JP2003013241A - Pretreatment solution for electroless nickel plating onto copper or copper alloy and method for electroless nickel plating - Google Patents
Pretreatment solution for electroless nickel plating onto copper or copper alloy and method for electroless nickel platingInfo
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- JP2003013241A JP2003013241A JP2001195855A JP2001195855A JP2003013241A JP 2003013241 A JP2003013241 A JP 2003013241A JP 2001195855 A JP2001195855 A JP 2001195855A JP 2001195855 A JP2001195855 A JP 2001195855A JP 2003013241 A JP2003013241 A JP 2003013241A
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- JP
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- Prior art keywords
- nickel plating
- electroless nickel
- copper
- silane coupling
- coupling agent
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅あるいは銅合金
上への無電解ニッケルめっき用前処理液、およびそれを
用いて銅あるいは銅合金を表面処理して、無電解ニッケ
ルめっきする方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pretreatment liquid for electroless nickel plating on copper or a copper alloy, and a method for surface-treating copper or a copper alloy using the same to perform electroless nickel plating.
【０００２】[0002]
【従来の技術】銅あるいは銅合金上に無電解ニッケルめ
っきを行うためには触媒の付与が必要であり、一般的に
は塩化パラジウムの塩酸溶液への浸漬による置換めっき
でパラジウムを付与する方法が使われている。しかしこ
の方法の場合、置換反応により溶出した銅が触媒液中に
徐々に蓄積するため、液平衡の関係で溶出した銅が置換
反応の妨げとなってくる。2. Description of the Related Art In order to perform electroless nickel plating on copper or a copper alloy, it is necessary to apply a catalyst. Generally, a method of applying palladium by displacement plating by immersing palladium chloride in a hydrochloric acid solution is known. It is used. However, in this method, since the copper eluted by the substitution reaction gradually accumulates in the catalyst solution, the copper eluted due to the liquid equilibrium hinders the substitution reaction.
【０００３】[0003]
【発明が解決しようとする課題】そのため触媒液を反復
使用して触媒付与をある一定時間で行い続けていると、
ある時点で無電解ニッケルめっきを行うのに十分な量の
パラジウム触媒が付着しなくなり、新しい触媒液の建浴
が必要となる。パラジウムは高価な貴金属であり、建浴
頻度が多くなるほどそれだけ使用量が多くなるため、こ
の建浴頻度を減らす方法が求められていた。Therefore, if the catalyst is continuously applied for a certain period of time by repeatedly using the catalyst solution,
At a certain point, a sufficient amount of palladium catalyst for performing electroless nickel plating does not adhere, and a new bath for the catalyst solution is required. Palladium is an expensive precious metal, and the more the bath is built, the more it is used. Therefore, there has been a demand for a method of reducing the bath frequency.
【０００４】本発明は、こうした実情の下に、銅あるい
は銅合金上に無電解ニッケルめっきを行う際に使用する
触媒液の建浴頻度を少なくする前処理液を提供すること
を目的とし、またその前処理液を用いて無電解ニッケル
めっき方法を提供することを目的とする。Under these circumstances, an object of the present invention is to provide a pretreatment liquid which reduces the frequency of bath preparation of a catalyst liquid used when electroless nickel plating is performed on copper or a copper alloy. It is an object of the present invention to provide an electroless nickel plating method using the pretreatment liquid.
【０００５】[0005]
【課題を解決するための手段】本発明者は、鋭意検討し
た結果、前記前処理剤として、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を利用することが有用で
あることを見出し、本発明に至った。As a result of extensive studies, the present inventor has found that it is useful to use a silane coupling agent having a functional group having a metal capturing ability as the pretreatment agent. 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
貴金属化合物を以下に示す重量比であらかじめ混合もし
くは反応させて得られた液からなる、銅あるいは銅合金
上への無電解ニッケルめっき用前処理液、
１／１０＜シランカップリング剤／貴金属化合物＜５／
１
（２）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）記載の無電解ニッケ
ルめっき用前処理液、（３）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）記載
の無電解ニッケルめっき用前処理液、（４）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）記載の無電解ニッケルめっき用前処理液、（５）
前記（１）〜（４）のいずれか一つに記載の無電解ニッ
ケルめっき用前処理剤で銅あるいは銅合金を表面処理し
た後、無電解ニッケルめっきすることを特徴とする無電
解ニッケルめっき方法、に関する。That is, the present invention provides (1) a liquid obtained 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 in the following weight ratios. Pretreatment liquid for electroless nickel plating on copper or copper alloy, 1/10 <silane coupling agent / noble metal compound <5 /
1 (2) A silane coupling agent having a functional group having a metal-capturing ability in one molecule is a silane coupling agent obtained by reacting an azole compound and an epoxysilane compound. (1) A pretreatment liquid for electroless nickel plating, (3) A pretreatment liquid for electroless nickel plating according to (1), wherein the functional group having a metal capturing ability is an imidazole group. ) The pretreatment liquid for electroless nickel plating according to (1) above, wherein the noble metal compound is a palladium compound,
A method for electroless nickel plating, comprising surface-treating copper or a copper alloy with the pretreatment agent for electroless nickel plating according to any one of (1) to (4), and then performing electroless nickel plating. About.
【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】本発明の前処理剤に使用する金属捕捉能を
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、メルカプト基などを有す
るシランカップリング剤が挙げられる。これらの中でも
アゾール基を有するものが好ましい。さらに、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。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 having a functional group having a metal-capturing ability used in the pretreatment agent of the present invention is not limited to these, but an amino group, a carboxyl group, an azole group, a hydroxyl group, and a mercapto. Examples thereof include a silane coupling agent having a group. Among these, those having an azole group are preferable. Further, as the azole group, imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, bendazole, indazole, benzimidazole, benzotriazole and the like. Can be mentioned. Among them, an imidazole group is particularly preferable. Further, the silane coupling agent, in addition to the noble metal ion trapping group,
A compound having a -SiX 1 X 2 X 3 group, X 1, X 2,
X 3 means an alkyl group, a halogen or an alkoxy group, and may be any functional group that can be fixed to the object to be plated.
X 1 , X 2 and X 3 may be the same or different.
【０００９】このようなシランカップリング剤自体は、
公知である。例えば、特開平６−２５６３５８号公報に
は、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が開示されている。
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、Such a silane coupling agent itself is
It is known. For example, JP-A-6-256358 discloses a silane coupling agent obtained by reacting an azole compound with an epoxysilane compound.
Further, as the epoxy group-containing silane compound to be reacted with such a nitrogen-containing heterocyclic azole compound,
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】（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）で示されるエポキシシラ
ンカップリング剤が好ましい。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。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。(Wherein R 1 and R 2 are hydrogen or have 1 to 1 carbon atoms)
The epoxy silane coupling agent represented by the alkyl group of 3 and n is 1 to 3) is preferable. The reaction between the azole compound and the epoxy group-containing silane compound is described in JP-A-6-
It can be carried out under the conditions described in JP-A-256358. For example, at 80 to 200 ° C., 0.1 to 10 mol of the epoxy group-containing silane compound is added dropwise to 1 mol of the azole compound, and the reaction is performed for 5 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. 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-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane.
【００１２】また、前記貴金属化合物としては、無電解
めっき液から銅あるいは銅合金表面にニッケルを析出さ
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、処理する溶
液中の濃度は５〜１００ｍｇ／Ｌが好ましい。The precious metal compound may be a chloride, hydroxide or oxide of palladium, silver, platinum, gold or the like which exhibits a catalytic effect when nickel is deposited on the surface of copper or copper alloy from an electroless plating solution. Ammonium complexes such as sulfates, ammonium salts and the like can be mentioned, but a palladium compound is preferable, and palladium chloride is particularly preferable. The noble metal compound is preferably used as an aqueous solution, and the concentration of the solution to be treated is preferably 5 to 100 mg / L.
【００１３】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
リング剤と貴金属イオンをあらかじめ混合もしくは反応
させた前処理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。銅あるいは銅合
金に対しては、浸漬処理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。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。前処理溶液中の
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．
００１〜１０重量％が使いやすい。０．００１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。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、触媒が被めっき物の表面か
ら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 the case of surface-treating the base material for electroless plating with a pretreatment liquid in which a silane coupling agent having a functional group having a metal-capturing ability in one molecule and a noble metal ion are mixed or reacted in advance, The solution is a solution prepared by dissolving a suitable solvent, for example, water, methyl alcohol, ethyl alcohol, 2-propanol, acetone, toluene, ethylene glycol, polyethylene glycol, dimethylformamide, dimethylsulfoxide, dioxane, or a mixture thereof. Can be used in.
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. For copper or copper alloys, a method of vaporizing the solvent after surface coating by dipping treatment is generally used, but the method is not limited to this, and a method of uniformly attaching a silane coupling agent to the surface can be used. I wish I had it. Depending on the adhered state, it may be possible to omit the drying step by only washing with water. The concentration of the silane coupling agent having a functional group having a metal-capturing ability in one molecule in the pretreatment solution is not limited to this, but may be 0.
001-10 wt% is easy to use. If it is less than 0.001% 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. In order to volatilize the solvent used after the surface treatment, it is sufficient to dry the surface by heating above the volatilization temperature of this solvent. 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, in order to prevent the catalyst from being brought into the plating solution from the surface of the object to be plated, it is necessary to sufficiently wash with water.
【００１４】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以下に示す重
量比であらかじめ混合もしくは反応させた、銅あるいは
銅合金上への無電解ニッケルめっき用前処理液を用いる
と、室温（１０〜３０℃）での前処理で無電解ニッケル
めっきが可能となる。
１／１０＜シランカップリング剤／貴金属化合物＜５／
１Before electroless nickel plating on copper or copper alloy, which is 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 in the following weight ratios. When the treatment liquid is used, electroless nickel plating can be performed by pretreatment at room temperature (10 to 30 ° C.). 1/10 <silane coupling agent / noble metal compound <5 /
1
【００１５】上記の重量比が１／１０未満の場合、シラ
ンカップリング剤の割合が少なすぎるため、金属捕捉能
が十分に働かない。また上記の重量比が５／１を超える
場合、シランカップリング剤同士の相互作用が大きくな
り、やはり金属捕捉能が十分に働かない。また、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以下に示す重量比であらかじめ混
合もしくは反応させた、銅あるいは銅合金上への無電解
ニッケルめっき用前処理液を用いると、室温（１０〜３
０℃）でのさらに短時間の前処理で無電解ニッケルめっ
きが可能となる。
１／２＜シランカップリング剤／貴金属化合物＜２／１
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（希硫酸洗浄など）を行っても良い。When the above weight ratio is less than 1/10, the ratio of the silane coupling agent is too small and the metal capturing ability does not work sufficiently. On the other hand, when the above weight ratio exceeds 5/1, the interaction between the silane coupling agents becomes large, and the metal capturing ability still does not work sufficiently. In addition, a pretreatment for electroless nickel plating on copper or copper alloy, which is 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 in the following weight ratios. When using liquid, room temperature (10-3
Electroless nickel plating becomes possible by pretreatment at 0 ° C. for a shorter time. 1/2 <silane coupling agent / noble metal compound <2/1 Needless to say, the surface to be plated (washing with dilute sulfuric acid or the like) may be washed before the plating pretreatment.
【００１６】[0016]
【実施例】被めっき素材として電解銅箔（厚さ２０μ
ｍ）を用い、これを５％希硫酸洗浄（１分間）、水洗
後、実施例１〜４、比較例１〜２に示す前処理液に２０
℃である一定時間浸漬、水洗し、以下に示す条件で無電
解ニッケルめっきを行った。[Example] Electroplated copper foil (thickness: 20μ)
m) was used, and this was washed with 5% dilute sulfuric acid (for 1 minute) and washed with water, and the pretreatment liquids shown in Examples 1 to 4 and Comparative Examples 1 to 20 were used.
It was immersed in water for a certain period of time at ℃, washed with water, and electroless nickel plating was performed under the following conditions.
【００１７】硫酸ニッケル：２０ｇ／Ｌ ＥＤＴＡ：１０ｇ／Ｌ 硫酸アンモニウム：４０ｇ／Ｌ 次亜リン酸ナトリウム：２０ｇ／Ｌ ｐＨ：９．０ 浴温：３０℃ めっき時間：１分間Nickel sulfate: 20 g / L EDTA: 10 g / L Ammonium sulfate: 40 g / L Sodium hypophosphite: 20 g / L pH: 9.0 Bath temperature: 30 ℃ Plating time: 1 minute
【００１８】実施例１
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５０ｍｇ／Ｌ、塩化パラジウムを５０ｍｇ／Ｌ含ん
だ水溶液。Example 1 An aqueous solution containing 50 mg / L of a silane coupling agent, which is a reaction product of equimolar amounts of imidazole and γ-glycidoxypropyltrimethoxysilane, and 50 mg / L of palladium chloride.
【００１９】実施例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４０ｍｇ／Ｌ、塩化パラジウムを４０ｍｇ／Ｌ含ん
だ水溶液。Example 2 An aqueous solution containing 40 mg / L of a silane coupling agent, which is a reaction product of equimolar amounts of imidazole and γ-glycidoxypropyltrimethoxysilane, and 40 mg / L of palladium chloride.
【００２０】実施例３
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３０ｍｇ／Ｌ、塩化パラジウムを３０ｍｇ／Ｌ含ん
だ水溶液。Example 3 An aqueous solution containing 30 mg / L of a silane coupling agent which is a reaction product of equimolar amounts of imidazole and γ-glycidoxypropyltrimethoxysilane and 30 mg / L of palladium chloride.
【００２１】実施例４
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２０ｍｇ／Ｌ、塩化パラジウムを２０ｍｇ／Ｌ含ん
だ水溶液。Example 4 An aqueous solution containing 20 mg / L of a silane coupling agent which is a reaction product of equimolar amounts of imidazole and γ-glycidoxypropyltrimethoxysilane and 20 mg / L of palladium chloride.
【００２２】比較例１
塩化パラジウムを５０ｍｇ／Ｌ、３６％濃塩酸を１０ｍ
Ｌ／Ｌ含んだ水溶液。Comparative Example 1 Palladium chloride (50 mg / L) and 36% concentrated hydrochloric acid (10 m) were added.
An aqueous solution containing L / L.
【００２３】比較例２
塩化パラジウムを４０ｍｇ／Ｌ、３６％濃塩酸を１０ｍ
Ｌ／Ｌ含んだ水溶液。Comparative Example 2 40 mg / L of palladium chloride and 10 m of 36% concentrated hydrochloric acid
An aqueous solution containing L / L.
【００２４】いずれの例でも前処理液への浸漬時間３０
秒以内でニッケルめっきが析出した。さらに銅の溶出の
影響を調べるため、前処理液中に塩化銅を徐々に添加し
た。前処理液中銅濃度とニッケルめっきが析出するのに
最低限必要な前処理液浸漬時間との関係を、表１及び図
１に示す。In each case, the immersion time in the pretreatment liquid was 30.
Nickel plating was deposited within seconds. Furthermore, in order to investigate the influence of copper elution, copper chloride was gradually added to the pretreatment solution. The relationship between the copper concentration in the pretreatment liquid and the minimum immersion time of the pretreatment liquid for nickel plating to deposit is shown in Table 1 and FIG.
【００２５】[0025]
【表１】 [Table 1]
【００２６】前処理液への浸漬時間６０秒で比較する
と、一般的な塩化パラジウム・塩酸前処理液を使用した
比較例１、２の場合、塩化パラジウム濃度が５０，４０
ｍｇ／Ｌであっても銅濃度が５００，２５０ｍｇ／Ｌま
でしかめっきが可能でないが、実施例１〜４に示すシラ
ンカップリング剤を含む前処理液の場合、同じ塩化パラ
ジウム濃度（実施例１、２）では銅濃度が５倍以上でも
めっきが可能であり、また塩化パラジウム濃度が２０ｍ
ｇ／Ｌ（実施例４）と低くても銅濃度が６００ｍｇ／Ｌ
までめっきが可能である。Comparing the immersion time in the pretreatment liquid for 60 seconds, in the case of Comparative Examples 1 and 2 using a general palladium chloride / hydrochloric acid pretreatment liquid, the palladium chloride concentration was 50,40.
Even if the concentration is mg / L, the copper concentration can be plated only up to 500 and 250 mg / L. However, in the case of the pretreatment liquid containing the silane coupling agent shown in Examples 1 to 4, the same palladium chloride concentration (Example 1 In 2), plating is possible even if the copper concentration is 5 times or more, and the palladium chloride concentration is 20 m.
Copper concentration is 600 mg / L even though it is as low as g / L (Example 4)
It is possible to plate up to.
【００２７】実施例１及び比較例１の前処理液１００ｍ
Ｌに電解銅箔（３０ｍｍ×４０ｍｍ×２０μｍ）を２０
℃で３００分間浸漬した時の銅溶出量（スターラー撹拌
速度０及び１００ｒｐｍ）を表２に示す。スターラー撹
拌速度０ｒｐｍの場合、実施例１の銅溶出量は比較例１
の半分以下であり、１００ｒｐｍの場合、その差はさら
に大きくなり約１／８となる。100 m of pretreatment liquid of Example 1 and Comparative Example 1
20 electrolytic copper foil (30 mm x 40 mm x 20 μm) on L
Table 2 shows the copper elution amount (stirrer stirring speed 0 and 100 rpm) when immersed at 300 ° C. for 300 minutes. When the stirrer stirring speed was 0 rpm, the copper elution amount of Example 1 was Comparative Example 1
Is less than half of the above, and at 100 rpm, the difference becomes even larger and becomes about 1/8.
【００２８】[0028]
【表２】 [Table 2]
【００２９】以上のように、本発明の前処理液を使用す
ることにより前処理液中への銅の溶出量が減少し、さら
に前処理液中の銅の許容濃度も増加する結果、前処理液
の建浴頻度を著しく減少することができ、高価なパラジ
ウム使用量を抑制することが可能となる。As described above, by using the pretreatment liquid of the present invention, the elution amount of copper into the pretreatment liquid is reduced and the allowable concentration of copper in the pretreatment liquid is also increased. The bathing frequency of the liquid can be significantly reduced, and the amount of expensive palladium used can be suppressed.
【００３０】[0030]
【発明の効果】以上説明したように、銅あるいは銅合金
上に無電解ニッケルめっきを行うためには触媒の付与が
必要であるが、従来はその触媒付与を銅あるいは銅合金
上にパラジウムなどを置換めっきすることにより行って
きた。As described above, in order to perform electroless nickel plating on copper or a copper alloy, it is necessary to add a catalyst. Conventionally, the catalyst is added to copper or a copper alloy by palladium or the like. This was done by displacement plating.
【００３１】しかし、この置換反応による触媒付着は、
すでに述べたように、触媒液中に銅イオンを蓄積させて
次第に触媒付着を妨げるようになり、その結果、高価な
触媒液の建浴を要することとなる。これに対して、本発
明の前処理液の場合は、置換めっきによる触媒付着でな
く、銅あるいは銅合金上にシランカップリング剤が固着
することにより、該シランカップリング剤に結合した触
媒も同時にその銅あるいは銅合金上に付着することによ
り行われるので、銅の溶出の影響を少なくすることがで
き、新しい触媒液（前処理液）の建浴頻度を著しく低減
することができる。However, the catalyst attachment by this substitution reaction is
As described above, copper ions are accumulated in the catalyst solution and the catalyst adhesion is gradually hindered. As a result, an expensive bath for the catalyst solution is required. On the other hand, in the case of the pretreatment liquid of the present invention, the catalyst attached by displacement plating is not adhered, but the silane coupling agent is fixed on copper or a copper alloy so that the catalyst bound to the silane coupling agent is also present. Since it is carried out by depositing on the copper or copper alloy, the influence of elution of copper can be reduced, and the frequency of building a new catalyst solution (pretreatment solution) can be significantly reduced.
【図１】前処理液中、銅濃度とニッケルめっきが析出す
るのに最低限必要な前処理液浸漬時間との関係を示すグ
ラフ。FIG. 1 is a graph showing a relationship between a copper concentration in a pretreatment liquid and a minimum immersion time of the pretreatment liquid for nickel plating to be deposited.
Claims (5)
するシランカップリング剤と貴金属化合物を以下に示す
重量比であらかじめ混合もしくは反応させて得られた液
からなる、銅あるいは銅合金上への無電解ニッケルめっ
き用前処理液。 １／１０＜シランカップリング剤／貴金属化合物＜５／
１1. A copper or copper alloy comprising a liquid obtained by previously mixing or reacting a silane coupling agent having a functional group having a metal-capturing ability in one molecule and a noble metal compound in the following weight ratios. Pretreatment liquid for electroless nickel plating. 1/10 <silane coupling agent / noble metal compound <5 /
1
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記載の無電解
ニッケルめっき用前処理液。2. The silane coupling agent having a functional group having a metal-capturing ability in one molecule is a silane coupling agent obtained by the reaction of an azole compound and an epoxysilane compound. Item 1. A pretreatment liquid for electroless nickel plating according to Item 1.
基であることを特徴とする請求項１記載の無電解ニッケ
ルめっき用前処理液。3. The pretreatment liquid for electroless nickel plating 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記載の無電解ニッケルめっき
用前処理液。4. The pretreatment liquid for electroless nickel plating according to claim 1, wherein the noble metal compound is a palladium compound.
電解ニッケルめっき用前処理剤で銅あるいは銅合金を表
面処理した後、無電解ニッケルめっきすることを特徴と
する無電解ニッケルめっき方法。5. An electroless nickel plating process, which comprises subjecting copper or a copper alloy to a surface treatment with the pretreatment agent for electroless nickel plating according to claim 1 and then performing electroless nickel plating. Plating method.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001195855A JP3758532B2 (en) | 2001-06-28 | 2001-06-28 | Pretreatment liquid for electroless nickel plating on copper or copper alloy and electroless nickel plating method |
| CNB028022629A CN1283832C (en) | 2001-06-28 | 2002-04-18 | Surface treatment agent, surface treated product and electroless nickel plating method using same |
| PCT/JP2002/003865 WO2003002780A1 (en) | 2001-06-28 | 2002-04-18 | Surface treatment agent, article surface-treated therewith and method of nickel plating using the agent |
| KR1020037001348A KR100568389B1 (en) | 2001-06-28 | 2002-04-18 | Surface treatment agent, surface treatment material using it and electroless nickel plating method |
| TW091112606A TWI229703B (en) | 2001-06-28 | 2002-06-11 | Surface treatment agent, and surface-treated article and electroless nickel plating method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001195855A JP3758532B2 (en) | 2001-06-28 | 2001-06-28 | Pretreatment liquid for electroless nickel plating on copper or copper alloy and electroless nickel plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003013241A true JP2003013241A (en) | 2003-01-15 |
| JP3758532B2 JP3758532B2 (en) | 2006-03-22 |
Family
ID=19033763
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001195855A Expired - Lifetime JP3758532B2 (en) | 2001-06-28 | 2001-06-28 | Pretreatment liquid for electroless nickel plating on copper or copper alloy and electroless nickel plating method |
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| Country | Link |
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| JP (1) | JP3758532B2 (en) |
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| US20070120880A1 (en) * | 2003-11-05 | 2007-05-31 | Toshifumi Kawamura | Inkjet ink composition |
| JP2007321189A (en) * | 2006-05-31 | 2007-12-13 | Technic Japan Inc | Catalytic agent for electroless plating |
| JPWO2008032839A1 (en) * | 2006-09-15 | 2010-01-28 | 宇部日東化成株式会社 | Metal layer-coated substrate and method for producing the same |
| JP2011509344A (en) * | 2007-12-21 | 2011-03-24 | ラム リサーチ コーポレーション | Activation solution for electroless plating of dielectric layers |
| US8182873B2 (en) | 2003-06-09 | 2012-05-22 | Nippon Mining & Metals Co., Ltd. | Method for electroless plating and metal-plated article |
| JP2015229788A (en) * | 2014-06-05 | 2015-12-21 | 奥野製薬工業株式会社 | Composition for forming electroless plating underlayer |
| US9382627B2 (en) | 2012-02-24 | 2016-07-05 | Lam Research Corporation | Methods and materials for anchoring gapfill metals |
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2001
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8182873B2 (en) | 2003-06-09 | 2012-05-22 | Nippon Mining & Metals Co., Ltd. | Method for electroless plating and metal-plated article |
| US20070120880A1 (en) * | 2003-11-05 | 2007-05-31 | Toshifumi Kawamura | Inkjet ink composition |
| JP2007321189A (en) * | 2006-05-31 | 2007-12-13 | Technic Japan Inc | Catalytic agent for electroless plating |
| JPWO2008032839A1 (en) * | 2006-09-15 | 2010-01-28 | 宇部日東化成株式会社 | Metal layer-coated substrate and method for producing the same |
| JP2011509344A (en) * | 2007-12-21 | 2011-03-24 | ラム リサーチ コーポレーション | Activation solution for electroless plating of dielectric layers |
| US9382627B2 (en) | 2012-02-24 | 2016-07-05 | Lam Research Corporation | Methods and materials for anchoring gapfill metals |
| JP2015229788A (en) * | 2014-06-05 | 2015-12-21 | 奥野製薬工業株式会社 | Composition for forming electroless plating underlayer |
| CN120099510A (en) * | 2025-05-12 | 2025-06-06 | 深圳金湖电镀有限公司 | Continuous high-phosphorus chemical nickel plating method capable of reducing crystallization of plating solution |
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