JP3758532B2 - Pretreatment liquid for electroless nickel plating on copper or copper alloy and electroless nickel plating method - Google Patents
Pretreatment liquid for electroless nickel plating on copper or copper alloy and electroless nickel plating method Download PDFInfo
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【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。
【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。
【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。
【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。
【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。
【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と溶媒からなる、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液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。
【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。
【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。
【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、
【００１０】
【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）
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。
【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。
【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。
【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＜５／１
【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（１０〜３０℃）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。
【００１６】
【実施例】
被めっき素材として電解銅箔（厚さ２０μｍ）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。
【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
【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。
【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。
【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。
【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。
【００２２】
比較例１
塩化パラジウムを５０ｍｇ／Ｌ、３６％濃塩酸を１０ｍＬ／Ｌ含んだ水溶液。
【００２３】
比較例２
塩化パラジウムを４０ｍｇ／Ｌ、３６％濃塩酸を１０ｍＬ／Ｌ含んだ水溶液。
【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。
【００２５】
【表１】
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５０，４０ｍｇ／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２０ｍｇ／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。
【００２７】
実施例１及び比較例１の前処理液１００ｍＬ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。
【００２８】
【表２】
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。
【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。
【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。
【図面の簡単な説明】
【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。[0001]
BACKGROUND 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 copper alloy using the same and electroless nickel plating.
[0002]
[Prior art]
In order to perform electroless nickel plating on copper or a copper alloy, it is necessary to apply a catalyst. In general, a method of applying palladium by displacement plating by dipping palladium chloride in a hydrochloric acid solution is used. However, in this method, the copper eluted by the substitution reaction gradually accumulates in the catalyst solution, so that the copper eluted due to the liquid equilibrium hinders the substitution reaction.
[0003]
[Problems to be solved by the invention]
For this reason, if the catalyst application is continued for a certain period of time by repeatedly using the catalyst solution, a sufficient amount of palladium catalyst for electroless nickel plating does not adhere at a certain point in time, and a new catalyst solution bath is created. Necessary. Palladium is an expensive noble metal, and the amount of use increases as the bathing frequency increases. Therefore, a method for reducing the bathing frequency has been demanded.
[0004]
Under such circumstances, the present invention aims to provide a pretreatment liquid that reduces the frequency of the catalyst solution used when performing electroless nickel plating on copper or a copper alloy, and the pretreatment thereof. An object is to provide an electroless nickel plating method using a liquid.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that it is useful to use a silane coupling agent having a functional group having a metal-capturing ability as the pretreatment agent, and have reached the present invention.
[0006]
That is, the present invention
(1) On a copper or copper alloy comprising a liquid and a solvent 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 at a weight ratio shown below. Pretreatment liquid for electroless nickel plating,
1/10 <silane coupling agent / noble metal compound <5/1
(2) The above-mentioned (1), wherein the silane coupling agent having a functional group having a metal-capturing ability in one molecule is a silane coupling agent obtained by a reaction between an azole compound and an epoxysilane compound. ) Pre-treatment solution for electroless nickel plating,
(3) The pretreatment liquid for electroless nickel plating according to the above (1), wherein the functional group having a metal capturing ability is an imidazole group,
(4) The pretreatment liquid for electroless nickel plating according to (1), wherein the noble metal compound is a palladium compound,
(5) After electrotreating copper or a copper alloy with the pretreatment liquid for electroless nickel plating according to any one of the above (1) to (4), electroless nickel plating is performed. Nickel plating method,
About.
[0007]
In the present invention, it is important to use the specific silane coupling agent. In other words, 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 expresses the activity of the plating catalyst. By being a silane coupling agent, the material to be plated It becomes possible to express the adhesiveness.
[0008]
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 includes an amino group, a carboxyl group, an azole group, a hydroxyl group, a mercapto group, and the like. The silane coupling agent which has is mentioned. Among these, those having an azole group are preferable. Further, examples of the azole group include imidazole, oxazole, thiazole, selenazole, pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole, bendazole, indazole, benzimidazole, benzotriazole and the like. Can be mentioned. Of these, an imidazole group is particularly preferable. Also, the a silane coupling agent, in addition to the noble metal ion capturing group, a compound having a -SiX 1 X 2 X 3 group, X 1, X 2, X 3 is an alkyl group, such as halogen or alkoxy group And 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.
[0009]
Such silane coupling agents are known per se. For example, JP-A-6-256358 discloses a silane coupling agent obtained by a reaction of an azole compound and an epoxy silane compound. In addition, as an epoxy group-containing silane compound to be reacted with such a nitrogen-containing heterocyclic azole compound,
[0010]
[Chemical 1]
(Wherein R 1 and R 2 are hydrogen or an alkyl group having 1 to 3 carbon atoms, n is 1 to 3)
The epoxysilane coupling agent shown by these is preferable. 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 10 mol of an epoxy group-containing silane compound is dropped at 80 to 200 ° C. with respect 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 required, but an organic solvent such as chloroform, dioxanemethanol or ethanol may be used. Other examples of the silane coupling agent having a metal scavenging ability used in the present invention include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane. N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane and the like.
[0012]
In addition, the noble metal compound includes palladium, silver, platinum, gold and other chlorides, hydroxides, oxides, sulfates that exhibit a catalytic effect when nickel is deposited on the surface of copper or a copper alloy from an electroless plating solution. And ammine complexes such as ammonium salts, among which palladium compounds, particularly palladium chloride, are preferred. The noble metal compound is preferably used as an aqueous solution, and the concentration in the solution to be treated is preferably 5 to 100 mg / L.
[0013]
When the surface of the substrate to be electrolessly plated is treated with a pretreatment liquid in which a silane coupling agent having a functional group having a metal capturing ability in one molecule as described above and a precious metal ion are mixed or reacted in advance, this liquid is suitable. It can be used in a solution obtained by dissolving in a suitable solvent such as water, methyl alcohol, ethyl alcohol, 2-propanol, acetone, toluene, ethylene glycol, polyethylene glycol, dimethylformamide, dimethyl sulfoxide, dioxane, or a mixture thereof. . When water is used, it is necessary to optimize the pH of the solution depending on the surface to be plated and the plating conditions. For copper or copper alloys, the method of volatilizing the solvent after surface coating by dipping is common, but this is not a limitation, and it is a method of uniformly attaching a silane coupling agent to the surface. I just need it. Depending on the state of adhesion, there may be a case where the drying step can be omitted only by 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 0.001 to 10% by weight is easy to use. If it is less than 0.001% by weight, the amount of the compound adhering to the surface of the substrate tends to be low, and the effect is difficult to obtain. On the other hand, if it exceeds 10% by weight, it is difficult to dry because the amount of adhesion is too much, or the powder tends to agglomerate. 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 the solvent. When water is used as a solvent, it is possible to omit the drying step and perform plating only by washing with water after the surface treatment. However, in this case, it is necessary to perform sufficient washing with water in order to prevent the catalyst from being brought into the plating solution from the surface of the object to be plated.
[0014]
A pretreatment solution for electroless nickel plating on copper or a copper alloy, 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 at a weight ratio shown below. When used, electroless nickel plating is possible by pretreatment at room temperature (10 to 30 ° C.).
1/10 <silane coupling agent / noble metal compound <5/1
[0015]
When the weight ratio is less than 1/10, the ratio of the silane coupling agent is too small, so that the metal capturing ability does not work sufficiently. Moreover, when said weight ratio exceeds 5/1, interaction between silane coupling agents will become large and a metal capture | capture ability will not fully work too. In addition, a pretreatment for electroless nickel plating on copper or a copper alloy, 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 at a weight ratio shown below. When the liquid is used, electroless nickel plating can be performed with a shorter pretreatment at room temperature (10 to 30 ° C.).
1/2 <silane coupling agent / noble metal compound <2/1
As a matter of course, the surface to be plated may be cleaned (such as dilute sulfuric acid cleaning) before the plating pretreatment.
[0016]
【Example】
Electrolytic copper foil (thickness 20 μm) is used as a material to be plated, and after washing with 5% dilute sulfuric acid (for 1 minute) and water, the pretreatment liquids shown in Examples 1 to 4 and Comparative Examples 1 to 2 are applied at 20 ° C. It was immersed for a certain period of time and washed with water, and electroless nickel plating was performed under the following conditions.
[0017]
Nickel sulfate: 20g / L
EDTA: 10g / L
Ammonium sulfate: 40 g / L
Sodium hypophosphite: 20 g / L
pH: 9.0
Bath temperature: 30 ° C
Plating time: 1 minute 【0018】
Example 1
An aqueous solution containing 50 mg / L of a silane coupling agent that is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane and 50 mg / L of palladium chloride.
[0019]
Example 2
An aqueous solution containing 40 mg / L of a silane coupling agent that is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane and 40 mg / L of palladium chloride.
[0020]
Example 3
An aqueous solution containing 30 mg / L of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, and 30 mg / L of palladium chloride.
[0021]
Example 4
An aqueous solution containing 20 mg / L of a silane coupling agent and 20 mg / L of palladium chloride, which are equimolar reaction products of imidazole and γ-glycidoxypropyltrimethoxysilane.
[0022]
Comparative Example 1
An aqueous solution containing 50 mg / L of palladium chloride and 10 mL / L of 36% concentrated hydrochloric acid.
[0023]
Comparative Example 2
An aqueous solution containing 40 mg / L of palladium chloride and 10 mL / L of 36% concentrated hydrochloric acid.
[0024]
In any example, nickel plating was deposited within 30 seconds of immersion time in the pretreatment liquid. Furthermore, in order to investigate the influence of copper elution, copper chloride was gradually added to the pretreatment liquid. Table 1 and FIG. 1 show the relationship between the copper concentration in the pretreatment liquid and the minimum pretreatment liquid immersion time necessary for precipitation of nickel plating.
[0025]
[Table 1]
When compared with a pretreatment liquid immersion time of 60 seconds, in the case of Comparative Examples 1 and 2 using a general palladium chloride / hydrochloric acid pretreatment liquid, the copper concentration was 50.40 mg / L even when the palladium chloride concentration was 50,40 mg / L. Although plating is possible only up to 500,250 mg / L, in the case of the pretreatment liquid containing the silane coupling agent shown in Examples 1 to 4, the copper concentration is 5 times or more at the same palladium chloride concentration (Examples 1 and 2). However, plating is possible, and even when the palladium chloride concentration is as low as 20 mg / L (Example 4), the plating can be performed up to a copper concentration of 600 mg / L.
[0027]
Table 2 shows copper elution amounts (
[0028]
[Table 2]
As described above, by using the pretreatment liquid of the present invention, the amount of copper eluted into the pretreatment liquid is reduced, and the allowable concentration of copper in the pretreatment liquid is also increased. The bath frequency can be significantly reduced, and the amount of expensive palladium used can be suppressed.
[0030]
【The invention's effect】
As described above, in order to perform electroless nickel plating on copper or a copper alloy, it is necessary to apply a catalyst. Conventionally, the catalyst is applied by replacing palladium or the like on copper or a copper alloy. I went.
[0031]
However, as described above, the catalyst adhesion due to this substitution reaction causes copper ions to accumulate in the catalyst liquid and gradually hinder the catalyst adhesion. As a result, an expensive catalyst liquid bath is required. . On the other hand, in the case of the pretreatment liquid of the present invention, the catalyst bonded to the silane coupling agent is not simultaneously adhered to the silane coupling agent by adhering the silane coupling agent on the copper or copper alloy, instead of attaching the catalyst by displacement plating. Since it is performed by adhering onto the copper or copper alloy, the influence of elution of copper can be reduced, and the frequency of the new catalyst solution (pretreatment solution) can be remarkably reduced.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the copper concentration in a pretreatment liquid and the minimum pretreatment liquid immersion time required for nickel plating to deposit.
Claims (5)
１／１０＜シランカップリング剤／貴金属化合物＜５／１A mixture of a silane coupling agent having a functional group having a metal-capturing ability in one molecule and a noble metal compound in a weight ratio shown below or a solvent and a solution obtained by mixing or reacting them in advance. Pretreatment solution for electrolytic nickel plating.
1/10 <silane coupling agent / noble metal compound <5/1
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 |
| 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, and surface-treated article and electroless nickel plating method using the same |
| CNB028022629A CN1283832C (en) | 2001-06-28 | 2002-04-18 | Surface treatment agent, rticle surface treated therewith and method of nickel plating using the agent |
| TW091112606A TWI229703B (en) | 2001-06-28 | 2002-06-11 | Surface treatment agent, and surface-treated article and electroless nickel plating method using the same |
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| 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 |
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| Publication Number | Publication Date |
|---|---|
| JP2003013241A JP2003013241A (en) | 2003-01-15 |
| JP3758532B2 true JP3758532B2 (en) | 2006-03-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004108986A1 (en) | 2003-06-09 | 2004-12-16 | Nikko Materials Co., Ltd. | Method for electroless plating and metal-plated article |
| JP4863715B2 (en) * | 2003-11-05 | 2012-01-25 | Ｊｘ日鉱日石金属株式会社 | Ink jet ink composition |
| JP2007321189A (en) * | 2006-05-31 | 2007-12-13 | Technic Japan Inc | Catalytic agent for electroless plating |
| WO2008032839A1 (en) * | 2006-09-15 | 2008-03-20 | Ube Nitto Kasei Co., Ltd. | Base material covered with metal layer and process for producing the same |
| US20090162681A1 (en) * | 2007-12-21 | 2009-06-25 | Artur Kolics | Activation solution for electroless plating on dielectric layers |
| US8895441B2 (en) | 2012-02-24 | 2014-11-25 | Lam Research Corporation | Methods and materials for anchoring gapfill metals |
| JP6352059B2 (en) * | 2014-06-05 | 2018-07-04 | 奥野製薬工業株式会社 | Composition for forming electroless plating underlayer |
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