JP2002226972A - Electroless plating method - Google Patents
Electroless plating methodInfo
- Publication number
- JP2002226972A JP2002226972A JP2001025070A JP2001025070A JP2002226972A JP 2002226972 A JP2002226972 A JP 2002226972A JP 2001025070 A JP2001025070 A JP 2001025070A JP 2001025070 A JP2001025070 A JP 2001025070A JP 2002226972 A JP2002226972 A JP 2002226972A
- Authority
- JP
- Japan
- Prior art keywords
- plated
- electroless plating
- coupling agent
- silane coupling
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、導電性の低い材料
や鏡面物（ガラス、半導体基板等）や粉体などの表面上
に金属めっきするための無電解めっき方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless plating method for metal plating on a surface of a material having low conductivity, a specular object (glass, semiconductor substrate, or the like), a powder, or the like.
【０００２】[0002]
【従来の技術】無電解金属めっき法は樹脂などの導電性
のない被めっき材の表面に金属めっき膜を形成する方法
の一つである。無電解めっきの前処理方法としてはパラ
ジウムなどの貴金属を触媒として予め被めっき材に付着
させておく活性化と呼ばれる処理を施す方法が一般的で
ある。これまで、貴金属を被めっき材に付着させる方法
としては、被めっき材をＳｎＣｌ2の塩酸性水溶液で処
理した後にＰｄＣｌ2水溶液に浸漬処理して表面にＰｄ
を付着させる方法や、ＳｎとＰｄとを含んだコロイド溶
液によりＰｄを表面に付着させる方法などが行なわれて
きた。2. Description of the Related Art An electroless metal plating method is one of methods for forming a metal plating film on a surface of a material to be plated having no conductivity such as a resin. As a pretreatment method for the electroless plating, a method of performing a process called activation in which a noble metal such as palladium is attached to a material to be plated in advance as a catalyst is generally used. Pd Previously, a noble metal as a method of attaching the material to be plated is a surface treatment by immersion in PdCl 2 solution after processing the material to be plated with hydrochloric acid aqueous solution of SnCl 2
And a method of attaching Pd to the surface using a colloidal solution containing Sn and Pd.
【０００３】ところが、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ことなどの問題
が多いため、最近では無電解めっきの触媒であるＰｄな
どの貴金属を表面に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）。However, these methods are highly toxic to Sn.
Since there are many problems such as the use of a noble metal and the complicated processing steps, recently, as a method of supporting a noble metal such as Pd, which is a catalyst for electroless plating, on the surface, a function capable of forming a complex with these noble metals is used. Various methods using a silane coupling agent having a group have been proposed (JP-B-59-52701, JP-A-60-181294, JP-A-61-194183, JP-A-3-44149).
【０００４】しかしながら、上記のシランカップリング
剤を使った方法によっても、被めっき材の素材やめっき
条件によっては密着性が良くかつ均一なめっき膜を得る
ことが困難な場合があった。これはシランカップリング
剤が被めっき材に効率良く均一かつ強固に結合されない
ためと考えられる。[0004] However, even with the above-mentioned method using a silane coupling agent, it may be difficult to obtain a good adhesion and uniform plating film depending on the material of the material to be plated and the plating conditions. This is probably because the silane coupling agent is not efficiently and uniformly and firmly bonded to the material to be plated.
【０００５】[0005]
【発明が解決しようとする課題】本発明はこうした実情
の下に、従来無電解めっきが適用しにくかった粉体、鏡
面物あるいは樹脂布などの基材に対しても金属めっき膜
を形成することが可能な新規な無電解めっき方法を提供
することを目的とするものであり、本発明によれば、カ
ップリング剤を用いても十分な接着力が得られにくい被
めっき材についても強固な接着力を有する金属めっき膜
を形成することが可能となる。SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a method for forming a metal plating film on a base material such as a powder, a mirror-like object, or a resin cloth, which is conventionally difficult to apply electroless plating. It is an object of the present invention to provide a new electroless plating method capable of performing the above-mentioned steps. It is possible to form a metal plating film having power.
【０００６】[0006]
【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、被めっき材をアルカリ金属塩を含有する溶液で前
処理した後、金属捕捉能を持つ官能基を分子中に有する
シランカップリング剤によって処理すると、触媒を固着
したカップリング剤が被めっき材に効率良く均一かつ強
固に固定されるため、無電解めっき膜の密着力が強くな
ることを見出し本発明に至った。Means for Solving the Problems As a result of intensive studies, the present inventor has found that after a material to be plated is pretreated with a solution containing an alkali metal salt, a silane coupling having a metal-capturing functional group in the molecule. It has been found that when the treatment is carried out with the agent, the coupling agent to which the catalyst is fixed is efficiently and uniformly and firmly fixed to the material to be plated, so that the adhesion of the electroless plating film is enhanced.
【０００７】すなわち、本発明は、 （１）被めっき材をアルカリ金属塩を含有する溶液で前
処理した後、一分子中に金属捕捉能を持つ置換基を有す
るシランカップリング剤を有効成分とする化合物で処理
し、次いで貴金属化合物の水溶液で処理して貴金属をシ
ランカップリング剤に捕捉させた後、該被めっき材を無
電解めっきすることを特徴とする無電解めっき方法。 （２）被めっき材をアルカリ金属塩を含有する溶液で前
処理した後、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とを予め混合または反応さ
せてなる処理剤によって被めっき材を表面処理し、次い
で該被めっき材を無電解めっきすることを特徴とする無
電解めっき方法。 （３）アルカリ金属塩がアルカリ金属のケイ酸塩化合
物、アルカリ金属の水酸化物あるいはそれらの混合物で
あることを特徴とする前記（１）又は（２）記載の無電
解めっき方法、 （４）一分子中に金属捕捉能を持つ置換基を有するシラ
ンカップリング剤が含窒素複素環式アゾール化合物とエ
ポキシ基含有シラン化合物との反応生成物であるアゾー
ル系シランカップリング剤であることを特徴とする前記
（１）または（２）記載の無電解めっき方法、 （５）含窒素複素環がイミダゾール環であることを特徴
とする前記（４）記載の無電解めっき方法、 （６）被めっき材が、ポリイミド、ポリエーテルイミ
ド、ポリフェニレンサルファイド、ポリブチレンテレフ
タレート、エポキシ樹脂、ガラス、アルミニウム、セラ
ミックスであることを特徴とする前記（１）又は（２）
記載の無電解めっき方法、に関する。That is, the present invention provides: (1) After pretreating a material to be plated with a solution containing an alkali metal salt, a silane coupling agent having a substituent capable of capturing metal in one molecule is used as an active ingredient. An electroless plating method, comprising: treating the material to be plated with a compound to be plated, then treating with an aqueous solution of a noble metal compound to trap the noble metal in the silane coupling agent, and then electrolessly plating the material to be plated. (2) After the material to be plated is pre-treated with a solution containing an alkali metal salt, the material to be plated is plated with a treating agent obtained by previously mixing or reacting a silane coupling agent having a functional group capable of capturing metals with a noble metal compound. An electroless plating method comprising: subjecting a material to a surface treatment; and then electrolessly plating the material to be plated. (3) The electroless plating method according to (1) or (2), wherein the alkali metal salt is a silicate compound of an alkali metal, a hydroxide of an alkali metal, or a mixture thereof. The silane coupling agent having a substituent capable of trapping metal in one molecule is an azole silane coupling agent which is a reaction product of a nitrogen-containing heterocyclic azole compound and an epoxy group-containing silane compound. (5) The electroless plating method according to (4), wherein the nitrogen-containing heterocyclic ring is an imidazole ring, (6) a material to be plated. Are polyimide, polyetherimide, polyphenylene sulfide, polybutylene terephthalate, epoxy resin, glass, aluminum, and ceramics. It said to be (1) or (2)
The present invention relates to the electroless plating method described above.
【０００８】本発明においては、特定のシランカップリ
ング剤、すなわち無電解めっき触媒となる金属捕捉能を
持つ官能基を有するシランカップリング剤を用いて被め
っき材を処理するにあたり、その前段階の処理としてア
ルカリ金属塩を含有する溶液で被めっき材を処理するこ
とに特徴がある。In the present invention, when a material to be plated is treated with a specific silane coupling agent, that is, a silane coupling agent having a functional group having a metal-capturing ability to serve as an electroless plating catalyst, a process prior to the treatment is performed. The treatment is characterized in that the material to be plated is treated with a solution containing an alkali metal salt.
【０００９】本件発明の無電解めっき方法の詳細は次の
とおりである。 〈アルカリ金属塩について〉アルカリ金属塩としては、
ナトリウム、カリウム、リチウムなどの水酸化物、ケイ
酸化合物などが使用でき、具体的には、水酸化物として
は、水酸化ナトリウム、炭酸水素ナトリウム、水酸化マ
グネシウム、水酸化カリウム、水酸化リチウムなどが、
また、ケイ酸化合物としては、オルトケイ酸ナトリウ
ム、メタケイ酸ナトリウム、二ケイ酸ナトリウム、水ガ
ラスなどが例示できる。これらの化合物は単独で使用し
てもよいし複数を組合わせても良い。The details of the electroless plating method of the present invention are as follows. <About the alkali metal salt> As the alkali metal salt,
Hydroxides such as sodium, potassium and lithium, silicate compounds and the like can be used. Specific examples of the hydroxide include sodium hydroxide, sodium hydrogen carbonate, magnesium hydroxide, potassium hydroxide and lithium hydroxide. But,
Examples of the silicate compound include sodium orthosilicate, sodium metasilicate, sodium disilicate, and water glass. These compounds may be used alone or in combination of two or more.
【００１０】〈ケイ酸化合物について〉ケイ酸化合物を
溶解させる溶媒としては水が好ましいが、アルコールな
どの有機溶媒に溶解させても良いし、水と有機溶媒の混
合溶媒に溶解させても良い。ケイ酸化合物の濃度は、
０．１〜５０ｇ／Ｌが好ましく、特に１〜１０ｇが好ま
しい。ケイ酸化合物の濃度が高い場合は、水洗後も過剰
のケイ酸化合物が残留することになり、金属捕捉能を持
つ置換基を有するカップリング剤の金属捕捉能を低下さ
せる。また、ケイ酸の濃度が低すぎる場合はケイ酸化合
物によるカップリング剤の固定能力が低下する。樹脂や
フィルムの濡れ性が悪い時は、クロム酸処理や脱脂処理
をケイ酸処理の前にすると良い。<Regarding Silicate Compound> As a solvent for dissolving the silicic acid compound, water is preferable, but it may be dissolved in an organic solvent such as alcohol, or may be dissolved in a mixed solvent of water and an organic solvent. The concentration of the silicate compound is
0.1 to 50 g / L is preferable, and 1 to 10 g is particularly preferable. When the concentration of the silicate compound is high, an excessive amount of the silicate compound remains even after washing with water, and the metal-capturing ability of the coupling agent having a substituent having metal-capturing ability is reduced. If the concentration of the silicic acid is too low, the ability of the silicic acid compound to fix the coupling agent is reduced. When the wettability of the resin or the film is poor, the chromic acid treatment or degreasing treatment may be performed before the silicic acid treatment.
【００１１】〈その他の任意的な付加工程について〉め
っき膜の密着力をより向上させるために、被めっき材表
面に対して予めクロム酸や過マンガン酸系などのエッチ
ャントを用いてエッチング処理を行い、これによるアン
カー効果を併用しても良い。また、めっきを行なう前の
段階で、被めっき材を還元剤を含む溶液で処理すること
が有効な場合がある。特に銅めっきの場合は、還元剤と
してジメチルアミン−ボラン溶液などで処理すると良
い。<Other optional additional steps> In order to further improve the adhesion of the plating film, the surface of the material to be plated is subjected to an etching treatment using an etchant such as chromic acid or permanganate in advance. Alternatively, the anchor effect may be used in combination. In some cases, it is effective to treat the material to be plated with a solution containing a reducing agent before plating. In particular, in the case of copper plating, it is preferable to treat with a dimethylamine-borane solution or the like as a reducing agent.
【００１２】[0012]
【実施例】実施例１ ポリエーテルスルフィド樹脂の板状体（商品名；レーデ
ル）を５０℃に加熱したクロム酸／硫酸の溶液に５分間
浸漬、水洗後、６０℃に加熱した１０ｇ／Ｌのメタケイ
酸ナトリウム水溶液に５分間浸漬し水洗した。その後、
６０℃に加熱した塩化パラジウム３００ｍｇ／Ｌを含む
０．５ｇ／Ｌのアゾール系シランカップリング剤の水溶
液に１０分間浸漬し水洗した後、無電解ニッケルめっき
液（商品名；ニコム７Ｎ−０／日鉱メタルプレーティン
グ製）を用い、７０℃で１０分間めっきした。得られた
ニッケルめっきポリエーテルスルフィド樹脂は金属光沢
を有していた。密着力はテープ引き剥がし試験により良
好であることを確認した。Example 1 A plate of polyether sulfide resin (trade name: Radel) was immersed in a solution of chromic acid / sulfuric acid heated to 50 ° C. for 5 minutes, washed with water, and then heated to 60 ° C. at 10 g / L. It was immersed in an aqueous solution of sodium metasilicate for 5 minutes and washed with water. afterwards,
After immersing in an aqueous solution of a 0.5 g / L azole-based silane coupling agent containing 300 mg / L of palladium chloride heated to 60 ° C. for 10 minutes and washing with water, an electroless nickel plating solution (trade name: Nicom 7N-0 / Nikko) (Made of metal plating) at 70 ° C. for 10 minutes. The obtained nickel-plated polyether sulfide resin had a metallic luster. The adhesion was confirmed to be good by a tape peeling test.
【００１３】実施例２ ポリイミドフィルム（商品名；カプトン２００Ｈ）を１
０ｇ／Ｌのメタケイ酸ナトリウム水溶液に５分間浸漬し
水洗した。その後、６０℃に加熱した塩化パラジウム３
００ｍｇ／Ｌを含む０．５ｇ／Ｌのアゾール系シランカ
ップリング剤の水溶液に１０分間浸漬し水洗した後、６
０℃に加熱した１０ｇ／Ｌのジメチルアミンボランの水
溶液に５分間浸漬した。その後、無電解銅めっき液（商
品名；ＫＣ−５００／日鉱メタルプレーティング製）を
用い、７２℃で５分間めっきした。得られた銅めっきポ
リイミドフィルムは金属光沢を有していた。密着力はテ
ープ引き剥がし試験により良好であることを確認した。Example 2 A polyimide film (trade name: Kapton 200H) was added to 1
It was immersed in a 0 g / L sodium metasilicate aqueous solution for 5 minutes and washed with water. Thereafter, palladium chloride 3 heated to 60 ° C.
After immersing for 10 minutes in an aqueous solution of an azole-based coupling agent of 0.5 g / L containing 00 mg / L and washing with water, 6
It was immersed in a 10 g / L aqueous solution of dimethylamine borane heated to 0 ° C. for 5 minutes. Thereafter, plating was performed at 72 ° C. for 5 minutes using an electroless copper plating solution (trade name; KC-500 / manufactured by Nikko Metal Plating). The obtained copper-plated polyimide film had a metallic luster. The adhesion was confirmed to be good by a tape peeling test.
【００１４】実施例３ ポリイミドフィルム（商品名；カプトン２００Ｈ）を５
ｇ／Ｌのメタケイ酸ナトリウム、５ｇ／Ｌの水酸化ナト
リウム水溶液に５分間浸漬し水洗した。その後、６０℃
に加熱した塩化パラジウム２０ｍｇ／Ｌを含む０．３ｇ
／Ｌのアゾール系シランカップリング剤の水溶液に１０
分間浸漬し水洗した後、６０℃に加熱した１０ｇ／Ｌの
ジメチルアミンボランの水溶液に５分間浸漬した。その
後、無電解銅めっき液（商品名；ＮＫＭ−５５４／日鉱
メタルプレーティング製）を用い、５０℃で２０分間め
っきした。得られた銅めっきポリイミドフィルムは金属
光沢を有していた。密着力はテープ引き剥がし試験によ
り良好であることを確認した。Example 3 A polyimide film (trade name: Kapton 200H) was added to 5
g / L sodium metasilicate and 5 g / L sodium hydroxide aqueous solution were immersed for 5 minutes and washed with water. Then 60 ° C
0.3g containing 20mg / L palladium chloride heated to
/ L aqueous solution of azole-based silane coupling agent
After immersion for 5 minutes and washing with water, the substrate was immersed in an aqueous solution of 10 g / L dimethylamine borane heated to 60 ° C. for 5 minutes. Thereafter, plating was performed at 50 ° C. for 20 minutes using an electroless copper plating solution (trade name: NKM-554 / Nikko Metal Plating). The obtained copper-plated polyimide film had a metallic luster. The adhesion was confirmed to be good by a tape peeling test.
【００１５】実施例４ ポリイミドフィルム（商品名；カプトン２００Ｈ）を６
０℃に加熱した ５ｇ／Ｌの水酸化ナトリウム水溶液に
５分間浸漬し水洗した後、引き続き６０℃に加熱した５
ｇ／Ｌのメタケイ酸ナトリウムに５分間浸漬し水洗し
た。６０℃に加熱した塩化パラジウム１００ｍｇ／Ｌを
含む０．３ｇ／Ｌのアゾール系シランカップリング剤の
水溶液に１０分間浸漬し水洗した後、６０℃に加熱した
１０ｇ／Ｌのジメチルアミンボランの水溶液に５分間浸
漬した。その後、無電解銅めっき液（商品名；ＮＫＭ−
５５４／日鉱メタルプレーティング製）を用い、５０℃
で２０分間めっきした。得られた銅めっきポリイミドフ
ィルムは金属光沢を有していた。密着力はテープ引き剥
がし試験により良好であることを確認した。Example 4 A polyimide film (trade name: Kapton 200H)
After being immersed in a 5 g / L aqueous sodium hydroxide solution heated to 0 ° C. for 5 minutes, washed with water, and subsequently heated to 60 ° C.
It was immersed in g / L sodium metasilicate for 5 minutes and washed with water. After immersing in an aqueous solution of a 0.3 g / L azole-based silane coupling agent containing 100 mg / L of palladium chloride heated to 60 ° C. for 10 minutes, washing with water, and then heating the aqueous solution of 10 g / L dimethylamine borane heated to 60 ° C. Dipped for 5 minutes. Then, electroless copper plating solution (trade name: NKM-
554 / day ore metal plating) at 50 ° C
For 20 minutes. The obtained copper-plated polyimide film had a metallic luster. The adhesion was confirmed to be good by a tape peeling test.
【００１６】実施例５ ポリイミドフィルム（商品名；ユーピレックス）を５０
℃に加熱した ２００ｇ／Ｌの水酸化ナトリウム水溶液
に５分間浸漬し水洗した後、６０℃に加熱した塩化パラ
ジウム４０ｍｇ／Ｌを含む０．３ｇ／Ｌのアゾール系シ
ランカップリング剤の水溶液に１０分間浸漬し水洗した
後、６０℃に加熱した１０ｇ／Ｌのジメチルアミンボラ
ンの水溶液に５分間浸漬した。その後、無電解銅めっき
液（商品名；ＮＫＭ−５５４／日鉱メタルプレーティン
グ製）を用い、５０℃で１０分間めっきした。得られた
銅めっきポリイミドフィルムは金属光沢を有していた。
密着力はテープ引き剥がし試験により良好であることを
確認した。Example 5 A polyimide film (trade name: Upilex) was added to 50
Immersed in a 200 g / L aqueous sodium hydroxide solution heated to 60 ° C. for 5 minutes, washed with water, and then heated in an aqueous solution of a 0.3 g / L azole-based silane coupling agent containing 40 mg / L of palladium chloride heated to 60 ° C. for 10 minutes. After being immersed and washed with water, it was immersed in a 10 g / L aqueous solution of dimethylamine borane heated to 60 ° C. for 5 minutes. Thereafter, plating was performed at 50 ° C. for 10 minutes using an electroless copper plating solution (trade name: NKM-554 / manufactured by Nikko Metal Plating). The obtained copper-plated polyimide film had a metallic luster.
The adhesion was confirmed to be good by a tape peeling test.
【００１７】実施例６ ポリブチレンテレフタレート板をクロム酸／硫酸の溶液
に５分間浸漬、水洗後、７０℃に加熱した ２００ｇ／
Ｌの水酸化ナトリウム、５０ｇ／Ｌのメタケイ酸ナトリ
ウムに１０分間浸漬し十分に水洗した。６０℃に加熱し
た塩化パラジウム１００ｍｇ／Ｌを含む０．５ｇ／Ｌの
アゾール系シランカップリング剤の水溶液に１０分間浸
漬し水洗した後、無電解ニッケルめっき液（商品名；ニ
コム７Ｎ−０／日鉱メタルプレーティング製）を用い７
０℃で３分間ニッケルめっき、さらに無電解銅めっき液
（商品名；ＫＣ−５００／日鉱メタルプレーティング
製）を用い７２℃で１０分間めっきした。電気めっきに
よりさらに３０μｍの銅めっきを行った。得られた銅め
っきポリブチレンテレフタレート板は金属光沢を有して
いた。密着力は９０度ピール試験により１．１ｋｇｆ／
ｃｍで良好であることを確認した。Example 6 A polybutylene terephthalate plate was immersed in a solution of chromic acid / sulfuric acid for 5 minutes, washed with water, and heated to 70 ° C.
L of sodium hydroxide and 50 g / L of sodium metasilicate for 10 minutes, and sufficiently washed with water. After immersion in an aqueous solution of a 0.5 g / L azole-based silane coupling agent containing 100 mg / L of palladium chloride heated to 60 ° C. for 10 minutes and washing with water, an electroless nickel plating solution (trade name: Nicom 7N-0 / Nikko) Using metal plating) 7
Nickel plating was performed at 0 ° C. for 3 minutes, and further plating was performed at 72 ° C. for 10 minutes using an electroless copper plating solution (trade name: KC-500 / manufactured by Nikko Metal Plating). Copper plating of 30 μm was further performed by electroplating. The obtained copper-plated polybutylene terephthalate plate had a metallic luster. Adhesion is 1.1kgf / by 90 degree peel test.
cm was good.
【００１８】比較例１ ポリイミドフィルム（商品名；カプトン２００Ｈ）を６
０℃に加熱した塩化パラジウム２００ｍｇ／Ｌを含む
０．５ｇ／Ｌのアゾール系シランカップリング剤の水溶
液に１０分間浸漬し水洗した後、６０℃に加熱した１０
ｇ／Ｌのジメチルアミンボランの水溶液に５分間浸漬し
た。その後、無電解銅めっき液（商品名；ＮＫＭ−５５
４／日鉱メタルプレーティング製）を用い、５０℃で３
０分間めっきした。銅めっき膜はめっき中にほとんど剥
離してしまった。Comparative Example 1 A polyimide film (trade name: Kapton 200H) was mixed with 6
After immersing in an aqueous solution of a 0.5 g / L azole-based silane coupling agent containing 200 mg / L of palladium chloride heated to 0 ° C. for 10 minutes, washing with water, and then heating to 60 ° C.
It was immersed in an aqueous solution of g / L dimethylamine borane for 5 minutes. Thereafter, an electroless copper plating solution (trade name: NKM-55)
4 / Nikko Metal Plating) at 50 ° C
Plated for 0 minutes. The copper plating film almost peeled off during plating.
【００１９】比較例２ ポリエーテルスルフィド樹脂（商品名；レーデル）を５
０℃に加熱したクロム酸／硫酸の溶液に５分間浸漬、水
洗後、６０℃に加熱した塩化パラジウム３００ｍｇ／Ｌ
を含む０．５ｇ／Ｌのアゾール系シランカップリング剤
の水溶液に１０分間浸漬し水洗した後、無電解ニッケル
めっき液（商品名；ニコム７Ｎ−０／日鉱メタルプレー
ティング製）を用い、７０℃で１０分間めっきした。得
られたニッケルめっきポリエーテルスルフィド樹脂は金
属光沢を有していたがめっき膜にはフクレがあり、密着
力はテープ引き剥がし試験により不良であった。Comparative Example 2 A polyether sulfide resin (trade name: Radel) was added to 5
Immerse in a chromic acid / sulfuric acid solution heated to 0 ° C. for 5 minutes, wash with water, and then heat palladium chloride at 60 ° C. 300 mg / L
Immersed in an aqueous solution of a 0.5 g / L azole-based coupling agent containing 0.5 g / L for 10 minutes, washed with water, and then heated to 70 ° C. using an electroless nickel plating solution (trade name: Nicom 7N-0 / Nikko Metal Plating). For 10 minutes. Although the obtained nickel-plated polyether sulfide resin had a metallic luster, the plating film had blisters, and the adhesion was poor by a tape peeling test.
【００２０】比較例３ ポリブチレンテレフタレート板をクロム酸／硫酸の溶液
に５分間浸漬、水洗後、６０℃に加熱した塩化パラジウ
ム１００ｍｇ／Ｌを含む０．５ｇ／Ｌのアゾール系シラ
ンカップリング剤の水溶液に１０分間浸漬し水洗した
後、無電解ニッケル液（商品名；ニコム７Ｎ−０／日鉱
メタルプレーティング製）を用い７０℃で３分間ニッケ
ルめっき、さらに無電解銅めっき液（商品名；ＫＣ−５
００／日鉱メタルプレーティング製）を用い７２℃で１
０分間めっきした。電気めっきによりさらに３０μｍの
銅めっきを行った。得られた銅めっきポリブチレンテレ
フタレート板は金属光沢を有していた。しかし、密着力
は９０度ピール試験により０．２ｋｇｆ／ｃｍで不良で
あった。Comparative Example 3 A polybutylene terephthalate plate was immersed in a solution of chromic acid / sulfuric acid for 5 minutes, washed with water, and heated to 60 ° C. with 0.5 mg / L of an azole silane coupling agent containing 100 mg / L of palladium chloride. After immersion in an aqueous solution for 10 minutes and washing with water, nickel plating is performed at 70 ° C. for 3 minutes using an electroless nickel solution (trade name: Nicom 7N-0 / Nikko Metal Plating), and further, an electroless copper plating solution (trade name: KC) -5
00 / day metal plating) at 72 ° C
Plated for 0 minutes. Copper plating of 30 μm was further performed by electroplating. The obtained copper-plated polybutylene terephthalate plate had a metallic luster. However, the adhesion was poor at 0.2 kgf / cm by a 90 degree peel test.
【００２１】[0021]
【発明の効果】以上説明したように、本発明の新規なめ
っき法によれば、簡単な工程で、従来めっきが不可能と
されていた粉体、鏡面物あるいは樹脂布などの基材に
も、無電解めっきを行うことが可能となる。さらに、本
発明のめっき方法によれば、シランカップリング剤を用
いても強固な接着力を有する金属めっき膜を形成するこ
とが可能となる。As described above, according to the novel plating method of the present invention, a simple process can be applied to a substrate such as a powder, a mirror-like object, or a resin cloth, which has been conventionally impossible to be plated. In addition, electroless plating can be performed. Further, according to the plating method of the present invention, it is possible to form a metal plating film having a strong adhesive force even using a silane coupling agent.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4K022 AA02 AA03 AA04 AA15 AA16 AA17 AA18 AA24 BA08 BA14 BA31 CA02 CA16 CA20 CA21 CA22 DA01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4K022 AA02 AA03 AA04 AA15 AA16 AA17 AA18 AA24 BA08 BA14 BA31 CA02 CA16 CA20 CA21 CA22 DA01
Claims (6)
溶液で前処理した後、一分子中に金属捕捉能を持つ置換
基を有するシランカップリング剤を有効成分とする化合
物で処理し、次いで貴金属化合物の水溶液で処理して貴
金属をシランカップリング剤に捕捉させた後、該被めっ
き材を無電解めっきすることを特徴とする無電解めっき
方法。After pretreating a material to be plated with a solution containing an alkali metal salt, the material to be plated is treated with a compound containing a silane coupling agent having a substituent capable of trapping metal in one molecule as an active ingredient, An electroless plating method, comprising: treating a material to be plated with electroless plating after treating the material with an aqueous solution of a noble metal compound to trap the noble metal in a silane coupling agent.
溶液で前処理した後、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とを予め混合また
は反応させてなる処理剤によって被めっき材を表面処理
し、次いで該被めっき材を無電解めっきすることを特徴
とする無電解めっき方法。2. A pre-treatment of a material to be plated with a solution containing an alkali metal salt, followed by a treatment agent obtained by previously mixing or reacting a silane coupling agent having a functional group having a metal-capturing ability with a noble metal compound. An electroless plating method, which comprises subjecting a material to be plated to a surface treatment and then electrolessly plating the material to be plated.
塩化合物、アルカリ金属の水酸化物あるいはそれらの混
合物であることを特徴とする請求項１又は請求項２記載
の無電解めっき方法。3. The electroless plating method according to claim 1, wherein the alkali metal salt is an alkali metal silicate compound, an alkali metal hydroxide or a mixture thereof.
するシランカップリング剤が含窒素複素環式アゾール化
合物とエポキシ基含有シラン化合物との反応生成物であ
るアゾール系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または請求項２記載の無電解めっき方法。4. A silane coupling agent having a substituent having a metal capturing ability in one molecule is an azole silane coupling agent which is a reaction product of a nitrogen-containing heterocyclic azole compound and an epoxy group-containing silane compound. The electroless plating method according to claim 1 or 2, wherein
とを特徴とする請求項４記載の無電解めっき方法。5. The electroless plating method according to claim 4, wherein the nitrogen-containing heterocycle is an imidazole ring.
ルイミド、ポリフェニレンサルファイド、ポリブチレン
テレフタレート、エポキシ樹脂、ガラス、アルミニウ
ム、セラミックスであることを特徴とする請求項１又は
請求項２記載の無電解めっき方法。6. The electroless plating according to claim 1, wherein the material to be plated is polyimide, polyetherimide, polyphenylene sulfide, polybutylene terephthalate, epoxy resin, glass, aluminum, or ceramic. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025070A JP2002226972A (en) | 2001-02-01 | 2001-02-01 | Electroless plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001025070A JP2002226972A (en) | 2001-02-01 | 2001-02-01 | Electroless plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002226972A true JP2002226972A (en) | 2002-08-14 |
Family
ID=18890125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001025070A Pending JP2002226972A (en) | 2001-02-01 | 2001-02-01 | Electroless plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002226972A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007335448A (en) * | 2006-06-12 | 2007-12-27 | Mitsubishi Gas Chem Co Inc | Process for producing printed wiring board |
| WO2008013210A1 (en) * | 2006-07-25 | 2008-01-31 | Ube Industries, Ltd. | Terminally modified hyperbranched polyimide, metal-plated terminally modified hyperbranched polyimide, and method for producing the same |
| JP2008156702A (en) * | 2006-12-22 | 2008-07-10 | Fujitsu Ltd | Housing made from resin and manufacturing method therefor |
| JP2009226658A (en) * | 2008-03-21 | 2009-10-08 | Ube Ind Ltd | Laminated film, surface-treated polyimide film used in laminated film, and method of treating surface of polyimide film |
| JP2010168612A (en) * | 2009-01-21 | 2010-08-05 | Fujitsu Ltd | Method for manufacturing electroless-plated product |
| JP2010277992A (en) * | 2009-04-30 | 2010-12-09 | Fujitsu Ltd | Conductive particle and its manufacturing method |
| US7867564B2 (en) | 2002-09-10 | 2011-01-11 | Nippon Mining & Metals Co., Ltd. | Metal plating method and pretreatment agent |
| US8182873B2 (en) | 2003-06-09 | 2012-05-22 | Nippon Mining & Metals Co., Ltd. | Method for electroless plating and metal-plated article |
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2001
- 2001-02-01 JP JP2001025070A patent/JP2002226972A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7867564B2 (en) | 2002-09-10 | 2011-01-11 | Nippon Mining & Metals Co., Ltd. | Metal plating method and pretreatment agent |
| US8182873B2 (en) | 2003-06-09 | 2012-05-22 | Nippon Mining & Metals Co., Ltd. | Method for electroless plating and metal-plated article |
| JP2007335448A (en) * | 2006-06-12 | 2007-12-27 | Mitsubishi Gas Chem Co Inc | Process for producing printed wiring board |
| WO2008013210A1 (en) * | 2006-07-25 | 2008-01-31 | Ube Industries, Ltd. | Terminally modified hyperbranched polyimide, metal-plated terminally modified hyperbranched polyimide, and method for producing the same |
| US8093349B2 (en) | 2006-07-25 | 2012-01-10 | Ube Industries, Ltd. | Terminally modified polybranched polyimide, metal-plated terminally modified polybranched polyimide, and method for producing the same |
| JP5359273B2 (en) * | 2006-07-25 | 2013-12-04 | 宇部興産株式会社 | Terminal-modified multi-branched polyimide, metal plating-coated terminal-modified multi-branched polyimide, and production methods thereof |
| KR101449961B1 (en) * | 2006-07-25 | 2014-10-14 | 우베 고산 가부시키가이샤 | Terminally modified polybranched polyimide, metal-plated terminally modified polybranched polyimide, and method for producing the same |
| JP2008156702A (en) * | 2006-12-22 | 2008-07-10 | Fujitsu Ltd | Housing made from resin and manufacturing method therefor |
| JP2009226658A (en) * | 2008-03-21 | 2009-10-08 | Ube Ind Ltd | Laminated film, surface-treated polyimide film used in laminated film, and method of treating surface of polyimide film |
| JP2010168612A (en) * | 2009-01-21 | 2010-08-05 | Fujitsu Ltd | Method for manufacturing electroless-plated product |
| JP2010277992A (en) * | 2009-04-30 | 2010-12-09 | Fujitsu Ltd | Conductive particle and its manufacturing method |
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