてきたが、現在のようにプリント
配線板への部品塔載がフラットパッケージ型へ進むにつ
れ、上記問題を無視しえぬ状況となってきている。For this reason, when performing electroless copper plating on through-holes, a situation often occurred in which the plating was difficult to adhere to the independent pattern portions. This not only deteriorates the appearance of the substrate, but also causes a height difference in the plating thickness between the land portion and the independent pattern portion as shown in FIG. 2 after plating. In the past, this problem has been largely ignored, but as parts are now mounted on printed wiring boards in a flat package format, the problem has become impossible to ignore.
発明の概要
銅箔上への無電解銅の析出電位は一α７ｖ（Ｖ、 Ｓ、
Ａｇ／ＡｇＣ１）以下であり、上記のよう力めつき不
良の原因は基板を無電解めっき液に浸漬した時独立パタ
ーン部の電極電位が−１７ｖ以下に下がらないことにあ
る。例えば、めっき不良が生ずる時の電極電位を実測す
ると、−（Ｌ２〜−０．５ Ｖ （Ｖ、 Ｓ、 Ａｇ／
ＡｇＣ１）であった。Summary of the invention The deposition potential of electroless copper on copper foil is -α7v (V, S,
Ag/AgC1) or less, and the cause of the force plating failure as described above is that the electrode potential of the independent pattern portion does not fall below -17V when the substrate is immersed in the electroless plating solution. For example, when we actually measure the electrode potential when plating defects occur, -(L2~-0.5 V (V, S, Ag/
AgC1).
従って、めっき不良を回避する為には、電極電位を全体
的に−０，７ｖ以下に充分下げる必要がある。Therefore, in order to avoid plating defects, it is necessary to lower the overall electrode potential sufficiently to below -0.7V.
こうした考えの下で、電極電位を充分に下げる方法を検
討した結果、無電解めっきの直前Ｋ、ホルマリン、次亜
リン酸乃至次亜リン酸塩及びヒドラジ／から選択される
還元剤の水溶液（プレディップ液）と基板と接触する前
処理を実施するのが効果的であることが判明した。Based on this idea, we investigated ways to lower the electrode potential sufficiently and found that immediately before electroless plating, an aqueous solution of a reducing agent selected from K, formalin, hypophosphorous acid or hypophosphite, and hydrazi. It has been found to be effective to perform a pretreatment in which the substrate is brought into contact with the dipping solution (dip solution).
斯くして、本発明は、銅基材へ銅の無電解めっきを行な
うに際して、無電解めっきの直前に、ホルマリン、次亜
リン酸、次亜リン酸塩、及びヒドラジ／の群から選択さ
れる還元剤の水溶液と銅基材とを接触することによりめ
っき析出不良を防止する無電解銅めっきの前処理方法を
提供する。Thus, the present invention provides that when performing electroless plating of copper on a copper substrate, immediately before electroless plating, an agent selected from the group of formalin, hypophosphorous acid, hypophosphite, and hydrazine is used. Provided is a pretreatment method for electroless copper plating that prevents poor plating deposition by bringing an aqueous solution of a reducing agent into contact with a copper base material.
本発明は、銅基材上に銅を無電解めっきする方法に係る
。ここで、銅基材とは、銅乃至銅合金の、箔、銅ペース
ト、銅めつき材を包括する。工業的には、プリント配線
板が主たる対象例である。第１図に示したように、プリ
ント配線板の製造においては、
■ 触媒付与処理したスルーホール
■ ■と接続している銅箔部
■ ■と接続していない独立パターン鋼箔部を無電解め
っきにより銅を付着する必要がある。スルーホール壁に
は触媒付与工程においてＰｄのコロイド層性粒子が付着
して、スルーホール壁の活性化と促進化をもたらしてお
り、その為スルーホールと接続する銅箔部はスルーホー
ルと電位的に等価であり、無電解めっきに際して銅が良
好に付着する。しかし、独立パターン部は、製造工程の
都合上、スルーホールへの触媒付与工程中レジストによ
り覆いかくされているため、触媒が付着しておらず、ス
ルーホールと接続した部位より電位が高くなり、そのた
め無電解めっき時に銅が付着しない。そこで、無電解め
っきに際しての銅付着部と銅非付着部との発現、即ちめ
っき析出不良を防止する対策が必要とされるのである。The present invention relates to a method of electroless plating copper onto a copper substrate. Here, the copper base material includes copper or copper alloy foil, copper paste, and copper plating material. Industrially, printed wiring boards are the main target example. As shown in Figure 1, in the production of printed wiring boards, ■ through-holes that have been treated with a catalyst ■ ■ copper foil parts connected to ■ ■ independent pattern steel foil parts that are not connected are electrolessly plated. Therefore, it is necessary to attach copper. Colloidal particles of Pd adhere to the through-hole walls during the catalyst application process, activating and promoting the through-hole walls. Therefore, the copper foil part connected to the through-holes has a potential difference with the through-holes. It is equivalent to , and copper adheres well during electroless plating. However, due to the manufacturing process, the independent pattern part is covered with resist during the process of applying catalyst to the through hole, so the catalyst is not attached and the potential is higher than the part connected to the through hole. Therefore, copper does not adhere during electroless plating. Therefore, there is a need for measures to prevent the occurrence of copper-adhered areas and non-copper-adhered areas during electroless plating, that is, to prevent poor plating deposition.
無電解銅めっきの前処理方法として、従来より過硫酸ア
ンモニウムを使用してのソフトエツチング、水洗、酸洗
、水洗の各工程が経由され、その後無電解鋼めっきが実
施されていたが、本発明に従えば無電解銅めっきの直前
に特定還元剤水溶液との接触処理が行われる。接触は、
浸漬、塗布、スプレィ等により行いうるが、浸漬即ちプ
レディップ法が好ましい。Conventionally, as a pretreatment method for electroless copper plating, the steps of soft etching using ammonium persulfate, water washing, pickling, and water washing were performed, and then electroless steel plating was performed. Accordingly, contact treatment with a specific reducing agent aqueous solution is performed immediately before electroless copper plating. The contact is
It can be carried out by dipping, coating, spraying, etc., but dipping or pre-dipping is preferred.
還元剤としては、ホルマリン、次亜リン酸、次亜リン酸
塩及びヒドラジンが好適である。これら還元剤を純水で
希釈または溶解して設定ｍ度とする。濃度は、還元液（
原液）Ｋ対する比率で２〜１００チの範囲で効果がある
が、濃度が低い場合プレディップ液への浸漬時間が長く
なるので１０〜１００チが好ましい。Suitable reducing agents include formalin, hypophosphorous acid, hypophosphite and hydrazine. These reducing agents are diluted or dissolved with pure water to a set degree of m. The concentration is determined by reducing solution (
It is effective in the range of 2 to 100 in the ratio to K (undiluted solution), but if the concentration is low, the immersion time in the pre-dip solution becomes long, so 10 to 100 is preferable.
プレディップの液温は常温で十分である。プレディップ
の浸漬時間は還元液の濃度により左右され、一義的に定
められないが、例えば還元液の濃度が高い場合（１ｏｏ
％）には５秒でそして還元液の濃度が低い場合（１０％
）には１分以上で効果がある。Room temperature is sufficient for pre-dipping. The immersion time for pre-dip depends on the concentration of the reducing solution and cannot be determined uniquely, but for example, when the concentration of the reducing solution is high (1oo
%) in 5 seconds and when the concentration of reducing solution is low (10%
) is effective for more than 1 minute.
こうして予備処理された銅基材に無電解めっきを行うと
、銅基材上に確実に無電解めっきが析出する。When electroless plating is performed on the copper base material pretreated in this manner, electroless plating is reliably deposited on the copper base material.
発明の効果
従って、本発明により、スルーホールに無電河銅めっき
を行うに際して、独立パターン部にめっきが付かない状
況はなくなるため、めっき後、ランド部と独立パターン
部との間にめっき厚高低差がなくなり、ＩＣ，抵抗等の
部品搭載時に部品自動装着機が誤動作することもなく、
信頼性が向上した。Effects of the Invention Therefore, according to the present invention, when electroless copper plating is performed on through-holes, there is no situation where the plating does not adhere to the independent pattern portion, so that after plating, there is no difference in the height of the plating thickness between the land portion and the independent pattern portion. This eliminates the problem of automatic component mounting machines malfunctioning when mounting components such as ICs and resistors.
Improved reliability.
なお、本発明は上記プリント配線板の製造分野に限定さ
れるものでなく、銅箔、銅めっき膜等を含めて銅基材上
に、触媒を使用することなく銅、ニッケル等の金属を無
電解めっきにより付着する必要がある場合に等しく応用
しうる。It should be noted that the present invention is not limited to the field of manufacturing printed wiring boards, but is also applicable to the production of copper substrates, including copper foils, copper plating films, etc., without the use of metals such as copper and nickel without using catalysts. It is equally applicable where deposition by electrolytic plating is required.
実施例１及び比較例１
独立パターン部を有する基板を使用して、そこへのめつ
き析出状況を調べる実験を行った。Example 1 and Comparative Example 1 An experiment was conducted using a substrate having an independent pattern portion to examine the state of plating and precipitation thereon.
１ 条件
■使用した還元性薬品 ・・・ホルマリン■ブレデ
ィップ液のホルマリン濃度
（３７チＨＣＨＯ原液に対する比率）（チ）・・・１０
０％
■プレデイツ・プ液の温度（’Ｃ）・・・１０．２５．
３５■プレデイツプ液への浸漬時間（ｓｅｅ）・・・５
．１０．５０．６０．１２０
■無電解めっき液組成
ＣｕＳＯ４−５Ｈ２０１０９／Ｉ
ＥＤＴＡ ３０ ｉ／ＩＨＣＨ０３
７％水溶液 ５ ｍｌ／ＩＰＨ（ＮａＯ
Ｈ） １２．８有機添加剤
少量■めっき温度 ７０℃
λ 方法
コンディショナー処理→水洗→酸洗→水洗の工程を終え
た基板を、３０秒以内にプレディップ液に浸漬し、所定
の条件で各１０枚処理した。処理後、３０秒以内に無電
解めっき液に浸漬し、３０μｍのめっきを行なった。め
っき後、独立パターン部へのめっきの析出の有無を観察
した。なお、プレディップ液への浸漬の効果を調べる為
に同時にプレディップ液へ浸漬し々い基板を無電解めっ
きし、独立パターン部へのめっきの析出の有無を観察し
た。1 Conditions ■Reducing chemicals used...Formalin ■Formalin concentration of Bredip solution (ratio to 37HCHO stock solution) (Ch)...10
0% ■Temperature of Predates liquid ('C)...10.25.
35 ■ Immersion time in pre-dip solution (see)...5
．． 10.50.60.120 ■Electroless plating solution composition CuSO4-5H20109/I EDTA 30 i/IHCH03
7% aqueous solution 5 ml/IPH (NaO
H) 12.8 Organic additives
Small amount ■Plating temperature: 70°C λ Method After completing the steps of conditioner treatment, water washing, pickling, and water washing, the substrates were immersed in the pre-dip solution within 30 seconds, and 10 substrates each were processed under predetermined conditions. After the treatment, it was immersed in an electroless plating solution within 30 seconds to perform plating with a thickness of 30 μm. After plating, the presence or absence of plating precipitation on the independent pattern portions was observed. In order to investigate the effect of immersion in the pre-dip solution, a substrate slightly immersed in the pre-dip solution was electrolessly plated at the same time, and the presence or absence of plating precipitation on the independent pattern portions was observed.
５、結果
プレディップ液に浸漬しない基板は、全て（１０枚）独
立パターン部の一部にめっきが析出せず不良となったが
、プレディップ液にａｍした基板は、各条件とも全ての
基板（１０枚）について独立パターン部にめっきが析出
し、良好であった。5. As a result, all (10) substrates that were not immersed in the pre-dip liquid were defective because plating did not precipitate on a part of the independent pattern part, but all of the substrates that were immersed in the pre-dip liquid were defective under each condition. For (10 sheets), plating was deposited on the independent pattern part, which was good.
実施例２及び比較例２
１ 条件
■使用した還元性薬品 ・・・ホルマリン■プレデ
ィップ液のホルマリン濃度
（３７チＨＣＨＯ原液に対する比率）（％）・・・２，
５．１０
■プレディップ液の温度（’Ｃ）・・・１０．２５．３
５■ブレデイツプ液への浸漬時間（ｓｅｃ）・・・３０
，６０，１２０
■めつき液及びめっき温度 実施例１と同じＺ 方法
コンディショナー処理→水洗→酸洗→水洗の工程を終え
た基板を、３０秒以内にプレディップ液に浸漬し、所定
の条件で各１０枚処理した。処理後、３０秒以内に無電
解めっき液に浸漬し、３０μｍのめっきを行々つた。め
っき後、独立パターン部へのめっきの析出の有無を観察
した。なお、プレディップ液への浸漬の効果を調べる為
に同時にプレディップ液へ浸漬しない基板を無電解めっ
きし、独立パターン部へのめっきの析出の有無を観察し
た。Example 2 and Comparative Example 2 1 Conditions ■Reducing chemicals used...Formalin ■Formalin concentration of pre-dip solution (ratio to 37HCHO stock solution) (%)...2,
5.10 ■ Temperature of pre-dip liquid ('C)...10.25.3
5 ■ Immersion time in brad dip solution (sec)...30
, 60, 120 ■ Plating solution and plating temperature Same as Example 1 Z Method After completing the process of conditioner treatment → water washing → pickling → water washing, the substrate is immersed in the pre-dip solution within 30 seconds, and then heated under the specified conditions. Ten sheets each were processed. After the treatment, it was immersed in an electroless plating solution within 30 seconds to perform plating to a thickness of 30 μm. After plating, the presence or absence of plating precipitation on the independent pattern portions was observed. In order to examine the effect of immersion in the pre-dip solution, a substrate that was not immersed in the pre-dip solution was electrolessly plated, and the presence or absence of plating precipitation on the independent pattern portions was observed.
五 結果
プレディップ液に浸漬しない基板は、全て（１０枚）独
立パターン部の一部にめっきが析出せず不良となったが
、プレディップ液に浸漬した基板は、各条件とも全ての
基板（１０枚）について独立パターン部にめっきが析出
し、良好であった。5. As a result, all (10) substrates that were not immersed in the pre-dip solution were defective because the plating did not precipitate on a part of the independent pattern part, but for the substrates that were immersed in the pre-dip solution, all of the substrates (10) were defective under each condition. Regarding 10 sheets), plating was deposited on the independent pattern part, which was good.
参考例
実施例１及び２の一部のサンプルについて電気化学的手
法による確認試験を行った。Reference Example Confirmation tests were conducted on some samples of Examples 1 and 2 using an electrochemical method.
無電解銅めっき液における、被めっき材の銅析出電位バ
ー ａ、 ７ Ｖ （Ｖ、 Ｓ、 Ａｇ／ＡｇＣ１）以
下である。さらに、銅箔を無電解めっき液に浸漬した時
の、無電解めっき初期の電極電位の変化と、無電解銅め
っきの析出の状態には、次の関係がある。The copper deposition potential bar a of the material to be plated in the electroless copper plating solution is 7 V (V, S, Ag/AgC1) or less. Furthermore, the following relationship exists between the change in electrode potential at the initial stage of electroless plating when copper foil is immersed in an electroless plating solution, and the state of precipitation of electroless copper plating.
（１）銅箔浸漬後、１０秒以内に電極電位が−０，７Ｖ
以下になる
・・・無電解銅めっきが析出する。(1) After dipping the copper foil, the electrode potential drops to -0.7V within 10 seconds.
The following results... Electroless copper plating is deposited.
（２）銅箔浸漬後、電極電位が−［Ｌ７Ｖ以下に力るの
に１０秒上を要する
・・・無電解銅めっきが析出する場
合としない場合がある。不安
定な状態である。(2) After immersing the copper foil, it takes 10 seconds for the electrode potential to drop to -[L7V or lower...electroless copper plating may or may not precipitate. It is in an unstable state.
（３）銅箔浸漬後、電極電位が−０，７ｖまで下がらな
・・・無電解銅めっきが析出しない。(3) After immersing the copper foil, the electrode potential does not drop to -0.7V...electroless copper plating does not precipitate.
本実施例では、以上の知見を踏まえて、プレディップ液
への浸漬の効果を電極電位測定により確認した。In this example, based on the above findings, the effect of immersion in the pre-dip liquid was confirmed by electrode potential measurement.
ｔ プレディップ条件
２ 使用した無電解銅めっき液
翫 実験方法
ソフトエツチング処理→水洗→酸洗→水洗の工程を終え
た銅箔をプレディップ液に浸漬し、ただちに無電解銅め
っき液に浸漬して無電解めっき初期の電極電位の変化を
測定した。t Pre-dip conditions 2 Electroless copper plating solution used Experimental method After completing the soft etching process → water washing → pickling → water washing, the copper foil was immersed in the pre-dip solution, and immediately immersed in the electroless copper plating solution. Changes in electrode potential at the initial stage of electroless plating were measured.
なおブランクとして、プレディップ処理を行なわない銅
箔の無電解めっき初期の電極電位の変化を測定した。As a blank, changes in electrode potential at the initial stage of electroless plating of copper foil without pre-dip treatment were measured.
４ 実験結果
Ｔａｂｌｅ ３
０・・・１０秒以内に電極電位が一α７ｖ以下に下がる
Δ・−・電極電位が−ｔ１７Ｖ以下に下がるのに１０秒
以上な敬する×・・・電極電位が一α７■まで下がらな
いプレディップ処理を行なわない銅箔の電極電位は−α
７ｖまで下がらないか、下がっても１０秒以上を要する
のに対して、プレディップ処理を行なった銅箔の電極電
位は、１０秒以内に−１７ｖ以下に下がっている。明ら
かにブレディップの効果が認められた。4 Experimental results Table 3 0...The electrode potential drops below 1α7V within 10 seconds Δ--It takes more than 10 seconds for the electrode potential to drop below -t17V ×...The electrode potential drops below 1α7V ■The electrode potential of copper foil without pre-dip treatment is -α
On the other hand, the electrode potential of the copper foil subjected to the pre-dip treatment decreased to -17 V or less within 10 seconds, whereas it either did not drop to 7 V or took 10 seconds or more even if it did. The effect of Bledip was clearly recognized.
実施例３及び比較例３
ｔ 条件
■使用した還元性薬品 ・・・ヒドラジン水化物■
プレディップ液のヒドラジン濃度
（ヒドラジン水化物・原液に対する比率）（チ）・・・
２．５．１０．２０
■プレデイツプ液の温度（℃）・・・１０．２５．３５
■ブレデイツプ液への浸漬時間（ｓｅｅ）・・・５．１
０．３０．６０．１２０
■めっき液及びめっき温度 実施例１と同じλ 方法
コンディショナー処理→水洗→酸洗→水洗の工程を終え
た基板を、３０秒以内にプレディップ液に浸漬し、所定
の条件で各１０枚処理した。処理後、３０秒以内に無電
解めっき液に浸漬し、３０μｍのめっきを行なった。め
っき後、独立パターン部へのめっきの析出の有無を観察
した。なお、プレディップ液への浸漬の効果を調べる為
に同時にプレディップ液へ浸漬しない基材を無電解めっ
きし、独立パターン部へのめっきの析出の有無を観察し
た。Example 3 and Comparative Example 3 t Condition ■Reducing chemical used...Hydrazine hydrate■
Hydrazine concentration in pre-dip solution (hydrazine hydrate/ratio to stock solution) (ch)...
2.5.10.20 ■ Temperature of pre-dip liquid (°C)...10.25.35
■Immersion time (see) in the brad dip solution...5.1
0.30.60.120 ■Plating solution and plating temperature Same as Example 1 Ten sheets each were processed under the following conditions. After the treatment, it was immersed in an electroless plating solution within 30 seconds to perform plating with a thickness of 30 μm. After plating, the presence or absence of plating precipitation on the independent pattern portions was observed. In order to examine the effect of immersion in the pre-dip solution, a base material that was not immersed in the pre-dip solution was electrolessly plated, and the presence or absence of plating precipitation on the independent pattern portions was observed.
五 結果
プレディップ液に浸漬しない基板は、全て（１０枚）独
立パターン部の一部にめっきが析出せず不良となったが
、プレディップ液に浸漬した基板は、各条件とも全ての
基板（１０枚）について独立ノくターン部にめっきが析
出し、良好であった。5. As a result, all (10) substrates that were not immersed in the pre-dip solution were defective because the plating did not precipitate on a part of the independent pattern part, but for the substrates that were immersed in the pre-dip solution, all of the substrates (10) were defective under each condition. For 10 sheets), plating was deposited on the independent turn portions, and the results were good.
ｔ 条件
■使用した還元性薬品 ・・・次亜リン酸溶液■プ
レディップ液の次亜リン酸濃度
（６０チ次亜リン酸原液に対する比率）（％）・・・２
，５，１０，２０
■ブレディップ液の温度（℃）・・・１０．２５．３５
■プレデイツプ液への浸漬時間（８ｅＣ）・・・５．１
０．３０．６０．１２０
■めっき液及びめっき＠度 実施例１と同じ２、 方
法
コンディショナー処理→水洗→酸洗→水洗の工程を終え
た基板を、３０秒以内にプレディップ液に浸漬し、所定
の条件で各１０枚処理した。処理後、３０秒以内に無電
解めっき液に浸漬し、３０μｍのめっきを行なった。め
っき後、独立パターン部へのめっきの析出の有無を観察
した。なお、プレディップ液への浸漬の効果を調べる為
に同時にプレディップ液へ浸漬しない基板を無電解めっ
きし、独立パターン部へのめっきの析出の有無を観察し
た。t Condition ■ Reducing chemicals used ... Hypophosphorous acid solution ■ Hypophosphorous acid concentration of pre-dip solution (ratio to 60% hypophosphorous acid stock solution) (%) ... 2
, 5, 10, 20 ■Temperature of the bread dip liquid (°C)...10.25.35
■Immersion time in pre-dip solution (8eC)...5.1
0.30.60.120 ■Plating solution and plating @ degree Same as Example 1 2. Method After completing the process of conditioner treatment → water washing → pickling → water washing, the substrate is immersed in the pre-dip solution within 30 seconds, Ten sheets each were processed under predetermined conditions. After the treatment, it was immersed in an electroless plating solution within 30 seconds to perform plating with a thickness of 30 μm. After plating, the presence or absence of plating precipitation on the independent pattern portions was observed. In order to examine the effect of immersion in the pre-dip solution, a substrate that was not immersed in the pre-dip solution was electrolessly plated, and the presence or absence of plating precipitation on the independent pattern portions was observed.
五 結果
プレディップ液に浸漬しない基板は、全て（１０枚）独
立パターン部の一部にめっきが析出せず不良となったが
、プレディップ液に浸漬した基板は、各条件とも全ての
基板（１０枚）について独立パターン部にめっきが析出
し、良好であった。5. As a result, all (10) substrates that were not immersed in the pre-dip solution were defective because the plating did not precipitate on a part of the independent pattern part, but for the substrates that were immersed in the pre-dip solution, all of the substrates (10) were defective under each condition. Regarding 10 sheets), plating was deposited on the independent pattern part, which was good.
第１図はプリント配線板の一部における独立パターン部
の存在状況を説明する上面図であり、第２図は同断面図
である。FIG. 1 is a top view illustrating the existence of an independent pattern portion in a part of a printed wiring board, and FIG. 2 is a sectional view thereof.
ｉ、ｎ：スルーホールi, n: Through hole
Claims (1)
解めつきの直前にホルマリン、次亜リン酸、次亜リン酸
塩、及びヒドラジンの群から選択される還元剤の水溶液
と銅基材とを接触することによりめつき析出不良を防止
する無電解銅めつきの前処理方法。1) When performing electroless plating of copper onto a copper substrate, immediately before electroless plating, an aqueous solution of a reducing agent selected from the group of formalin, hypophosphorous acid, hypophosphite, and hydrazine and a copper base A pretreatment method for electroless copper plating that prevents defects in plating precipitation due to contact with the metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28948485A JPS62149884A (en) | 1985-12-24 | 1985-12-24 | Pretreatment for electroless copper plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28948485A JPS62149884A (en) | 1985-12-24 | 1985-12-24 | Pretreatment for electroless copper plating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62149884A true JPS62149884A (en) | 1987-07-03 |
Family
ID=17743874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28948485A Pending JPS62149884A (en) | 1985-12-24 | 1985-12-24 | Pretreatment for electroless copper plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62149884A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004099466A3 (en) * | 2003-05-05 | 2005-02-24 | Blue29 Corp | Method for electroless deposition of phosphorus-containing metal films onto copper with palladium-free activation |
| JP2009167522A (en) * | 2007-12-21 | 2009-07-30 | Shinko Electric Ind Co Ltd | Copper film forming method |
| JP2016154992A (en) * | 2016-06-08 | 2016-09-01 | 株式会社北電子 | Game machine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58104170A (en) * | 1981-12-05 | 1983-06-21 | バイエル・アクチエンゲゼルシヤフト | Method of activating substrate surface for electroless plating |
| JPS58113366A (en) * | 1981-12-23 | 1983-07-06 | バイエル・アクチエンゲゼルシヤフト | Method of activating substrate surface for electroless plating |
-
1985
- 1985-12-24 JP JP28948485A patent/JPS62149884A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58104170A (en) * | 1981-12-05 | 1983-06-21 | バイエル・アクチエンゲゼルシヤフト | Method of activating substrate surface for electroless plating |
| JPS58113366A (en) * | 1981-12-23 | 1983-07-06 | バイエル・アクチエンゲゼルシヤフト | Method of activating substrate surface for electroless plating |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004099466A3 (en) * | 2003-05-05 | 2005-02-24 | Blue29 Corp | Method for electroless deposition of phosphorus-containing metal films onto copper with palladium-free activation |
| JP2009167522A (en) * | 2007-12-21 | 2009-07-30 | Shinko Electric Ind Co Ltd | Copper film forming method |
| JP2016154992A (en) * | 2016-06-08 | 2016-09-01 | 株式会社北電子 | Game machine |
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