JP5453602B2 - Electroless Cu plating solution and electroless Cu plating method - Google Patents
Electroless Cu plating solution and electroless Cu plating method Download PDFInfo
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本発明は、無電解Ｃｕめっき液および無電解Ｃｕめっき方法に関するものである。 The present invention relates to an electroless Cu plating solution and an electroless Cu plating method .
発明者は、めっき液中に分散剤と微細炭素繊維もしくはその誘導体とを添加して、該分散剤によりめっき液中に微細炭素繊維（カーボンナノチューブ：ＣＮＴ）もしくはその誘導体（以下、これらをＣＮＴと総称する）を分散させ、めっきを施して、基材表面に、微細炭素繊維もしくはその誘導体が混入しているめっき皮膜を形成するめっき方法を提案している（特許文献１）。
そして、この特許文献１では、無電解Ｃｕめっき皮膜中にＣＮＴを混入できることにも言及している。
The inventor adds a dispersing agent and fine carbon fibers or derivatives thereof to the plating solution, and the dispersing agent adds fine carbon fibers (carbon nanotubes: CNT) or derivatives thereof (hereinafter referred to as CNTs). In general, a plating method has been proposed in which a plating film in which fine carbon fibers or derivatives thereof are mixed is formed on the surface of a base material (Patent Document 1).
And this patent document 1 mentions that CNT can be mixed in an electroless Cu plating film.
特許文献１に示されるめっき方法は、好適には、分散剤にポリアクリル酸を用いてＣｕめっき液中にＣＮＴを分散させ、めっきを施すことによって、Ｃｕめっき皮膜中にＣＮＴを取り込むものである。分散剤にポリアクリル酸を用いることによって、ＣＮＴをＣｕめっき液中に良好に分散させることができる。
しかしながら、無電解Ｃｕめっきの場合には、電解Ｃｕめっきとはめっきの原理が異なり、電解Ｃｕめっきの場合ほどは、Ｃｕめっき皮膜中にＣＮＴを良好に取り込むことはできなかった。
The plating method shown in Patent Document 1 preferably takes CNT into the Cu plating film by dispersing and dispersing CNT in the Cu plating solution using polyacrylic acid as a dispersant. . By using polyacrylic acid as the dispersant, CNT can be favorably dispersed in the Cu plating solution.
However, in the case of electroless Cu plating, the principle of plating is different from that of electrolytic Cu plating, and CNT could not be taken into the Cu plating film as well as in the case of electrolytic Cu plating.
本発明は、上記課題を解決すべくなされたものであり、その目的とするところは、ＣＮＴをめっき皮膜中に良好に取り込むことのできる無電解Ｃｕめっき液および無電解Ｃｕめっき方法を提供するにある。 The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an electroless Cu plating solution and an electroless Cu plating method capable of satisfactorily incorporating CNT into a plating film. is there.
本発明に係る無電解Ｃｕめっき液は、ＣＮＴと、該ＣＮＴを分散させるトリメチルセチルアンモニウム塩を含むことを特徴とする。
トリメチルセチルアンモニウム塩は、トリメチルセチルアンモニウムクロリドが好適である。
The electroless Cu plating solution according to the present invention includes CNT and a trimethyl cetyl ammonium salt in which the CNT is dispersed.
The trimethyl cetyl ammonium salt is preferably trimethyl cetyl ammonium chloride.
また本発明に係る無電解Ｃｕめっき方法は、上記いずれかの無電解Ｃｕめっき液を用いて無電解めっきを行い、被めっき物に、ＣＮＴが埋没した無電解Ｃｕめっき皮膜を形成することを特徴とする。 In addition, the electroless Cu plating method according to the present invention is characterized in that electroless plating is performed using any one of the above electroless Cu plating solutions, and an electroless Cu plating film in which CNTs are buried is formed on an object to be plated. And
また本発明に係る無電解Ｃｕめっき方法は、上記いずれかの無電解Ｃｕめっき液を用いて無電解めっきを行い、被めっき物に、表面にＣＮＴの先端が突出した無電解Ｃｕめっき皮膜を形成することを特徴とする。 In addition, the electroless Cu plating method according to the present invention performs electroless plating using any one of the above electroless Cu plating solutions, and forms an electroless Cu plating film on the surface of which the tip of CNT protrudes. It is characterized by doing.
本発明によれば、無電解めっきであっても、被めっき物に、ＣＮＴが埋没した状態や、先端が突出した状態で良好に取り込まれたＣｕめっき皮膜を形成することができる。この被めっき物は、電磁波シールド性や摺動特性に優れる。
また、無電解Ｃｕめっきであることから、被めっき物が複雑な形状のものであっても均一な膜厚が得られる。
According to the present invention, it is possible to form a Cu plating film that is satisfactorily captured in a state in which CNTs are buried or in a state in which the tip protrudes even in electroless plating. This object to be plated is excellent in electromagnetic shielding properties and sliding properties.
Moreover, since it is electroless Cu plating, a uniform film thickness can be obtained even if the object to be plated has a complicated shape.
以下本発明の好適な実施の形態を添付図面を参照して詳細に説明する。
本実施の形態における無電解Ｃｕめっき液は、ＣＮＴと、該ＣＮＴを分散させるトリメチルセチルアンモニウム塩を含むことを特徴とする。
トリメチルセチルアンモニウム塩としては、トリメチルセチルアンモニウムクロリドが好適である。
Preferred embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
The electroless Cu plating solution in the present embodiment includes CNT and a trimethyl cetyl ammonium salt in which the CNT is dispersed.
As the trimethyl cetyl ammonium salt, trimethyl cetyl ammonium chloride is preferred.
トリメチルセチルアンモニウム塩の添加量は、1.0×10−３Ｍ〜2.0×10−３Ｍ程度が好適である。
ＣＮＴの種類は特に限定されないが、ＶＧＣＦ（商標）のような、太さが１００ｎｍ〜２００ｎｍで、長さが１０μｍ〜２０μｍの大きなサイズのＣＮＴもめっき皮膜中に取り込むことができる。
このような大きなサイズのＣＮＴは、長さを３〜４μｍ程度のものに調整したものの方が、めっき皮膜中に良好に取り込むことができた。
なお、本実施の形態において、ＣＮＴとは、カーボンナノチューブの他、フッ素化カーボンナノチューブなど、カーボンナノチューブの誘導体も含むものとする。
Amount of trimethyl cetyl ammonium salt, 1.0 × 10 -3 M~2.0 × 10 -3 degree M is preferred.
The type of CNT is not particularly limited, but a large CNT having a thickness of 100 nm to 200 nm and a length of 10 μm to 20 μm, such as VGCF (trademark), can be taken into the plating film.
Such a large-sized CNT having a length adjusted to about 3 to 4 μm could be taken into the plating film better.
Note that in this embodiment, CNT includes carbon nanotube derivatives such as fluorinated carbon nanotubes in addition to carbon nanotubes.
トリメチルセチルアンモニウム塩はカチオン系の界面活性剤である。
このトリメチルセチルアンモニウム塩は、ＣＮＴを無電解Ｃｕめっき液中に良好に分散させることができる。
上記のように、トリメチルセチルアンモニウム塩はカチオン系の界面活性剤であって、めっき液中で正に帯電し、直鎖状の長い分子でＣＮＴによく絡みつき、ＣＮＴを正に帯電させると考えられる。そして、ＣＮＴがこのように正に帯電することから、ＣＮＴが無電解Ｃｕめっき皮膜に強く吸着され、この状態でさらにめっき皮膜が積み上がっていくことから、ＣＮＴがめっき皮膜中に良好に取り込まれると考えられる。直鎖状の長い分子であることから、ＶＧＣＦ（商標）のような太いＣＮＴであっても、ＣＮＴによく絡みつき、ＣＮＴが良好にめっき皮膜中に取り込まれる一因となっていると考えられる。なお、ＶＧＣＦ（商標）を３〜４μｍ程度に短く切断した方が、めっき皮膜中への取り込み性は良好であった。
Trimethyl cetyl ammonium salt is a cationic surfactant.
This trimethyl cetyl ammonium salt can disperse CNTs well in the electroless Cu plating solution.
As described above, trimethylcetylammonium salt is a cationic surfactant, and is considered to be positively charged in the plating solution, entangled with CNTs with long linear molecules, and positively charged with CNTs. . Since the CNT is positively charged in this way, the CNT is strongly adsorbed by the electroless Cu plating film, and the plating film is further piled up in this state, so that the CNT is satisfactorily taken into the plating film. it is conceivable that. Since it is a linear long molecule, even a thick CNT such as VGCF (trademark) is likely to be entangled with the CNT well, and the CNT is well taken into the plating film. In addition, when the VGCF (trademark) was cut to about 3 to 4 μm, the incorporation into the plating film was better.
なお、カチオン系界面活性剤は種々あるが、トリメチルセチルアンモニウム塩が、ＣＮＴの分散性、ＣＮＴのめっき皮膜中への取り込み性において良好であった。
上記のように、正に帯電したＣＮＴは、一端においてめっき皮膜に強く吸着され、この状態でめっき皮膜が積み上がっていくことから、ＣＮＴはめっき皮膜中で斜めに取り込まれるものが多いと考えられる。
Although there are various cationic surfactants, trimethylcetylammonium salt was good in CNT dispersibility and CNT uptake into the plating film.
As described above, positively charged CNTs are strongly adsorbed on the plating film at one end, and the plating film is piled up in this state, so it is considered that CNTs are often taken obliquely in the plating film. .
めっき条件によって、ＣＮＴが無電解Ｃｕめっき皮膜内に完全に埋没している状態や、無電解Ｃｕめっき皮膜表面にＣＮＴの先端が突出している状態に調整できる。ＣＮＴ先端がめっき皮膜表面に突出している場合には、ＣＮＴは、摩擦係数が小さいことから、被めっき物表面の摩擦係数も小さく、摺動特性に優れる被めっき物を得ることができる。 Depending on the plating conditions, the CNT can be adjusted to be completely buried in the electroless Cu plating film or the CNT tip can protrude from the surface of the electroless Cu plating film. When the tip of the CNT protrudes from the surface of the plating film, since the CNT has a small friction coefficient, the object to be plated having a small friction coefficient on the surface of the object to be plated and excellent sliding characteristics can be obtained.
また、ＣＮＴは導電性に優れ、ＣＮＴそれ自体で１００ＭＨｚ〜７５ＧＨｚ程度の高周波の優れた電磁波シールド性を有することから、本実施の形態のように、無電解Ｃｕめっき皮膜中にＣＮＴを取り込ませた場合、２μｍ程度のめっき皮膜の厚さで、１００ｋＨｚ〜数ＧＨｚ程度までの高い周波数の電磁波シールド性を有することが期待できる。 Moreover, since CNT is excellent in electrical conductivity and has excellent electromagnetic shielding properties of high frequency of about 100 MHz to 75 GHz by itself, the CNT is taken into the electroless Cu plating film as in this embodiment. In this case, it can be expected to have a high frequency electromagnetic shielding property of about 100 kHz to several GHz with a thickness of the plating film of about 2 μm.
また、無電解Ｃｕめっきであることから、被めっき物が複雑な形状のものであっても均一な膜厚が得られる。
また、被めっき物が金属、非金属に関わらずめっきが可能であり、各種電気・電子機器における電磁波シールド効果が期待できる。
Moreover, since it is electroless Cu plating, a uniform film thickness can be obtained even if the object to be plated has a complicated shape.
Moreover, regardless of whether the object to be plated is metal or non-metal, plating is possible, and an electromagnetic wave shielding effect in various electric / electronic devices can be expected.
無電解Ｃｕめっき液の組成の一例を下記に示す。
CuSO４・5H２O 0.06Ｍ
CHOCOOH・H２O 0.03Ｍ
EDTA・2Na 0.1Ｍ
分散剤TMSAC 1.7×10−３、1.7×10−４、1.7×10−５Ｍ
CNT 2g/l
なお、TMSACは、トリメチルセチルアンモニウムクロリドである。
また、ＣＮＴは、ILIJIN社製のＭＷＣＮＴ：直径10〜15ｎｍ、長さ10〜20μｍのものを用いた。
An example of the composition of the electroless Cu plating solution is shown below.
CuSO 4 · 5H 2 O 0.06M
CHOCOOH ・ H 2 O 0.03M
EDTA ・ 2Na 0.1M
Dispersant TMSAC 1.7 × 10 −3 , 1.7 × 10 −4 , 1.7 × 10 −5 M
CNT 2g / l
TMSAC is trimethylcetylammonium chloride.
As the CNT, MWCNT manufactured by ILIJIN: diameter 10 to 15 nm and length 10 to 20 μm was used.
めっき条件は次のとおり。
基板
銅板（３．３ｃｍ×３ｃｍ）
前処理
通常法（酸性ＳｎＣｌ２溶液を用いた感受性化＋酸性ＰｄＣｌ２溶液を用いた活性化）
めっき条件
温度：５０℃、ｐＨ：１２．１、時間：120分、攪拌：スターラー攪拌（1500rpm）
膜の評価
微細構造：ＦＥ−ＳＥＭ（電界放出型走査電子顕微鏡）
The plating conditions are as follows.
Substrate copper plate (3.3cm x 3cm)
Normal method of pretreatment (sensitization using acidic SnCl 2 solution + activation using acidic PdCl 2 solution)
Plating conditions Temperature: 50 ° C., pH: 12.1, Time: 120 minutes, Stirring: Stirrer stirring (1500 rpm)
Evaluation microstructure of film : FE-SEM (field emission scanning electron microscope)
図１に分散剤添加量の違いによる無電解Ｃｕめっき皮膜のＳＥＭ写真を示す。
図１（Ａ）は、分散剤（TMSAC）を1.7×10−３Ｍ添加したもので、図１（Ｂ）はその拡大写真である。図１（Ｂ）に示されるように、ＣＮＴは、めっき膜表面に露出気味ではあるが、Ｃｕめっき膜中に取り込まれている。
FIG. 1 shows SEM photographs of the electroless Cu plating film depending on the amount of the dispersant added.
FIG. 1 (A) shows a dispersion agent (TMSAC) added with 1.7 × 10 −3 M, and FIG. 1 (B) is an enlarged photograph thereof. As shown in FIG. 1 (B), CNTs appear to be exposed on the plating film surface, but are taken into the Cu plating film.
図１（Ｃ）は、分散剤（TMSAC）を1.7×10−４Ｍ添加したもので、図１（Ｄ）はその拡大写真である。図１（Ｄ）に示されるように、ＣＮＴは、めっき膜表面に若干露出気味ではあるが、Ｃｕめっき膜中に取り込まれている。
図１（Ｅ）は、分散剤（TMSAC）を1.7×10−５Ｍ添加したもので、図１（Ｆ）はその拡大写真である。図１（Ｆ）に示されるように、ＣＮＴは、Ｃｕめっき膜中に取り込まれている。
FIG. 1 (C) shows a dispersion (TMSAC) added with 1.7 × 10 −4 M, and FIG. 1 (D) is an enlarged photograph thereof. As shown in FIG. 1D, the CNT is slightly exposed on the surface of the plating film, but is taken into the Cu plating film.
FIG. 1 (E) shows a dispersion (TMSAC) added with 1.7 × 10 −5 M, and FIG. 1 (F) is an enlarged photograph thereof. As shown in FIG. 1 (F), the CNTs are taken into the Cu plating film.
上記実施例では、被めっき物に銅板を用いたが、ＡＢＳ樹脂等の樹脂材の表面にも同様に良好な無電解Ｃｕめっき皮膜を形成することができた。 In the above example, a copper plate was used as the object to be plated, but a good electroless Cu plating film could be formed on the surface of a resin material such as ABS resin as well.
なお、比較例として、分散剤に、カチオン系界面活性剤の一種である、ベンジルセチルジメチルアンモニウムクロリドを用い、実施例と同様にしてＣＮＴを無電解Ｃｕめっき液中に分散させたが、ＣＮＴの分散性は良好なものの、ＣＮＴのめっき皮膜中への取り込みはほとんどなかった。
また、カチオン系ではないが、ポリエチレングリコールモノ−ｐ−ノニルフェニルエーテルや、ポリアクリルアミドを分散剤として用いたところ、ＣＮＴを無電解Ｃｕめっき液中に良好に分散させることはできなかった。
As a comparative example, benzyl cetyldimethylammonium chloride, which is a kind of cationic surfactant, was used as a dispersant, and CNT was dispersed in an electroless Cu plating solution in the same manner as in the examples. Although the dispersibility was good, CNT was hardly taken into the plating film.
Moreover, although not cationic, when polyethylene glycol mono-p-nonylphenyl ether or polyacrylamide was used as a dispersant, CNT could not be well dispersed in the electroless Cu plating solution.
Claims (4)
ＣＮＴと、
該ＣＮＴを分散させるトリメチルセチルアンモニウム塩を含むことを特徴とする無電解Ｃｕめっき液。 In electroless Cu plating solution,
CNT,
An electroless Cu plating solution comprising a trimethylcetylammonium salt in which the CNT is dispersed.
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