JP2017193750A - Electroplating bath for forming porous cylindrical iron group element plating film and method for forming porous cylindrical iron group element plating film using the same - Google Patents
Electroplating bath for forming porous cylindrical iron group element plating film and method for forming porous cylindrical iron group element plating film using the same Download PDFInfo
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- JP2017193750A JP2017193750A JP2016084509A JP2016084509A JP2017193750A JP 2017193750 A JP2017193750 A JP 2017193750A JP 2016084509 A JP2016084509 A JP 2016084509A JP 2016084509 A JP2016084509 A JP 2016084509A JP 2017193750 A JP2017193750 A JP 2017193750A
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- group element
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- iron group
- element plating
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- 238000007747 plating Methods 0.000 title claims abstract description 107
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000009713 electroplating Methods 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 9
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 50
- 229910052759 nickel Inorganic materials 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 238000000635 electron micrograph Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZWRDBWDXRLPESY-UHFFFAOYSA-N n-benzyl-n-ethylethanamine Chemical compound CCN(CC)CC1=CC=CC=C1 ZWRDBWDXRLPESY-UHFFFAOYSA-N 0.000 description 1
- WYZDCUGWXKHESN-UHFFFAOYSA-N n-benzyl-n-methyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(C)CC1=CC=CC=C1 WYZDCUGWXKHESN-UHFFFAOYSA-N 0.000 description 1
- GOTQULLXGZGQMK-UHFFFAOYSA-N n-benzyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C(C)C)CC1=CC=CC=C1 GOTQULLXGZGQMK-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、鉄族元素めっき皮膜の表面に複数の直管状体がある多孔質直管状鉄族元素めっき皮膜を形成するための電気めっき技術に関する。 The present invention relates to an electroplating technique for forming a porous straight tubular iron group element plating film having a plurality of straight tubular bodies on the surface of an iron group element plating film.
鉄族元素めっき皮膜は、装飾、摺動部材の被覆、電気化学センサー、蓄電デバイス等の種々の用途に用いられている。 Iron group element plating films are used in various applications such as decoration, coating of sliding members, electrochemical sensors, and power storage devices.
一般に、装飾めっきにおいては、めっき皮膜は平滑であることが求められるが、フィルター、熱交換器、蓄電デバイス等においては、感度や性能が高くなるため比表面積が大きいことが求められる。 In general, in decorative plating, the plating film is required to be smooth, but in filters, heat exchangers, power storage devices, and the like, the sensitivity and performance are increased, so that the specific surface area is required to be large.
鉄族元素の中でも、例えば、ニッケルめっき皮膜の比表面積を大きくする技術としては、例えば、ニッケルめっき浴に特定の構造の疎水性基を有する水溶性第４級アンモニウム化合物からなる添加剤を添加した電気めっき浴でめっき皮膜表面に１μｍ前後の多数の微細孔を形成する技術（特許文献１）等が知られている。 Among the iron group elements, for example, as a technique for increasing the specific surface area of the nickel plating film, for example, an additive made of a water-soluble quaternary ammonium compound having a hydrophobic group having a specific structure was added to a nickel plating bath. A technique (Patent Document 1) or the like for forming a large number of fine holes of about 1 μm on the surface of a plating film with an electroplating bath is known.
しかしながら、蓄電デバイスにも多種多様なものがあるため、上記のような微細孔や筒状体以外の形状で鉄族元素めっき皮膜の比表面積を大きくできる技術も求められている。 However, since there are a wide variety of power storage devices, there is also a demand for a technique that can increase the specific surface area of the iron group element plating film in a shape other than the fine holes and the cylindrical body as described above.
従って、本発明の課題は鉄族元素めっき皮膜の比表面積を大きくできる技術を提供することである。 Therefore, the subject of this invention is providing the technique which can enlarge the specific surface area of an iron group element plating film.
本発明者らは、上記課題を解決するために鋭意研究した結果、鉄族元素めっき浴に特定の構造の第３級アミンを含有させることにより、これまでにない表面形状を有し、比表面積の大きい鉄族元素めっき皮膜が得られることを見出し、本発明を完成させた。 As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have an unprecedented surface shape by including a tertiary amine having a specific structure in an iron group element plating bath, and have a specific surface area. The present inventors have found that an iron group element plating film having a large thickness can be obtained and completed the present invention.
すなわち、本発明は、鉄族元素めっき浴に、以下の式（I）
で示される第３級アミンを含有させたことを特徴とする多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴である。
That is, the present invention provides an iron group element plating bath having the following formula (I):
An electroplating bath for forming a porous straight tubular iron group element plating film characterized by containing a tertiary amine represented by
また、本発明は、基材を、上記多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴中、０．５〜４Ａ／ｄｍ２で１０分間以上電気めっきすることを特徴とする多孔質直管状鉄族元素めっき皮膜の形成方法である。 Further, the present invention provides a porous straight plate characterized by electroplating a substrate at 0.5 to 4 A / dm 2 for 10 minutes or more in the above-mentioned electroplating bath for forming a porous straight tubular iron group element plating film. This is a method for forming a tubular iron group element plating film.
更に、本発明は、基材上にされた鉄族元素めっき皮膜であって、鉄族元素めっき皮膜の表面に複数の直管状体があることを特徴とする多孔質直管状鉄族元素めっき皮膜である。 Furthermore, the present invention is an iron group element plating film formed on a substrate, wherein there are a plurality of straight tubular bodies on the surface of the iron group element plating film. It is.
本発明の多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴によれば、表面に鉄族元素めっきにより形成された複数の直管状体がある鉄族元素めっき皮膜を得ることができる。この鉄族元素めっき皮膜は比表面積が大きく、また、直管状であるため電極活物質を内部にまで充填できることや通気性に優れ、例えば、蓄電デバイス、フィルター、熱交換器等に好適に利用することができる。 According to the electroplating bath for forming a porous straight tubular iron group element plating film of the present invention, an iron group element plating film having a plurality of straight tubular bodies formed by iron group element plating on the surface can be obtained. This iron group element plating film has a large specific surface area, and since it is a straight tube, it can be filled with an electrode active material to the inside and has excellent air permeability, and is suitably used for, for example, an electricity storage device, a filter, a heat exchanger, etc. be able to.
本発明の多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴は、鉄族元素めっき浴に、以下の式（I）で示される第３級アミンを含有させたものである。
上記式（I）中、Ｒ１は炭素数１〜６の直鎖または分岐鎖アルキル基を示し、Ｒ２は炭素数１〜６の直鎖または分岐鎖アルキル基、あるいは置換基を有してもよいアリール基を示し、Ｒ３は置換基を有していてもよいアリール基を示す。なお、Ｒ２〜Ｒ３の置換基としては、アルキル基、アリール基、アルコキシ基、ハロゲン原子等が挙げられ、これらの中でもアルキル基、アリール基が好ましい。より具体的に、Ｒ１はメチル基、エチル基、n-プロピル基、イソプロピル基が好ましく、メチル基、エチル基がより好ましい。Ｒ２はメチル基、エチル基、n-プロピル基、イソプロピル基、ベンジル基が好ましく、メチル、エチル基がより好ましい。Ｒ３はベンジル基、フェニル基、ナフチル基が好ましく、ベンジル基がより好ましい。 In the above formula (I), R 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms, and R 2 has a linear or branched alkyl group having 1 to 6 carbon atoms or a substituent. And R 3 represents an aryl group which may have a substituent. As the substituent of R 2 to R 3, an alkyl group, an aryl group, an alkoxy group and a halogen atom. Among these alkyl groups, an aryl group is preferable. More specifically, R 1 is preferably a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and more preferably a methyl group or an ethyl group. R 2 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group or a benzyl group, and more preferably a methyl or ethyl group. R 3 is preferably a benzyl group, a phenyl group or a naphthyl group, more preferably a benzyl group.
上記式（I）で示される第３級アミンの中でも、Ｎ，Ｎ−ジメチルベンジルアミン、Ｎ，Ｎ−ジエチルベンジルアミン、ジイソプロピルベンジルアミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、Ｎ−メチルジベンジルアミンがより好ましい。これらの成分（ａ）は１種または２種以上を組み合わせてもよい。 Among the tertiary amines represented by the above formula (I), N, N-dimethylbenzylamine, N, N-diethylbenzylamine, diisopropylbenzylamine, N, N-dimethylaniline, N, N-diethylaniline, N -Methyldibenzylamine is more preferred. These components (a) may be used alone or in combination of two or more.
上記式（I）で示される第３級アミンは、鉄族元素めっき浴中に、０.００１〜０.１５ｍｏｌ／Ｌ、好ましくは０.００５〜０.１ｍｏｌ／Ｌで含有させればよい。 The tertiary amine represented by the above formula (I) may be contained in the iron group element plating bath at 0.001 to 0.15 mol / L, preferably 0.005 to 0.1 mol / L.
本発明に用いられる鉄族元素めっき浴としては、鉄族元素（ニッケル、コバルト、鉄）を析出させることのめっき浴であれば特に限定されず、例えば、公知のニッケルめっき浴、コバルトめっき浴、鉄めっき浴が挙げられる。これらの鉄族元素めっき浴の中でもニッケルめっき浴、コバルトめっき浴が好ましい。 The iron group element plating bath used in the present invention is not particularly limited as long as it is a plating bath for depositing iron group elements (nickel, cobalt, iron). For example, a known nickel plating bath, cobalt plating bath, An iron plating bath is mentioned. Among these iron group element plating baths, nickel plating baths and cobalt plating baths are preferable.
なお、これら鉄族元素めっき浴には、鉄族元素を２種以上含有させたり、鉄族元素以外の別の金属元素を含有させて合金めっき浴としても良い。また、これら鉄族元素めっき浴には、例えば、サッカリン酸ナトリウム等の添加剤を含有させてもよい。 These iron group element plating baths may contain two or more kinds of iron group elements, or may contain other metal elements other than iron group elements to form an alloy plating bath. These iron group element plating baths may contain additives such as sodium saccharinate.
また、鉄族元素めっき浴のｐＨは、特に限定されないが、式（I）で示される第３級アミンを鉄族元素めっき浴中で安定に存在させるため、０〜４．０、好ましくは１．０〜２．５とする。 Further, the pH of the iron group element plating bath is not particularly limited. However, since the tertiary amine represented by the formula (I) is stably present in the iron group element plating bath, 0 to 4.0, preferably 1 is preferable. .0 to 2.5.
具体的なニッケルめっき浴としては、硫酸浴、スルファミン酸浴等が挙げられる。 Specific examples of the nickel plating bath include a sulfuric acid bath and a sulfamic acid bath.
上記硫酸ニッケルめっき浴の好ましい態様としては、例えば、以下のものが挙げられる。
硫酸ニッケル １４０〜４００ｇ／Ｌ
塩化ニッケル ２０〜６０ｇ／Ｌ
ホウ酸 １５〜５０ｇ／Ｌ
As a preferable aspect of the said nickel sulfate plating bath, the following are mentioned, for example.
Nickel sulfate 140-400g / L
Nickel chloride 20-60g / L
Boric acid 15-50g / L
上記スルファミン酸ニッケルめっき浴の好ましい態様としては、例えば、以下のものが挙げられる。
スルファミン酸ニッケル １４０〜４００ｇ／Ｌ
塩化ニッケル ５〜２０ｇ／Ｌ
ホウ酸 １５〜５０ｇ／Ｌ
As a preferable aspect of the said nickel sulfamate plating bath, the following are mentioned, for example.
Nickel sulfamate 140-400g / L
Nickel chloride 5-20g / L
Boric acid 15-50g / L
具体的なコバルトめっき浴としては、スルファミン酸浴等が挙げられる。 Specific examples of the cobalt plating bath include a sulfamic acid bath.
上記スルファミン酸コバルトめっき浴の好ましい態様としては、例えば、以下のものが挙げられる。
スルファミン酸コバルト １４０〜４００ｇ／Ｌ
塩化コバルト ５〜２０ｇ／Ｌ
ホウ酸 １５〜５０ｇ／Ｌ
As a preferable aspect of the said cobalt sulfamate plating bath, the following are mentioned, for example.
Cobalt sulfamate 140-400 g / L
Cobalt chloride 5-20g / L
Boric acid 15-50g / L
具体的な鉄めっき浴としては、硫酸浴等が挙げられる。 Specific examples of the iron plating bath include a sulfuric acid bath.
上記塩化物鉄めっき浴の好ましい態様としては、例えば、以下のものが挙げられる。
硫酸第一鉄 １４０〜４００ｇ／Ｌ
塩化第一鉄 ２０〜６０ｇ／Ｌ
塩化アンモニウム ５〜３０ｇ／Ｌ
As a preferable aspect of the said chloride iron plating bath, the following are mentioned, for example.
Ferrous sulfate 140-400g / L
Ferrous chloride 20-60g / L
Ammonium chloride 5-30g / L
本発明の多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴は、式（I）で示される第３級アミンを、鉄族元素めっき浴に用いられる酸性の成分を溶解させた水溶液に予め溶解させる以外は、通常の鉄族元素めっき浴と同様にして各種成分の混合やｐＨの調整等して調製することができる。 In the electroplating bath for forming a porous straight tubular iron group element plating film of the present invention, a tertiary amine represented by the formula (I) is previously added to an aqueous solution in which an acidic component used in the iron group element plating bath is dissolved. Except for dissolving, it can be prepared by mixing various components and adjusting pH in the same manner as a normal iron group element plating bath.
以上説明した本発明の多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴で、基材を、０．５〜４Ａ／ｄｍ２、好ましくは１〜２．５Ａ／ｄｍ２で１０分間以上、好ましくは２０〜１２０分間電気めっきすることにより多孔質直管状鉄族元素めっき皮膜を形成することができる。また、めっき浴の温度は、特に限定されないが、例えば、２０〜５０℃、好ましくは３０〜４０℃である。更に、めっきの際には、通常のように対流を起こすような撹拌は行わず、できるだけ撹拌をしないことが好ましく、無撹拌がより好ましい。 In the electroplating bath for forming a porous straight tubular iron group element plating film of the present invention described above, the substrate is 0.5 to 4 A / dm 2 , preferably 1 to 2.5 A / dm 2 for 10 minutes or more, Preferably, a porous straight tubular iron group element plating film can be formed by electroplating for 20 to 120 minutes. Moreover, the temperature of a plating bath is although it does not specifically limit, For example, 20-50 degreeC, Preferably it is 30-40 degreeC. Further, during plating, it is preferable not to stir as much as possible to cause convection as usual, to stir as much as possible, and to stir without stirring.
本発明の多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴で電気めっきすることのできる基材としては、特に限定されないが、例えば、少なくとも基材の表面が、銅、ニッケル、真鍮等の金属、ＡＢＳ、ポリイミド等の樹脂等で形成されたもの等である。 The base material that can be electroplated in the electroplating bath for forming the porous straight tubular iron group element plating film of the present invention is not particularly limited. For example, at least the surface of the base material is made of copper, nickel, brass, or the like. It is formed of a resin such as metal, ABS, or polyimide.
なお、多孔質直管状鉄族元素めっき皮膜とは、鉄族元素めっき皮膜の表面に鉄族元素めっきにより形成された直管状体があり、これが複数あることにより多孔質となっているものである。ここで直管状とは、上面に開口部を有し、その開口部が一直線に下面まで続くパイプのような形状をいう。具体的な多孔質直管状鉄族元素めっき皮膜としては、直管状体の大きさ（最大幅）が２〜１５μｍ程度、高さが１μｍ以上であり、直管状体の開口の大きさが０.３〜１０μｍ程度であり、これが密集、好ましくは隙間なく１ｍｍ２あたり１００００〜１０００００個程度密集しているものである。 In addition, the porous straight tubular iron group element plating film has a straight tubular body formed by iron group element plating on the surface of the iron group element plating film, and is porous due to the presence of a plurality thereof. . Here, the straight tube means a shape like a pipe having an opening on the upper surface and the opening continues in a straight line to the lower surface. As a specific porous straight tubular iron group element plating film, the size (maximum width) of the straight tubular body is about 2 to 15 μm, the height is 1 μm or more, and the size of the opening of the straight tubular body is 0.00. This is about 3 to 10 μm, which is dense, preferably about 10,000 to 100,000 per mm 2 without gaps.
この多孔質直管状鉄族元素めっき皮膜は、通常の鉄族元素めっき皮膜と同様に、装飾、摺動部材の被覆等の用途に用いることができる。特に、この多孔質直管状鉄族元素めっき皮膜は、これに更に金属や樹脂の層を積層すれば、直管状体の内部にそれが入り込み、アンカー効果が生じてピール強度は向上する。 This porous straight tubular iron group element plating film can be used for applications such as decoration and coating of sliding members, in the same manner as ordinary iron group element plating films. In particular, if this porous straight tubular iron group element plating film is further laminated with a layer of metal or resin, it penetrates into the inside of the straight tubular body, an anchor effect is produced, and the peel strength is improved.
また、この多孔質直管状鉄族元素めっき皮膜は、比表面積が大きいため、熱交換器、フィルター、触媒用担体や、全固体二次電池等の二次電池、燃料電池、電気二重層キャパシター等の蓄電デバイス等の用途に用いると感度や性能が向上するため好ましい。 Moreover, since this porous straight tubular iron group element plating film has a large specific surface area, a heat exchanger, a filter, a carrier for a catalyst, a secondary battery such as an all-solid secondary battery, a fuel cell, an electric double layer capacitor, etc. It is preferable to use it for applications such as power storage devices because the sensitivity and performance are improved.
以下、本発明を実施例を挙げて説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples at all.
実 施 例 １
多孔質直管状ニッケルめっき皮膜の形成：
（１）電気めっき浴の調製
水に、硫酸ニッケル２８０ｇ／Ｌ、塩化ニッケル４５ｇ／Ｌ、ホウ酸４０ｇ／Ｌ、Ｎ，Ｎ−ジメチルベンジルアミン２ｇ／Ｌとなるように混合し、最後に、硫酸でｐＨを２.０に調整して多孔質直管状ニッケルめっき皮膜形成用電気めっき浴を得た。
Example 1
Formation of porous straight tubular nickel plating film:
(1) Preparation of electroplating bath Mixing with water so that nickel sulfate 280 g / L, nickel chloride 45 g / L, boric acid 40 g / L, N, N-dimethylbenzylamine 2 g / L, and finally sulfuric acid The pH was adjusted to 2.0 to obtain an electroplating bath for forming a porous straight tubular nickel plating film.
（２）電解めっき
上記（１）で得た電気めっき浴を４０℃にしたものに、銅板を浸漬して電流密度１.２Ａ／ｄｍ２で６０分間めっきした。なお、めっき中は無撹拌とした。この電気めっき後の表面を電子顕微鏡で観察したところ（図１）、ニッケルめっき皮膜の表面に、ニッケルめっきで形成され、上面に開口部を有する直管状体が複数あることが分かった。直管状体の大きさ（最大幅）は３．５〜９μｍ程度であり、直管状体の開口の大きさは１．５〜６．５μｍ程度であり、これが１ｍｍ２あたり２７０００個程度隙間なく密集していた。また、直管状体の断面を電子顕微鏡で観察したところ（図２）、直管状体の開口は一直線に基板間で続くパイプのような形状であった。更に、直管状体の高さは２０μｍ程度であった。
(2) Electroplating A copper plate was immersed in the electroplating bath obtained in (1) above at 40 ° C. and plated at a current density of 1.2 A / dm 2 for 60 minutes. The agitation was not performed during plating. When the surface after this electroplating was observed with an electron microscope (FIG. 1), it was found that there were a plurality of straight tubular bodies formed by nickel plating on the surface of the nickel plating film and having openings on the upper surface. The size of the straight tubular body (maximum width) is about 3.5～9Myuemu, the size of the aperture of the straight tubular body is about 1.5～6.5Myuemu, this 1 mm 2 per 27000 or so without gaps dense Was. Further, when the cross section of the straight tubular body was observed with an electron microscope (FIG. 2), the opening of the straight tubular body was shaped like a pipe that continued between the substrates. Furthermore, the height of the straight tubular body was about 20 μm.
実 施 例 ２
多孔質直管状ニッケルめっき皮膜の形成：
（１）電気めっき浴の調製
水に、スルファミン酸ニッケル４５０ｇ／Ｌ、塩化ニッケル１０ｇ／Ｌ、ホウ酸４０ｇ／Ｌ、Ｎ，Ｎ−ジメチルベンジルアミン４ｇ／Ｌとなるように混合し、最後に、スルファミン酸でｐＨを２.０に調整して多孔質直管状ニッケルめっき皮膜形成用電気めっき浴を得た。
Example 2
Formation of porous straight tubular nickel plating film:
(1) Preparation of electroplating bath Mix in water so that nickel sulfamate 450 g / L, nickel chloride 10 g / L, boric acid 40 g / L, N, N-dimethylbenzylamine 4 g / L, and finally, The pH was adjusted to 2.0 with sulfamic acid to obtain an electroplating bath for forming a porous straight tubular nickel plating film.
（２）電解めっき
上記（１）で得た電気めっき浴を４０℃にしたものに、銅板を浸漬して電流密度１.２Ａ／ｄｍ２で６０分間めっきした。なお、めっき中は無撹拌とした。この電気めっき後の表面を電子顕微鏡で観察したところ（図３）、ニッケルめっき皮膜の表面に、ニッケルめっきで形成され、上面に開口部を有する直管状体が複数あることが分かった。直管状体の大きさ（最大幅）は３．５〜９μｍ程度であり、直管状体の開口の大きさは１．２〜４．０μｍ程度であり、これが１ｍｍ２あたり３９０００個程度隙間なく密集していた。また、直管状体の断面を電子顕微鏡で観察したところ、直管状体の開口は一直線に基板間で続くパイプのような形状であった。更に、直管状体の高さは２０μｍ程度であった。
(2) Electroplating A copper plate was immersed in the electroplating bath obtained in (1) above at 40 ° C. and plated at a current density of 1.2 A / dm 2 for 60 minutes. The agitation was not performed during plating. When the surface after this electroplating was observed with an electron microscope (FIG. 3), it was found that there were a plurality of straight tubular bodies formed by nickel plating on the surface of the nickel plating film and having openings on the upper surface. The size of the straight tubular body (maximum width) is about 3.5～9Myuemu, the size of the aperture of the straight tubular body is about 1.2～4.0Myuemu, this 1 mm 2 per 39000 or so without gaps dense Was. When the cross section of the straight tubular body was observed with an electron microscope, the opening of the straight tubular body was shaped like a pipe that continued between the substrates. Furthermore, the height of the straight tubular body was about 20 μm.
実 施 例 ３
多孔質直管状コバルトめっき皮膜の形成：
（１）電気めっき浴の調製
水に、スルファミン酸コバルト４２０ｇ／Ｌ、塩化コバルト１０ｇ／Ｌ、ホウ酸４０ｇ／Ｌ、Ｎ，Ｎ−ジメチルベンジルアミン５ｇ／Ｌとなるように混合し、最後に、スルファミン酸でｐＨを１.６に調整して多孔質直管状コバルトめっき皮膜形成用電気めっき浴を得た。
Example 3
Formation of porous straight tubular cobalt plating film:
(1) Preparation of electroplating bath Mixing in water so that cobalt sulfamate 420 g / L, cobalt chloride 10 g / L, boric acid 40 g / L, N, N-dimethylbenzylamine 5 g / L, and finally, The pH was adjusted to 1.6 with sulfamic acid to obtain an electroplating bath for forming a porous straight tubular cobalt plating film.
（２）電解めっき
上記（１）で得た電気めっき浴を４０℃にしたものに、銅板を浸漬して電流密度２.４Ａ／ｄｍ２で６０分間めっきした。なお、めっき中は無撹拌とした。この電気めっき後の表面を電子顕微鏡で観察したところ（図４）、コバルトめっき皮膜の表面に、コバルトめっきで形成され、上面に開口部を有する直管状体が複数あることが分かった。直管状体の大きさ（最大幅）は３．５〜７．５μｍ程度であり、直管状体の開口の大きさは１．５〜３．５μｍ程度であり、これが１ｍｍ２あたり３５０００個程度隙間なく密集していた。また、直管状体の断面を電子顕微鏡で観察したところ、直管状体の開口は一直線に基板間で続くパイプのような形状であった。更に、直管状体の高さは８μｍ程度であった。
(2) Electrolytic plating A copper plate was immersed in the electroplating bath obtained in (1) above at 40 ° C. and plated at a current density of 2.4 A / dm 2 for 60 minutes. The agitation was not performed during plating. When the surface after electroplating was observed with an electron microscope (FIG. 4), it was found that there were a plurality of straight tubular bodies formed by cobalt plating on the surface of the cobalt plating film and having openings on the upper surface. The size (maximum width) of the straight tubular body is about 3.5 to 7.5 μm, and the size of the opening of the straight tubular body is about 1.5 to 3.5 μm, which is about 35000 gaps per 1 mm 2. It was dense. When the cross section of the straight tubular body was observed with an electron microscope, the opening of the straight tubular body was shaped like a pipe that continued between the substrates. Furthermore, the height of the straight tubular body was about 8 μm.
比 較 例 １
ニッケルめっき皮膜の形成：
実施例１（１）の電気めっき浴の調製において、第３級アミンであるＮ，Ｎ−ジメチルベンジルアミン２ｇ／Ｌに代えて第４級アンモニウム塩であるベンジルトリエチルアンモニウムクロライド２ｇ／Ｌを用いる以外は同様にしてニッケルめっき皮膜形成用電気めっき浴を得た。
Comparative Example 1
Formation of nickel plating film:
In the preparation of the electroplating bath of Example 1 (1), benzyltriethylammonium chloride 2 g / L which is a quaternary ammonium salt is used in place of 2 g / L which is a tertiary amine N, N-dimethylbenzylamine. In the same manner, an electroplating bath for forming a nickel plating film was obtained.
上記で得た電気めっき浴を４０℃にしたものに、銅板を浸漬して電流密度１.２Ａ／ｄｍ２で６０分間めっきした。なお、めっき中は無撹拌とした。この電気めっき後の表面を電子顕微鏡で観察したところ（図５）、皮膜が多孔質であることが分かった。しかし、この皮膜の断面を電子顕微鏡で観察したところ（図６）、多孔質となっているのはニッケルめっきが海綿状に析出したためであることが分かった。 A copper plate was immersed in the electroplating bath obtained above at 40 ° C. and plated at a current density of 1.2 A / dm 2 for 60 minutes. The agitation was not performed during plating. When the surface after this electroplating was observed with an electron microscope (FIG. 5), it was found that the film was porous. However, when the cross section of this film was observed with an electron microscope (FIG. 6), it was found that the porous layer was formed by the nickel plating deposited in a spongy manner.
実 施 例 ４
多孔質直管状鉄めっき皮膜の形成：
（１）電気めっき浴の調製
水に、硫酸第一鉄２５０ｇ／Ｌ、塩化第一鉄４０ｇ／Ｌ、塩化アンモニウム２０ｇ／Ｌ、Ｎ，Ｎ−ジメチルベンジルアミン５ｇ／Ｌとなるように混合し、最後に、硫酸でｐＨを２．０に調整して多孔質直管状鉄めっき皮膜形成用電気めっき浴を得た。
Example 4
Formation of porous straight tubular iron plating film:
(1) Preparation of electroplating bath In water, the mixture was mixed with 250 g / L of ferrous sulfate, 40 g / L of ferrous chloride, 20 g / L of ammonium chloride, and 5 g / L of N, N-dimethylbenzylamine. Finally, the pH was adjusted to 2.0 with sulfuric acid to obtain an electroplating bath for forming a porous straight tubular iron plating film.
本発明によれば、比表面積の大きい鉄族元素めっき皮膜が得られるため、熱交換器、フィルター、蓄電デバイス等の製造に好適に利用することができる。
以 上
According to the present invention, since an iron group element plating film having a large specific surface area can be obtained, it can be suitably used for the manufacture of heat exchangers, filters, power storage devices and the like.
that's all
Claims (7)
で示される第３級アミンを含有させたことを特徴とする多孔質直管状鉄族元素めっき皮膜形成用電気めっき浴。 In the iron group element plating bath, the following formula (I)
An electroplating bath for forming a porous straight tubular iron group element plating film characterized by containing a tertiary amine represented by
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| JPS58130296A (en) * | 1982-01-29 | 1983-08-03 | C Uyemura & Co Ltd | Forming agent for patterned electroplating film |
| JPH05179480A (en) * | 1991-02-26 | 1993-07-20 | Pentel Kk | Tin-nickel binary alloy electroplating liquid composition |
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