JP2010236025A - Pretreatment agent for electroless plating and electroless plating method using the same - Google Patents

Pretreatment agent for electroless plating and electroless plating method using the same Download PDF

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JP2010236025A
JP2010236025A JP2009085527A JP2009085527A JP2010236025A JP 2010236025 A JP2010236025 A JP 2010236025A JP 2009085527 A JP2009085527 A JP 2009085527A JP 2009085527 A JP2009085527 A JP 2009085527A JP 2010236025 A JP2010236025 A JP 2010236025A
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substrate
electroless plating
pretreatment agent
pretreatment
catalyst
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Hisafumi Kawamura
寿文 河村
Tatsu Murakami
竜 村上
Masashi Oikawa
匡 及川
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Nippon Mining Holdings Inc
Eneos Corp
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Nippon Mining and Metals Co Ltd
Nippon Mining Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a pretreatment liquid which can make a uniform metal film having adequate adhesiveness formed on the surface of a substrate by electroless plating treatment even when the substrate is a resin substrate containing a filler and the like, and also provide a pretreatment agent which can make the uniform metal film having adequate adhesiveness formed on the surface of the substrate by electroless plating treatment even when a concentration of Pd is low in a catalyst-giving process conducted after the pretreatment. <P>SOLUTION: The pretreatment agent for electroless-plating the substrate includes an anionic phosphate-ester surface active agent and gives the zeta potential of less than 0 mV to the surface of the treated substrate. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は無電解めっき用前処理剤、特に基板樹脂の無電解銅めっき性を向上させる無電解めっき用前処理剤、及びこれを用いた無電解めっき方法に関する。   The present invention relates to a pretreatment agent for electroless plating, in particular, a pretreatment agent for electroless plating that improves electroless copper plating properties of a substrate resin, and an electroless plating method using the same.

近年、環境意識が高まり、基板材料のハロゲンフリー化が進められている。また電子機器の高性能化、高密度実装化への要求に伴い基板材料に対して高い信頼性が求められ、高いガラス転移点（Ｔｇ）を有する材料が使用されている。このようにハロゲンフリー化、高Ｔｇ化された材料を用いた基板は、通常、主成分のエポキシ樹脂やシアネート樹脂などの樹脂成分とシリカ（ＳｉＯ2）やアルミナ（Ａｌ2Ｏ3）などのフィラー成分、ガラス繊維などの成分で構成されている。それら基板成分（表面）ごとにめっき活性が異なり、その上に無電解めっきにより、均一で、密着性が良好な金属膜を形成することが困難になってきている。
また、従来より無電解めっきの前処理として被めっき物を前処理し、触媒を付与し、無電解めっきを行う。触媒としてはＰｄ等が用いられており、めっき性を確保するためには触媒液中のＰｄ濃度を１００〜２００ｍｇ／Ｌ程度に上げて用いているが、Ｐｄは高価であり、触媒液中のＰｄ濃度が低くても効果的に触媒を付与することができることが望まれている。 In recent years, environmental awareness has increased and halogen-free substrate materials have been promoted. In addition, with the demand for higher performance and higher density mounting of electronic devices, high reliability is required for substrate materials, and materials having a high glass transition point (Tg) are used. Substrates using such halogen-free and high-Tg materials are usually resin components such as the main components of epoxy resins and cyanate resins, and fillers such as silica (SiO 2 ) and alumina (Al 2 O 3 ). It is comprised by components, such as an ingredient and glass fiber. Plating activity differs for each substrate component (surface), and it has become difficult to form a uniform metal film with good adhesion by electroless plating thereon.
In addition, as a pretreatment for electroless plating, an object to be plated is pretreated, a catalyst is applied, and electroless plating is performed. Pd or the like is used as the catalyst, and the Pd concentration in the catalyst solution is increased to about 100 to 200 mg / L in order to ensure plating properties. However, Pd is expensive and is used in the catalyst solution. It is desired that the catalyst can be effectively applied even when the Pd concentration is low.

基材と無電解めっきにより形成する金属被膜との密着性を向上させる無電解めっき用前処理剤として、特許文献１にカチオン性高分子と電子供与性基を有する樹脂とカチオン系界面活性剤及び／またはノニオン系界面活性剤を有する水性処理液が記載されている。界面活性剤は、繊維布帛のような形状を有する基材に処理液を浸透させるために使用するものであり、アニオン系界面活性剤はカチオン性高分子との凝集が懸念されるため好ましくない。
また、特許文献２には脱脂・洗浄効果を有し、触媒を確実に付着させる前処理剤として、ノニオン系界面活性剤と陽イオン性樹脂と金属イオンの錯化剤を含む前処理液が記載されている。
特許文献３には、無電解めっきにより導体パターンを十分に被覆することができる前処理方法として、ノニオン系界面活性剤を含有する溶液を接触させる第１の工程と、カチオン系界面活性剤を含有する溶液に接触させる第２の工程を有する前処理方法が記載されている。この方法は２工程を必要とし、工程が煩雑となる。 As a pretreatment agent for electroless plating that improves the adhesion between a substrate and a metal film formed by electroless plating, Patent Document 1 discloses a cationic polymer, a resin having an electron-donating group, a cationic surfactant, and An aqueous treatment liquid having a nonionic surfactant is described. The surfactant is used for infiltrating the treatment liquid into a substrate having a shape such as a fiber fabric, and the anionic surfactant is not preferable because it may cause aggregation with the cationic polymer.
Patent Document 2 describes a pretreatment liquid that has a degreasing / cleaning effect and includes a nonionic surfactant, a cationic resin, and a metal ion complexing agent as a pretreatment agent for reliably attaching a catalyst. Has been.
Patent Document 3 includes a first step of contacting a solution containing a nonionic surfactant as a pretreatment method capable of sufficiently covering a conductor pattern by electroless plating, and a cationic surfactant. A pretreatment method having a second step of contacting with the solution to be described is described. This method requires two steps, and the steps are complicated.

特開２００４−９１８７７号公報JP 2004-91877 A 特開２００６−２４９５２０号公報JP 2006-249520 A 特開２００６−２２１７号公報JP 2006-2217 A

本発明は、無電解めっきにより、フィラー等を含む樹脂基板においても、基板表面に均一で、密着性が良好な金属膜を形成することができる前処理液を提供することを目的とする。
また、前処理した後に行う触媒付与において、Ｐｄ濃度が低くても無電解めっきにより基板表面に均一で、密着性が良好な金属膜を形成することが可能となる前処理剤を提供することを目的とする。 An object of the present invention is to provide a pretreatment liquid capable of forming a uniform metal film with good adhesion on a substrate surface even on a resin substrate containing a filler or the like by electroless plating.
In addition, in the catalyst application performed after the pretreatment, a pretreatment agent that can form a metal film that is uniform and has good adhesion on the substrate surface by electroless plating even when the Pd concentration is low is provided. Objective.

本発明者は鋭意検討を行った結果、特定の界面活性剤を含有する前処理剤を用いることにより上記課題が解決できることを見出し、本発明に至った。   As a result of intensive studies, the present inventor has found that the above problem can be solved by using a pretreatment agent containing a specific surfactant, and has reached the present invention.

即ち、本発明は以下のとおりである。
（１）基板の無電界めっき用前処理剤であって、アニオン系リン酸エステル界面活性剤を含み、処理した基板表面のゼータ電位が０ｍＶ未満となることを特徴とする無電解めっき用前処理剤。
（２）前記アニオン系リン酸エステル界面活性剤がアニオン系芳香族リン酸エステル類であることを特徴とする前記（１）記載の無電解めっき用前処理剤。
（３）前記（１）又は（２）記載の無電解めっき用前処理剤を用い、基版を処理した後、Ｐｄ濃度が１０ｍｇ／Ｌ以上４０ｍｇ／Ｌ以下のＰｄ含有触媒液を用いて触媒を付与し、無電解めっきを行うことを特徴とする無電解めっき方法。 That is, the present invention is as follows.
(1) A pretreatment agent for electroless plating of a substrate, comprising an anionic phosphate ester surfactant, wherein the zeta potential of the treated substrate surface is less than 0 mV, Agent.
(2) The pretreatment agent for electroless plating according to (1) above, wherein the anionic phosphate ester surfactant is an anionic aromatic phosphate ester.
(3) After treating the base plate using the pretreatment agent for electroless plating described in (1) or (2) above, a catalyst is used using a Pd-containing catalyst solution having a Pd concentration of 10 mg / L to 40 mg / L. An electroless plating method characterized by applying electroless plating.

本発明の無電解めっき用前処理剤を用いて処理することにより、基板全体のめっき性が改善され、フィラー等を含む樹脂基板においても、基板表面に均一で、密着性が良好な金属膜を無電解めっきで形成することができる。
また、前処理した後に行う触媒付与において、Ｐｄ濃度が低くても無電解めっきにより基板表面に均一で、密着性が良好な金属膜を形成することが可能となる。 By using the pretreatment agent for electroless plating according to the present invention, the plating property of the entire substrate is improved, and even in a resin substrate containing a filler, a metal film that is uniform on the substrate surface and has good adhesion is formed. It can be formed by electroless plating.
In addition, in the catalyst application performed after the pretreatment, even when the Pd concentration is low, it is possible to form a metal film that is uniform and has good adhesion on the substrate surface by electroless plating.

実施例１で得られた基板のＳＥＭ写真である。2 is a SEM photograph of the substrate obtained in Example 1. 実施例２で得られた基板のＳＥＭ写真である。4 is a SEM photograph of the substrate obtained in Example 2. 実施例３で得られた基板のＳＥＭ写真である。4 is a SEM photograph of the substrate obtained in Example 3. 比較例１で得られた基板のＳＥＭ写真である。4 is a SEM photograph of the substrate obtained in Comparative Example 1. 比較例４で得られた基板のＳＥＭ写真である。6 is a SEM photograph of a substrate obtained in Comparative Example 4.

本発明の無電解めっき用前処理剤は、アニオン系リン酸エステル界面活性剤を含み、該前処理剤で処理した基板表面のゼータ電位が０ｍＶ未満となる。
アニオン系リン酸エステル界面活性剤としては、ポリオキシエチレンアルキルフェニルエーテルリン酸塩等のアニオン系芳香族リン酸エステル類、及びアルキルリン酸エステル塩、ポリオキシエチレンアルキルエーテルリン酸塩等のアニオン系脂肪族リン酸エステル類が挙げられるが、本発明の所定の効果を得るためにはアニオン系芳香族リン酸エステル類が好ましい。
アニオン系芳香族リン酸エステル類としては、例えば（株）ＡＤＥＫＡ製ＣＳ１４１Ｅ、ＣＳ２７９等を好ましく用いることができる。 The pretreatment agent for electroless plating of the present invention contains an anionic phosphate ester surfactant, and the zeta potential of the substrate surface treated with the pretreatment agent is less than 0 mV.
Anionic phosphate ester surfactants include anionic aromatic phosphates such as polyoxyethylene alkylphenyl ether phosphates, and anionic phosphates such as alkyl phosphate ester salts and polyoxyethylene alkyl ether phosphates. Aliphatic phosphates are mentioned, but anionic aromatic phosphates are preferable for obtaining the predetermined effect of the present invention.
As anionic aromatic phosphates, for example, CS141E, CS279 manufactured by ADEKA Corporation can be preferably used.

本発明の前処理剤は、アニオン系リン酸エステル界面活性剤の水溶液として用い、前処理液中アニオン系リン酸エステル界面活性剤を１ｍｇ／Ｌ〜３ｇ／Ｌ含有することが好ましく、１０ｍｇ／Ｌ〜３００ｍｇ／Ｌ含有することがより好ましい。含有量が１ｍｇ／Ｌ未満では表面の電位コントロールが不十分で、無電解めっきした際にムラになる。また、３ｇ／Ｌを超えると、効果があるが、洗浄が大変であることと、それにより表面に残存し易くなり、無電解めっきにより形成しためっきの密着性が低下する。
本発明の前処理剤は、アニオン系リン酸エステル界面活性剤以外にポリエチレングリコール等のノニオン系界面活性剤や、ジアミンやホスホン酸などのキレート剤、錯化剤を含有してもよい。 The pretreatment agent of the present invention is used as an aqueous solution of an anionic phosphate ester surfactant, and preferably contains 1 mg / L to 3 g / L of an anionic phosphate ester surfactant in the pretreatment solution. It is more preferable to contain -300 mg / L. If the content is less than 1 mg / L, the surface potential control is insufficient, and unevenness occurs when electroless plating is performed. Further, if it exceeds 3 g / L, there is an effect, but cleaning is difficult, and it tends to remain on the surface, and the adhesion of the plating formed by electroless plating is lowered.
The pretreatment agent of the present invention may contain a nonionic surfactant such as polyethylene glycol, a chelating agent such as diamine and phosphonic acid, and a complexing agent in addition to the anionic phosphate ester surfactant.

本発明の前処理剤で処理した基板表面のゼータ電位（界面動電位）は０ｍＶ未満であり、好ましくは０〜−１００ｍＶであり、更に好ましくは−１０〜−５０ｍＶである。処理した基板表面のゼータ電位が０ｍＶ以上であると触媒の吸着が弱くなる。   The zeta potential (interface potential) of the substrate surface treated with the pretreatment agent of the present invention is less than 0 mV, preferably 0 to −100 mV, and more preferably −10 to −50 mV. When the zeta potential of the treated substrate surface is 0 mV or more, the adsorption of the catalyst becomes weak.

ゼータ電位の測定は、例えば大塚電子製ゼータ電位測定装置（ＥＬＳ）等の装置を用いて、平板試料用セルユニットにて基板試料面に電気泳動を行い、その数値からゼータ電位を求めることができる。   The zeta potential can be measured, for example, by using a device such as a zeta potential measuring device (ELS) manufactured by Otsuka Electronics Co., Ltd., by performing electrophoresis on the surface of the substrate sample in a flat sample cell unit, and obtaining the zeta potential from the numerical value. .

本発明の前処理剤を用いた前処理方法としては、前処理剤に基板を浸漬すればよい。前処理としては、３５〜５５℃で、１〜１０分程度浸漬することが好ましい。   As a pretreatment method using the pretreatment agent of the present invention, the substrate may be immersed in the pretreatment agent. As pretreatment, it is preferable to immerse at 35 to 55 ° C. for about 1 to 10 minutes.

前記前処理液を用いて前処理した後に、Ｐｄ等の触媒を付与する。Ｐｄ触媒液としては公知のものを用いることができる。例えば、Ｐｄイオン化合物系の触媒液を好ましく用いることができる。
本発明の前処理剤を用いて処理することにより、Ｐｄの触媒付与を行う触媒液のＰｄ濃度を１０〜４０ｍｇ／Ｌとすることができる。４０ｍｇ／Ｌを超えてもめっき性に何ら問題はないが、不必要にＰｄ吸着量を増加させるだけでコスト面で不利である。 After pretreatment using the pretreatment liquid, a catalyst such as Pd is applied. A well-known thing can be used as a Pd catalyst liquid. For example, a Pd ion compound-based catalyst solution can be preferably used.
By performing the treatment using the pretreatment agent of the present invention, the Pd concentration of the catalyst solution for applying the catalyst of Pd can be set to 10 to 40 mg / L. Even if it exceeds 40 mg / L, there is no problem in the plating property, but it is disadvantageous in terms of cost only by increasing the Pd adsorption amount unnecessarily.

基板は、ビルドアップ基板樹脂等の樹脂基板が好ましい。樹脂基板としては、主成分のエポキシ樹脂やシアネート樹脂などの樹脂成分とシリカ（ＳｉＯ2）やアルミナ（Ａｌ2Ｏ3）などのフィラー成分、ガラス繊維などの成分で構成されている樹脂基板が挙げられ、例えば、ＳｉＯ2系フィラーが充填されたエポキシ樹脂の基板を好適に用いることができる。基板は、過マンガン酸などの通常の方法でデスミア処理したのち、本発明の前処理剤で処理することが好ましい。 The substrate is preferably a resin substrate such as a build-up substrate resin. Examples of the resin substrate include a resin substrate composed of a resin component such as an epoxy resin or cyanate resin as a main component, a filler component such as silica (SiO 2 ) or alumina (Al 2 O 3 ), or a component such as glass fiber. For example, an epoxy resin substrate filled with a SiO 2 filler can be preferably used. The substrate is preferably treated with the pretreatment agent of the present invention after desmear treatment by a usual method such as permanganic acid.

触媒を付与した後に行う無電解めっきは、銅、ニッケル、スズ等の無電解めっきであるが、無電解銅めっきが好ましく、この際に用いる無電解銅めっき液としては、公知の無電解めっき液を用い、公知の方法で行うことができる。
本発明の処理剤で処理した後、Ｐｄ濃度が１０〜４０ｍｇ／Ｌの触媒液を用いて触媒を付与しても、無電解銅めっきにより、フィラー等への付きまわりもよく、均一に成膜することができ、また密着性がよいめっき膜を得ることができる。 The electroless plating performed after the catalyst is applied is electroless plating of copper, nickel, tin, etc., but electroless copper plating is preferable. As the electroless copper plating solution used in this case, a known electroless plating solution is used. It can carry out by a well-known method.
Even after the treatment with the treatment agent of the present invention, a catalyst is applied using a catalyst solution having a Pd concentration of 10 to 40 mg / L. In addition, a plating film with good adhesion can be obtained.

以下に実施例を示し、本発明をさらに詳細に説明する。
実施例１
シリカ系フィラーを含有するエポキシ樹脂からなるプリント基板用の基板（ＧＸ１８、味の素ファインテクノ製）をデスミア処理した後、アニオン系芳香族リン酸エステル型界面活性剤（ＣＳ１４１Ｅ、（株）ＡＤＥＫＡ製）を１ｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、表面のゼータ電位を測定した。ゼータ電位は−１０ｍＶであった。その後、Ｐｄ濃度が３０ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した。その後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真を図１に示す。図１に見るように、輝点部位がなく、フィラーに付きまわりよくめっきされていることがわかる。 The following examples illustrate the present invention in more detail.
Example 1
After desmearing a printed circuit board substrate (GX18, manufactured by Ajinomoto Fine Techno) made of an epoxy resin containing a silica-based filler, an anionic aromatic phosphate ester surfactant (CS141E, manufactured by ADEKA Corporation) It was treated with a pretreatment agent containing 1 g / L (45 ° C., 3 minutes), and the zeta potential of the surface was measured. The zeta potential was −10 mV. Thereafter, Pd was imparted by a catalyst (CB process, manufactured by Nikko Metal Co., Ltd.) having a Pd concentration of 30 mg / L. Thereafter, electroless copper plating was performed to form a copper layer having a thickness of 0.3 μm. A SEM photograph is shown in FIG. As shown in FIG. 1, it can be seen that there is no bright spot portion and the filler is plated well.

実施例２
実施例１と同様のプリント基板用の基板をデスミアした後、アニオン系芳香族リン酸エステル型界面活性剤（ＣＳ２７９、（株）ＡＤＥＫＡ製）を１ｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、表面のゼータ電位を測定した。ゼータ電位は−２０ｍＶであった。その後、Ｐｄ濃度が３８ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した。その後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真を図２に示す。図２に見るように、輝点部位がなく、フィラーに付きまわりよくめっきされていることがわかる。 Example 2
After desmearing the same printed circuit board substrate as in Example 1, it was treated with a pretreatment agent containing 1 g / L of an anionic aromatic phosphate type surfactant (CS279, manufactured by ADEKA Corporation) (45 At 3 ° C., and the zeta potential on the surface was measured. The zeta potential was −20 mV. Thereafter, Pd was applied by a catalyst (CB process, manufactured by Nikko Metal Co., Ltd.) having a Pd concentration of 38 mg / L. Thereafter, electroless copper plating was performed to form a copper layer having a thickness of 0.3 μm. An SEM photograph is shown in FIG. As shown in FIG. 2, it can be seen that there is no bright spot portion and the filler is plated well.

実施例３
実施例１と同様のプリント基板用の基板をデスミアした後、アニオン系芳香族リン酸エステル型界面活性剤（ＣＳ１４１Ｅ、（株）ＡＤＥＫＡ製）を０．５ｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、表面のゼータ電位を測定した。ゼータ電位は−５ｍＶであった。その後、Ｐｄ濃度が３０ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した。その後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真を図３に示す。図３に見るように、輝点部位がなく、フィラーに付きまわりよくめっきされていることがわかる。 Example 3
After desmearing the same printed circuit board substrate as in Example 1, it was treated with a pretreatment agent containing 0.5 g / L of an anionic aromatic phosphate ester surfactant (CS141E, manufactured by ADEKA Corporation). (45 ° C., 3 minutes), the zeta potential of the surface was measured. The zeta potential was −5 mV. Thereafter, Pd was applied by a catalyst (CB process, manufactured by Nikko Metal Co., Ltd.) having a Pd concentration of 30 mg / L. Thereafter, electroless copper plating was performed to form a copper layer having a thickness of 0.3 μm. A SEM photograph is shown in FIG. As shown in FIG. 3, it can be seen that there is no bright spot portion and the filler is plated well.

比較例１
実施例１と同様のプリント基板用の基板をデスミアした後、ノニオン系エチレングリコール型界面活性剤（ＰＥＧ１０００）を１ｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、ゼータ電位を測定した。ゼータ電位は５ｍＶであった。その後その後Ｐｄ濃度が３８ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真を図４に示す。ＳＥＭ写真において、輝点となっているところが表面がめっきされていない部分であり、フィラー上のめっき析出が不十分であった。
比較例２
実施例１と同様のプリント基板用の基板をデスミアした後、ノニオン系エチレングリコール型界面活性剤（ＰＥＧ１０００）を１０ｍｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、ゼータ電位を測定した。ゼータ電位は−５ｍＶであった。その後その後Ｐｄ濃度が３８ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真において、表面がめっきされていない部分があり、フィラー上のめっき析出が不十分であった。 Comparative Example 1
After desmearing the same printed circuit board substrate as in Example 1, it was treated with a pretreatment agent containing 1 g / L of a nonionic ethylene glycol surfactant (PEG1000) (45 ° C., 3 minutes), and the zeta potential was It was measured. The zeta potential was 5 mV. After that, after applying Pd with a catalyst (CB process, manufactured by Nikko Metal Co., Ltd.) having a Pd concentration of 38 mg / L, electroless copper plating was performed to form a 0.3 μm thick copper layer. An SEM photograph is shown in FIG. In the SEM photograph, the bright spot was a portion where the surface was not plated, and the plating deposition on the filler was insufficient.
Comparative Example 2
After desmearing the same printed circuit board substrate as in Example 1, it was treated with a pretreatment agent containing 10 mg / L of a nonionic ethylene glycol surfactant (PEG1000) (45 ° C., 3 minutes), and the zeta potential was It was measured. The zeta potential was −5 mV. Thereafter, Pd was applied by a catalyst (CB process, manufactured by Nikko Metal Co., Ltd.) having a Pd concentration of 38 mg / L, and then electroless copper plating was performed to form a copper layer having a thickness of 0.3 μm. In the SEM photograph, there was a portion where the surface was not plated, and plating deposition on the filler was insufficient.

比較例３
実施例１と同様のプリント基板用の基板をデスミアした後、アニオン系アルキルベンゼンスルホン酸塩型界面活性剤（ネオペレックスＧ−２５、ＫＡＯ製）を１ｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、表面のゼータ電位を測定した。せータ電位は−５ｍＶであった。その後Ｐｄ濃度が３８ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真において表面がめっきされていない部分があり、フィラーへのめっき析出が不十分であった。 Comparative Example 3
After desmearing the same printed circuit board substrate as in Example 1, it was treated with a pretreatment agent containing 1 g / L of an anionic alkylbenzene sulfonate surfactant (Neopelex G-25, manufactured by KAO) (45 At 3 ° C., and the zeta potential on the surface was measured. The setter potential was -5 mV. Then, after applying Pd with a catalyst (CB process, manufactured by Nikko Metal Co., Ltd.) having a Pd concentration of 38 mg / L, electroless copper plating was performed to form a copper layer having a thickness of 0.3 μm. In the SEM photograph, there was a portion where the surface was not plated, and plating deposition on the filler was insufficient.

比較例４
実施例１と同様のプリント基板用の基板をデスミアした後、アニオン系アルキルベンゼンスルホン酸塩型界面活性剤（ネオペレックスＧ−２５、ＫＡＯ製）を１ｍｇ／Ｌ含んだ前処理剤で処理し（４５℃、３分）、表面のゼータ電位を測定した。せータ電位は−０．５ｍＶであった。その後Ｐｄ濃度が３８ｍｇ／Ｌのキャタリスト（ＣＢプロセス、日鉱金属（株）製）にてＰｄを付与した後無電解銅めっきを行い、膜厚０．３μｍの銅層を形成した。ＳＥＭ写真を図５に示す。輝点となっているところが表面がめっきされていない部分であり、フィラーへのめっき析出が不十分であった。 Comparative Example 4
After desmearing the same printed circuit board substrate as in Example 1, it was treated with a pretreatment agent containing 1 mg / L of an anionic alkylbenzene sulfonate surfactant (Neopelex G-25, manufactured by KAO) (45 At 3 ° C., and the zeta potential on the surface was measured. The setter potential was -0.5 mV. Thereafter, Pd was applied by a catalyst having a Pd concentration of 38 mg / L (CB process, manufactured by Nikko Metal Co., Ltd.) and then electroless copper plating was performed to form a copper layer having a thickness of 0.3 μm. An SEM photograph is shown in FIG. The bright spot is a portion where the surface is not plated, and plating deposition on the filler was insufficient.

Claims (3)

基板の無電界めっき用前処理剤であって、アニオン系リン酸エステル界面活性剤を含み、処理した基板表面のゼータ電位が０ｍＶ未満となることを特徴とする無電解めっき用前処理剤。   A pretreatment agent for electroless plating of a substrate, comprising an anionic phosphate ester surfactant, wherein the zeta potential of the treated substrate surface is less than 0 mV. 前記アニオン系リン酸エステル界面活性剤がアニオン系芳香族リン酸エステル類であることを特徴とする請求項１記載の無電解めっき用前処理剤。   2. The pretreatment agent for electroless plating according to claim 1, wherein the anionic phosphate ester surfactant is an anionic aromatic phosphate ester. 請求項１又は２記載の無電解めっき用前処理剤を用い、基板を処理した後、Ｐｄ濃度が１０ｍｇ／Ｌ以上４０ｍｇ／Ｌ以下のＰｄ含有触媒液を用いて触媒を付与し、無電解めっきを行うことを特徴とする無電解めっき方法。   After processing the substrate using the pretreatment agent for electroless plating according to claim 1 or 2, a catalyst is applied using a Pd-containing catalyst solution having a Pd concentration of 10 mg / L or more and 40 mg / L or less, and electroless plating is performed. An electroless plating method characterized in that:
JP2009085527A 2009-03-31 2009-03-31 Pretreatment agent for electroless plating and electroless plating method using the same Withdrawn JP2010236025A (en)

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