JP2003193245A - Pretreatment agent for planting and electroless plasting method using the same - Google Patents
Pretreatment agent for planting and electroless plasting method using the sameInfo
- Publication number
- JP2003193245A JP2003193245A JP2001388972A JP2001388972A JP2003193245A JP 2003193245 A JP2003193245 A JP 2003193245A JP 2001388972 A JP2001388972 A JP 2001388972A JP 2001388972 A JP2001388972 A JP 2001388972A JP 2003193245 A JP2003193245 A JP 2003193245A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- agent
- silane coupling
- pretreatment agent
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、無電解めっきの触
媒となる貴金属化合物を捕捉する機能とめっき基体上に
固着する機能を同一分子内に併せ有するシランカップリ
ング剤と、貴金属化合物を混合もしくは反応させた液を
３０℃以上で連続使用する場合、その液に過酸化水素を
添加することにより、液安定性を向上させためっき前処
理剤、およびそれを用いた無電解めっき方法に関するも
のである。TECHNICAL FIELD The present invention relates to a method of mixing a noble metal compound with a silane coupling agent having in the same molecule a function of capturing a noble metal compound which serves as a catalyst for electroless plating and a function of fixing to a plating substrate. The present invention relates to a plating pretreatment agent having improved liquid stability by adding hydrogen peroxide to the reacted liquid when continuously used at 30 ° C. or higher, and an electroless plating method using the same. is there.
【０００２】[0002]
【従来の技術】無電解めっき法は導電性のない下地に金
属被膜を形成する方法の一つであり、樹脂基板にプリン
ト配線を形成する方法などに利用されている。この無電
解めっきの前処理としては、パラジウムなどの貴金属を
触媒としてあらかじめ下地に付着させておく活性化と呼
ばれる方法が一般的である。これまで、ＳｎＣｌ2の塩
酸性水溶液で処理した後ＰｄＣｌ2水溶液に浸漬処理し
てＰｄを吸着させたり、ＳｎとＰｄを含んだコロイド溶
液によりＰｄを表面に担持させる方法が使われてきた。
これらの方法は毒性が高いＳｎを使用することや処理工
程が複雑であるなど問題が多い。そこで最近、無電解め
っきの触媒であるＰｄなどの貴金属を担持させる方法と
して、これらの貴金属類と錯体を形成できる官能基を有
するシランカップリング剤を使った方法がいろいろと提
案されている（特公昭５９−５２７０１、特開昭６０−
１８１２９４、特開昭６１−１９４１８３、特開平３−
４４１４９号公報）。2. Description of the Related Art The electroless plating method is one of the methods for forming a metal coating on an underlayer having no conductivity, and is used as a method for forming a printed wiring on a resin substrate. As a pretreatment for this electroless plating, a method called activation in which a noble metal such as palladium is previously attached as a catalyst to a substrate is generally used. Previously, or to adsorb Pd was immersed in PdCl 2 solution was treated with hydrochloric acid aqueous solution of SnCl 2, a method for supporting Pd on the surface it has been used by a colloidal solution containing Sn and Pd.
These methods have many problems such as using highly toxic Sn and complicated processing steps. Therefore, recently, various methods using a silane coupling agent having a functional group capable of forming a complex with these noble metals have been proposed as a method for supporting a noble metal such as Pd which is a catalyst for electroless plating (special feature: JP-A-59-52701, JP-A-60-
181294, JP-A-61-194183, JP-A-3-
44149 publication).
【０００３】本発明者らも、シランカップリング剤と貴
金属化合物をあらかじめ混合もしくは反応させためっき
前処理剤を使った方法について、いくつか提案している
（特願２０００−１６４５、特願２０００−２３８０４
７号）。しかし、これらの液には、経時変化を起こしや
すく、沈殿が発生するなど液安定性が不十分であるとい
う問題点があった。本発明者等は、前記金属化合物とそ
れを捕捉する機能を有するシランカップリング剤をあら
かじめ混合もしくは反応させた液の経時変化の原因は、
貴金属化合物の還元反応にあることを突き止めた。そし
てその対策として、酸化剤を加えることにより経時変化
が抑制され、液安定性が向上することを見出し、すでに
提案している（特願２００１−２３１１２９号）。The inventors of the present invention have also proposed several methods using a plating pretreatment agent in which a silane coupling agent and a noble metal compound are mixed or reacted in advance (Japanese Patent Application Nos. 2000-1645 and 2000-2000). 23804
No. 7). However, these liquids have a problem that the liquid stability is insufficient such that they easily change with time and precipitates. The present inventors, the cause of the change with time of the liquid obtained by previously mixing or reacting the metal compound and a silane coupling agent having a function of capturing it,
It was found that there was a reduction reaction of the noble metal compound. As a countermeasure against this, it has been found that addition of an oxidizing agent suppresses the change over time and improves the liquid stability, and has already proposed it (Japanese Patent Application No. 2001-231129).
【０００４】[0004]
【発明が解決しようとする課題】前記めっき前処理剤は
シランカップリング剤の機能により被めっき材に吸着す
るが、被めっき材によっては３０℃以上に加温しないと
シランカップリング剤を十分固定できない場合がある。
しかし、このように前記めっき前処理剤を３０℃以上で
連続使用した場合、経時変化の抑制が不十分になるとい
う問題点があった。本発明は、無電解めっきのためのめ
っき前処理剤のこうした問題点を改善することを技術的
課題とするものである。The plating pretreatment agent is adsorbed on the material to be plated by the function of the silane coupling agent, but depending on the material to be plated, the silane coupling agent is sufficiently fixed unless it is heated to 30 ° C. or higher. Sometimes you can't.
However, when the plating pretreatment agent is continuously used at 30 ° C. or higher as described above, there is a problem that the change over time is insufficiently suppressed. The present invention has a technical object to improve such problems of the pretreatment agent for electroless plating.
【０００５】[0005]
【課題を解決するための手段】本発明者らは鋭意検討し
た結果、前記貴金属化合物とそれを捕捉する機能を有す
るシランカップリング剤をあらかじめ混合もしくは反応
させた液を３０℃以上で連続使用する場合、過酸化水素
のような強力な酸化剤を加えないと経時変化を抑制でき
ないことを見出し、本発明に至った。Means for Solving the Problems As a result of intensive studies by the present inventors, a liquid obtained by previously mixing or reacting the noble metal compound with a silane coupling agent having a function of capturing the noble metal compound is continuously used at 30 ° C. or higher. In this case, it was found that the change with time cannot be suppressed unless a strong oxidizing agent such as hydrogen peroxide is added, and the present invention has been completed.
【０００６】すなわち、本発明は、（１）一分子中に金
属捕捉能を持つ官能基を有するシランカップリング剤と
貴金属化合物をあらかじめ混合もしくは反応させた液に
過酸化水素を添加してなり、かつ、３０℃以上で連続使
用することを特徴とするめっき前処理剤、（２）めっき
前処理剤中の過酸化水素の濃度が０．１〜１０００ｍｇ
／Ｌであることを特徴とする前記（１）記載のめっき前
処理剤、（３）一分子中に金属捕捉能を持つ官能基を有
するシランカップリング剤がアゾール系化合物とエポキ
シシラン系化合物との反応により得られたシランカップ
リング剤であることを特徴とする前記（１）又は（２）
記載のめっき前処理剤、（４）金属捕捉能を持つ官能基
がイミダゾール基であることを特徴とする前記（１）〜
（３）のいずれかに記載のめっき前処理剤、（５）貴金
属化合物がパラジウム化合物であることを特徴とする前
記（１）〜（４）のいずれかに記載のめっき前処理剤、
（６）前記（１）〜（５）のいずれかに記載のめっき前
処理剤を用い被めっき物のめっき前処理を３０℃以上で
行った後、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、に関する。That is, according to the present invention, (1) hydrogen peroxide is added to a liquid in which a silane coupling agent having a functional group capable of capturing a metal in one molecule and a noble metal compound are mixed or reacted in advance. And a pretreatment agent for plating, which is used continuously at 30 ° C. or higher, and (2) a concentration of hydrogen peroxide in the pretreatment agent is 0.1 to 1000 mg.
/ L, the pretreatment agent for plating according to (1) above, and (3) the silane coupling agent having a functional group having a metal capturing ability in one molecule is an azole compound and an epoxysilane compound. (1) or (2), which is a silane coupling agent obtained by the reaction of
The pretreatment agent for plating described in (4) above, wherein the functional group having a metal capturing ability is an imidazole group.
The pretreatment agent for plating according to any one of (3), (5) the pretreatment agent for plating according to any one of (1) to (4) above, wherein the noble metal compound is a palladium compound.
(6) The electroless plating is performed after the pretreatment of the object to be plated with the pretreatment agent for plating according to any one of (1) to (5) above 30 ° C. An electrolytic plating method.
【０００７】本発明においては、前記特定のシランカッ
プリング剤を用いることが重要である。すなわち、金属
捕捉能を持つ官能基が分子内に存在することにより、め
っき触媒の活性を効果的に発現する電子状態、配向を取
ることが可能となり、シランカップリング剤であること
により被めっき材との密着性を発現することが可能とな
る。In the present invention, it is important to use the specific silane coupling agent. That is, the presence of a functional group having a metal-capturing ability in the molecule makes it possible to take an electronic state and orientation that effectively develops the activity of the plating catalyst. It becomes possible to express the adhesiveness with.
【０００８】本発明に有用な金属捕捉能を持つ官能基と
しては、これらに制限されるものではないが、アミノ
基、カルボキシル基、アゾール基、水酸基、メルカプト
基などが挙げられる。これらの中でもアゾール基が好ま
しい。アゾール基としては、イミダゾール、オキサゾー
ル、チアゾール、セレナゾール、ピラゾール、イソオキ
サゾール、イソチアゾール、トリアゾール、オキサジア
ゾール、チアジアゾール、テトラゾール、オキサトリア
ゾール、チアトリアゾール、ベンダゾール、インダゾー
ル、ベンズイミダゾール、ベンゾトリアゾールなどが挙
げられる。中でもイミダゾール基が特に好ましい。The functional group having metal-capturing ability useful in the present invention includes, but is not limited to, amino group, carboxyl group, azole group, hydroxyl group, mercapto group and the like. Of these, an azole group is preferable. Examples of the azole group include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, bendazole, indazole, benzimidazole and benzotriazole. . Among them, an imidazole group is particularly preferable.
【０００９】また、前記シランカップリング剤とは、前
記貴金属イオン捕捉基の他に、−ＳｉＸ1Ｘ2Ｘ3基を有
する化合物であり、Ｘ1、Ｘ2、Ｘ3はアルキル基、ハロ
ゲンやアルコキシ基などを意味し、被めっき物への固定
が可能な官能基であれば良い。Ｘ1、Ｘ2、Ｘ3は同一で
もまた異なっていても良い。The silane coupling agent is a compound having a —SiX 1 X 2 X 3 group in addition to the noble metal ion-trapping group, wherein X 1 , X 2 and X 3 are alkyl groups, halogens and It means an alkoxy group or the like and may be any functional group that can be fixed to an object to be plated. X 1 , X 2 and X 3 may be the same or different.
【００１０】このようなシランカップリング剤として
は、例えば、アゾール系化合物とエポキシシラン系化合
物との反応で得られたシランカップリング剤を例示する
ことができる（特開平６−２５６３５８号公報）。ま
た、このような含窒素複素環式アゾール化合物と反応さ
せるエポキシ基含有シラン化合物としては、As such a silane coupling agent, for example, a silane coupling agent obtained by a reaction of an azole compound and an epoxysilane compound can be exemplified (JP-A-6-256358). Further, as the epoxy group-containing silane compound to be reacted with such a nitrogen-containing heterocyclic azole compound,
【００１１】[0011]
【化１】
（式中、Ｒ1、Ｒ2は水素又は炭素数が１〜３のアルキル
基、ｎは１〜３の整数）で示されるエポキシシランカッ
プリング剤が好ましい。[Chemical 1] (In the formula, R 1 and R 2 are hydrogen or an alkyl group having 1 to 3 carbon atoms, n is an integer of 1 to 3), and an epoxy silane coupling agent is preferable.
【００１２】前記アゾール化合物と前記エポキシ基含有
シラン化合物との反応は、特開平６−２５６３５８号公
報に説示されている条件で行うことができる。例えば、
８０〜２００℃でアゾール化合物１モルに対して０．１
〜１０モルのエポキシ基含有シラン化合物を滴下して５
分〜２時間反応させる。その際、溶媒は特に不要である
が、クロロホルム、ジオキサンメタノール、エタノール
等の有機溶媒を用いてもよい。The reaction between the azole compound and the epoxy group-containing silane compound can be carried out under the conditions described in JP-A-6-256358. For example,
0.1 to 1 mol of azole compound at 80 to 200 ° C
-10 mol of epoxy group-containing silane compound is added dropwise and 5
Allow to react for minutes to 2 hours. At that time, a solvent is not particularly necessary, but an organic solvent such as chloroform, dioxane methanol, ethanol or the like may be used.
【００１３】本発明に使用する金属捕捉能を有するシラ
ンカップリング剤のその他の例として、γ−アミノプロ
ピルトリメトキシシラン、γ−アミノプロピルトリエト
キシシラン、Ｎ−β（アミノエチル）γ−アミノプロピ
ルトリメトキシシラン、Ｎ−β（アミノエチル）γ−ア
ミノプロピルトリエトキシシラン、γ−メルカプトプロ
ピルトリメトキシシラン等が挙げられる。Other examples of the silane coupling agent having a metal capturing ability used in the present invention include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and N-β (aminoethyl) γ-aminopropyl. Examples thereof include trimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane.
【００１４】また、前記貴金属化合物としては、無電解
めっき液から銅やニッケルなどを析出させる際に触媒効
果を示すパラジウム、銀、白金、金などの塩化物、水酸
化物、酸化物、硫酸塩、アンモニウム塩などのアンミン
錯体などが挙げられるが、特にパラジウム化合物、中で
も塩化パラジウムが好ましい。貴金属化合物は水溶液と
して用いることが好ましく、めっき前処理剤中の濃度は
１〜３００ｍｇ／Ｌが好ましい。本明細書において、め
っき前処理剤中の濃度とは、被めっき物を前処理する際
の溶液中の濃度をいう。The precious metal compound is a chloride, hydroxide, oxide or sulfate of palladium, silver, platinum, gold or the like which exhibits a catalytic effect when copper or nickel is deposited from the electroless plating solution. Ammonium complexes such as ammonium salts are preferred, but palladium compounds are preferred, and palladium chloride is particularly preferred. The noble metal compound is preferably used as an aqueous solution, and the concentration in the plating pretreatment agent is preferably 1 to 300 mg / L. In the present specification, the concentration in the pretreatment agent for plating refers to the concentration in the solution when pretreating the object to be plated.
【００１５】無電解めっきする下地を前記したような一
分子中に金属捕捉能を持つ官能基を有するシランカップ
リング剤と貴金属化合物をあらかじめ混合もしくは反応
させた液で表面処理する場合、この液は適当な溶媒、例
えば、水、メチルアルコール、エチルアルコール、２−
プロパノール、アセトン、トルエン、エチレングリコー
ル、ポリエチレングリコール、ジメチルホルムアミド、
ジメチルスルホキシド、ジオキサンなどやこれらを混合
した溶液などに溶解させた溶液で使用できる。水を使用
する場合、特に被めっき面及びめっき条件により溶液の
ｐＨを最適化する必要がある。When the surface of the substrate for electroless plating is surface-treated with a liquid in which a silane coupling agent having a functional group having a metal-capturing ability in one molecule and a noble metal compound are mixed or reacted in advance, this liquid is Suitable solvent such as water, methyl alcohol, ethyl alcohol, 2-
Propanol, acetone, toluene, ethylene glycol, polyethylene glycol, dimethylformamide,
It can be used as a solution obtained by dissolving dimethyl sulfoxide, dioxane, or the like, or a mixed solution thereof. When using water, it is necessary to optimize the pH of the solution especially depending on the surface to be plated and the plating conditions.
【００１６】布状や板状の下地に対しては、浸漬処理や
刷毛塗り等で表面コートした後に溶媒を揮発させる方法
が一般的であるが、これに限定されるものではなく表面
に均一にシランカップリング剤を付着させる方法であれ
ばよい。また、粉体に対しては、浸漬処理後溶媒を揮発
させて強制的に溶液中に含まれるシランカップリング剤
を下地表面に付着させる方法の他にこのシランカップリ
ング剤の均一な成膜性により浸漬処理状態で下地表面に
吸着が可能であることから、処理後溶媒をろ過分離して
湿った粉体を乾燥させる方法も可能である。付着状態に
よっては水洗のみで、乾燥工程を省略できる場合もあ
る。For a cloth-like or plate-like substrate, the method of dipping or brushing the surface to coat the surface and then evaporating the solvent is generally used. However, the method is not limited to this, and the surface is evenly distributed. Any method of attaching a silane coupling agent may be used. For powder, in addition to the method of volatilizing the solvent after the dipping treatment to forcibly attach the silane coupling agent contained in the solution to the surface of the substrate, the uniform film forming property of this silane coupling agent is obtained. Since it can be adsorbed to the surface of the base in the immersion treatment state, a method of filtering and separating the solvent after treatment to dry the moist powder is also possible. Depending on the adhered state, it may be possible to omit the drying step by only washing with water.
【００１７】めっき前処理剤中の一分子中に金属捕捉能
を持つ官能基を有するシランカップリング剤の濃度はこ
れに限ったものではないが、０．０００１〜１０重量％
が使いやすい。０．０００１重量％未満の場合、基材の
表面に付着する化合物量が低くなりやすく、効果が得に
くい。また、１０重量％を超えると付着量が多すぎて乾
燥しにくかったり、粉末の凝集を起こしやすくなる。The concentration of the silane coupling agent having a functional group capable of capturing a metal in one molecule of the pretreatment agent for plating is not limited to this, but is 0.0001 to 10% by weight.
Is easy to use. If it is less than 0.0001% by weight, the amount of the compound attached to the surface of the base material tends to be low, and the effect is difficult to obtain. On the other hand, if the amount exceeds 10% by weight, the amount of adhesion is too large and it is difficult to dry, or the powder easily aggregates.
【００１８】本発明においては、一分子中に金属捕捉能
を持つ官能基を有するシランカップリング剤と貴金属化
合物をあらかじめ混合もしくは反応させた液を３０℃以
上で連続使用する場合、過酸化水素を添加することによ
り、触媒効果を示す貴金属の還元反応による経時変化が
抑制され、液の安定性が向上する。過酸化水素は酸化力
が強く、また分解後は水と酸素になるため不純物の発生
もなく、本発明のめっき前処理剤に対し貴金属化合物の
還元を抑制する以外の影響が全くない。添加する過酸化
水素のめっき前処理剤中の濃度は０．１〜１０００ｍｇ
／Ｌが好ましい。０．１ｍｇ／Ｌより少ない場合は過酸
化水素の効果が十分に発揮されず、また、１０００ｍｇ
／Ｌより多い場合はシランカップリング剤が分解する恐
れがある。In the present invention, when a liquid prepared by previously mixing or reacting a silane coupling agent having a functional group having a metal-capturing ability in one molecule with a noble metal compound is continuously used at 30 ° C. or higher, hydrogen peroxide is added. By adding, the change over time due to the reduction reaction of the noble metal exhibiting the catalytic effect is suppressed, and the stability of the liquid is improved. Hydrogen peroxide has a strong oxidizing power, and since it becomes water and oxygen after decomposition, it does not generate impurities and has no effect on the pretreatment agent for plating of the present invention other than suppressing the reduction of the noble metal compound. The concentration of hydrogen peroxide added in the pretreatment agent for plating is 0.1 to 1000 mg.
/ L is preferred. If less than 0.1 mg / L, the effect of hydrogen peroxide will not be fully exerted,
If it is more than / L, the silane coupling agent may be decomposed.
【００１９】表面処理後に使用した溶剤を揮発させるに
はこの溶媒の揮発温度以上に加熱して表面を乾燥すれば
十分である。溶剤として水を用いた場合は乾燥工程を省
略し、表面処理後水洗するだけでめっきを行うことも可
能である。ただしこの際、触媒をめっき液中に持ち込ま
ないようにするため、水洗を十分に行う必要がある。In order to volatilize the solvent used after the surface treatment, it is sufficient to heat the solvent to a temperature above the volatilization temperature and dry the surface. When water is used as the solvent, it is possible to omit the drying step and perform the plating simply by washing with water after the surface treatment. However, at this time, it is necessary to sufficiently wash with water in order to prevent the catalyst from being brought into the plating solution.
【００２０】当然のことながら、めっき前処理を行う前
に被めっき面の洗浄を行っても良い。特に密着性が要求
される場合は、従来のクロム酸などによるエッチング処
理を用いても良い。無電解めっきを行う場合に、本発明
のめっき前処理剤での処理後、還元剤を含む溶液で処理
することが有効である場合もある。特に銅めっきの場合
は、還元剤としてジメチルアミン−ボラン溶液、次亜リ
ン酸ナトリウム溶液などで処理すると良い。また、本発
明の無電解めっき方法により無電解めっきを最初に行っ
て金属薄膜を形成させ、導電性のない下地にある程度の
導電性を持たせた後、電気めっきや卑なる金属との置換
めっきを行うことも可能である。本発明により、無電解
めっきで銅、ニッケル、コバルト、スズ、金などの金属
をめっきすることができる。As a matter of course, the surface to be plated may be washed before the pretreatment for plating. Particularly when adhesion is required, conventional etching treatment with chromic acid or the like may be used. When performing electroless plating, it may be effective to treat with a solution containing a reducing agent after the treatment with the plating pretreatment agent of the present invention. Particularly in the case of copper plating, it is advisable to treat with a dimethylamine-borane solution, sodium hypophosphite solution or the like as a reducing agent. In addition, electroless plating is first performed by the electroless plating method of the present invention to form a metal thin film, and a non-conductive underlayer is given a certain degree of conductivity, and then electroplating or displacement plating with a base metal It is also possible to do According to the present invention, metals such as copper, nickel, cobalt, tin and gold can be plated by electroless plating.
【００２１】[0021]
【発明の実施の形態】実施例１〜３、比較例１〜２
イミダゾールとγ−グリシドキシプロピルトリメトキシ
シランとの等モル反応生成物であるシランカップリング
剤を２５０ｍｇ／Ｌ、塩化パラジウムを５０ｍｇ／Ｌ含
んだ水溶液に、酸化剤として過酸化水素または過硫酸ナ
トリウムを添加した場合の液の安定性を、６０℃保持
（最長１０日）したときの経時変化を観察することによ
り調べた。実施例及び比較例を表１にまとめた。BEST MODE FOR CARRYING OUT THE INVENTION Examples 1 to 3 and Comparative Examples 1 to 2 250 mg / L of silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, and palladium chloride The stability of the solution when hydrogen peroxide or sodium persulfate was added as an oxidant to an aqueous solution containing 50 mg / L was examined by observing the change with time when kept at 60 ° C. (up to 10 days). Examples and comparative examples are summarized in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例１〜３に示すように、過酸化水素を
適量添加した系では１０日間の６０℃保持でいずれも沈
殿発生は無かった。それに対し、比較例１に示すよう
に、過酸化水素無添加の系では４日で沈殿が発生した。
また比較例２に示すように、過硫酸ナトリウムを１００
ｍｇ／Ｌ添加した系ではｐＨを１．０まで下げても７日
で沈殿が発生した。この系は２０〜２５℃程度の室温放
置では３０日でも沈殿の発生はなかった（特願２００１
−２３１１２９号）。比較例２により、室温よりも高い
温度で保持した場合、過酸化水素のような酸化力の強い
酸化剤を添加しないと沈殿の発生を防ぐことができない
ことがわかる。As shown in Examples 1 to 3, no precipitation occurred in the system to which an appropriate amount of hydrogen peroxide was added, which was maintained at 60 ° C. for 10 days. On the other hand, as shown in Comparative Example 1, precipitation occurred in the system containing no hydrogen peroxide in 4 days.
Also, as shown in Comparative Example 2, 100% sodium persulfate was added.
In the system containing mg / L, precipitation occurred in 7 days even if the pH was lowered to 1.0. When this system was left at room temperature of about 20 to 25 ° C., no precipitation occurred even after 30 days (Japanese Patent Application No. 2001-2001).
No. 231129). Comparative Example 2 shows that when the temperature is kept higher than room temperature, precipitation cannot be prevented unless an oxidizing agent having a strong oxidizing power such as hydrogen peroxide is added.
【００２４】また、表１の試験後にこれらの液をめっき
前処理剤として用いてガラスクロスに無電解ニッケルめ
っきを行った。処理は、めっき前処理剤浸漬（６０℃、
１５分間）、水洗、無電解ニッケルめっき（日鉱メタル
プレーティング（株）製無電解ニッケルめっき液ニコム
７Ｎ−０使用、７０℃、１５分間）の順番で行った。無
電解ニッケルめっきは実施例１〜３のいずれの液を用い
た場合も、均一性、密着性ともに問題なく行うことがで
きた。After the tests shown in Table 1, the glass cloth was subjected to electroless nickel plating using these solutions as a pretreatment agent for plating. Treatment is immersion in pretreatment agent for plating (60 ° C,
15 minutes), washing with water, and electroless nickel plating (using Nicom 7N-0 electroless nickel plating solution manufactured by Nikko Metal Plating Co., Ltd., 70 ° C., 15 minutes). The electroless nickel plating was able to be performed without problems in both uniformity and adhesiveness when any of the solutions of Examples 1 to 3 was used.
【００２５】[0025]
【発明の効果】シランカップリング剤と貴金属化合物を
あらかじめ混合もしくは反応させためっき前処理剤は、
触媒効果を示す貴金属の還元反応による経時変化が起こ
り、沈殿が発生するなど液安定性に問題があった。これ
に対し、めっき前処理剤に酸化剤を添加することで貴金
属の還元反応はある程度抑制される。しかし、３０℃以
上の温度で連続使用する場合、酸化力の弱い酸化剤添加
では十分な液安定性が得られない。本発明では、このめ
っき前処理剤に酸化力の強い過酸化水素を添加すること
で３０℃以上の温度でも貴金属の還元反応を抑制し、そ
の結果液安定性が向上した。The plating pretreatment agent in which the silane coupling agent and the noble metal compound are mixed or reacted in advance is
There was a problem with the liquid stability, such as a change over time due to the reduction reaction of the noble metal exhibiting a catalytic effect, and precipitation occurring. On the other hand, by adding an oxidizing agent to the plating pretreatment agent, the reduction reaction of the noble metal is suppressed to some extent. However, when continuously used at a temperature of 30 ° C. or higher, sufficient liquid stability cannot be obtained by adding an oxidizing agent having a weak oxidizing power. In the present invention, by adding hydrogen peroxide having a strong oxidizing power to this pretreatment agent for plating, the reduction reaction of the noble metal is suppressed even at a temperature of 30 ° C. or higher, and as a result, the liquid stability is improved.
フロントページの続き Ｆターム(参考） 4K022 AA36 BA03 BA06 BA08 BA14 BA21 CA06 CA15 CA16 CA20 CA21 CA22 DA01 Continued front page F-term (reference) 4K022 AA36 BA03 BA06 BA08 BA14 BA21 CA06 CA15 CA16 CA20 CA21 CA22 DA01
Claims (6)
するシランカップリング剤と貴金属化合物をあらかじめ
混合もしくは反応させた液に過酸化水素を添加してな
り、かつ、３０℃以上で連続使用することを特徴とする
めっき前処理剤。1. A solution prepared by previously mixing or reacting a noble metal compound with a silane coupling agent having a functional group having a metal-capturing ability in one molecule, and adding hydrogen peroxide to the solution, and continuously at 30 ° C. or higher. Pretreatment agent for plating, which is used.
０．１〜１０００ｍｇ／Ｌであることを特徴とする請求
項１記載のめっき前処理剤。2. The pretreatment agent for plating according to claim 1, wherein the concentration of hydrogen peroxide in the pretreatment agent for plating is 0.1 to 1000 mg / L.
するシランカップリング剤がアゾール系化合物とエポキ
シシラン系化合物との反応により得られたシランカップ
リング剤であることを特徴とする請求項１又は２記載の
めっき前処理剤。3. A silane coupling agent having a functional group capable of capturing a metal in one molecule is a silane coupling agent obtained by a reaction of an azole compound and an epoxysilane compound. The pretreatment agent for plating according to Item 1 or 2.
基であることを特徴とする請求項１〜３のいずれかに記
載のめっき前処理剤。4. The plating pretreatment agent according to claim 1, wherein the functional group having a metal capturing ability is an imidazole group.
ことを特徴とする請求項１〜４のいずれかに記載のめっ
き前処理剤。5. The plating pretreatment agent according to claim 1, wherein the noble metal compound is a palladium compound.
前処理剤を用い被めっき物のめっき前処理を３０℃以上
で行った後、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。6. An electroless plating characterized by performing electroless plating after performing a plating pretreatment of an object to be plated at 30 ° C. or higher using the plating pretreatment agent according to any one of claims 1 to 5. Plating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001388972A JP2003193245A (en) | 2001-12-21 | 2001-12-21 | Pretreatment agent for planting and electroless plasting method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001388972A JP2003193245A (en) | 2001-12-21 | 2001-12-21 | Pretreatment agent for planting and electroless plasting method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003193245A true JP2003193245A (en) | 2003-07-09 |
Family
ID=27597312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001388972A Pending JP2003193245A (en) | 2001-12-21 | 2001-12-21 | Pretreatment agent for planting and electroless plasting method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003193245A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073431A1 (en) * | 2004-01-29 | 2005-08-11 | Nippon Mining & Metals Co., Ltd. | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
| WO2007138795A1 (en) * | 2006-05-31 | 2007-12-06 | Technic Japan Inc. | Catalytic agent for electroless plating |
| JP2009102675A (en) * | 2007-10-22 | 2009-05-14 | Konica Minolta Holdings Inc | Plating method, plating solution and conductive pattern sheet |
| JP2009173999A (en) * | 2008-01-24 | 2009-08-06 | Nippon Mining & Metals Co Ltd | Method for producing metal-coated polyimide resin substrate having excellent resistance to thermal aging |
-
2001
- 2001-12-21 JP JP2001388972A patent/JP2003193245A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005073431A1 (en) * | 2004-01-29 | 2005-08-11 | Nippon Mining & Metals Co., Ltd. | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
| EP1760171A1 (en) * | 2004-01-29 | 2007-03-07 | Nippon Mining & Metals Co., Ltd. | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
| KR100796894B1 (en) * | 2004-01-29 | 2008-01-22 | 닛코킨조쿠 가부시키가이샤 | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
| EP1760171A4 (en) * | 2004-01-29 | 2008-01-23 | Nippon Mining Co | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
| JPWO2005073431A1 (en) * | 2004-01-29 | 2008-04-24 | 日鉱金属株式会社 | Pretreatment agent for electroless plating, electroless plating method using the same, and electroless plated product |
| US7713340B2 (en) | 2004-01-29 | 2010-05-11 | Nippon Mining & Metals Co., Ltd. | Pretreating agent for electroless plating, method of electroless plating using the same and product of electroless plating |
| JP4711415B2 (en) * | 2004-01-29 | 2011-06-29 | Ｊｘ日鉱日石金属株式会社 | Electroless plating pretreatment agent, electroless plating method using the same, and electroless plated product |
| WO2007138795A1 (en) * | 2006-05-31 | 2007-12-06 | Technic Japan Inc. | Catalytic agent for electroless plating |
| JP2007321189A (en) * | 2006-05-31 | 2007-12-13 | Technic Japan Inc | Catalytic agent for electroless plating |
| JP2009102675A (en) * | 2007-10-22 | 2009-05-14 | Konica Minolta Holdings Inc | Plating method, plating solution and conductive pattern sheet |
| JP2009173999A (en) * | 2008-01-24 | 2009-08-06 | Nippon Mining & Metals Co Ltd | Method for producing metal-coated polyimide resin substrate having excellent resistance to thermal aging |
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