JP6084899B2 - Electroplating bath for iron-nickel alloy having low thermal expansion coefficient and high hardness, and electroplating method using the same - Google Patents
Electroplating bath for iron-nickel alloy having low thermal expansion coefficient and high hardness, and electroplating method using the same Download PDFInfo
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims description 66
- 238000009713 electroplating Methods 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 10
- -1 unsaturated sulfonic acid compound Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims 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 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- IRJHRRSZWWXNJL-UHFFFAOYSA-N prop-2-yne-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC#C IRJHRRSZWWXNJL-UHFFFAOYSA-N 0.000 claims description 2
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 2
- 238000007747 plating Methods 0.000 description 31
- 239000000203 mixture Substances 0.000 description 14
- 229910001374 Invar Inorganic materials 0.000 description 10
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000176 sodium gluconate Substances 0.000 description 4
- 235000012207 sodium gluconate Nutrition 0.000 description 4
- 229940005574 sodium gluconate Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 2
- 229940085605 saccharin sodium Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-BJUDXGSMSA-N Iron-55 Chemical compound [55Fe] XEEYBQQBJWHFJM-BJUDXGSMSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FYHLDUXIKXBAAT-UHFFFAOYSA-N prop-1-yne-1-sulfonic acid Chemical compound CC#CS(O)(=O)=O FYHLDUXIKXBAAT-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、低熱膨張係数および高硬度を有する鉄−ニッケル合金を形成させるための電気メッキ液およびこれを用いた電気メッキ方法に関する。 The present invention relates to an electroplating solution for forming an iron-nickel alloy having a low thermal expansion coefficient and high hardness, and an electroplating method using the same.
鉄−ニッケル合金は、特定の組成（インバー組成）になると低熱膨張係数および高硬度となることが知られている。このインバー組成の鉄−ニッケル合金は温度によって寸法が変化しないため、フォトマスク、バイメタル等に利用されている。 It is known that an iron-nickel alloy has a low coefficient of thermal expansion and high hardness when it has a specific composition (invar composition). The iron-nickel alloy having this invar composition is used for a photomask, a bimetal, and the like because its dimensions do not change with temperature.
このようなインバー組成の鉄−ニッケル合金は、通常溶製合金であるが、メッキによりインバー組成の鉄−ニッケル合金を直接析出させることができれば、用途が広がることは明らかである。 The iron-nickel alloy having such an invar composition is usually a melted alloy, but it is clear that the use is widened if the iron-nickel alloy having the invar composition can be directly deposited by plating.
しかしながら、溶製で得られる鉄−ニッケル合金と、メッキで得られる鉄−ニッケル合金とは合金相が異なるため、単純にインバー組成と同じ組成になるような鉄−ニッケル合金をメッキで得ても、溶製のものと同様の性質は得られない。 However, the iron-nickel alloy obtained by melting and the iron-nickel alloy obtained by plating have different alloy phases. Therefore, even if an iron-nickel alloy having the same composition as the Invar composition is obtained by plating. , Properties similar to those produced by melting cannot be obtained.
これまでメッキでインバー組成と同様の性質の鉄−ニッケル合金を析出させる技術としては、ニッケル塩、第一鉄塩、錯化剤および緩衝剤を含む水溶液中に平均粒径３μｍ以下の微粒子を分散させた鉄−ニッケル合金メッキ液で電気メッキを行った後、４００℃以上の熱処理を行う方法が報告されている（特許文献１、非特許文献１）。この技術により低熱膨張係数および高硬度を有する鉄−ニッケル合金が得られている。 Until now, as a technique for depositing an iron-nickel alloy having the same properties as the Invar composition by plating, fine particles having an average particle size of 3 μm or less are dispersed in an aqueous solution containing a nickel salt, a ferrous salt, a complexing agent and a buffering agent. There has been reported a method of performing a heat treatment at 400 ° C. or higher after electroplating with an iron-nickel alloy plating solution (Patent Document 1, Non-Patent Document 1). This technique has yielded an iron-nickel alloy having a low coefficient of thermal expansion and high hardness.
しかしながら、上記技術では、メッキ液に微粒子を含有させることが必須であったり、撹拌の条件を制御することが必須であったり、更にはメッキ後にも熱処理が必須であるため、工程が煩雑であった。そのため、より簡便にインバー組成と同様の性質の鉄−ニッケル合金をメッキで得る技術が求められていた。 However, in the above technique, it is essential to contain fine particles in the plating solution, it is essential to control the stirring conditions, and furthermore, heat treatment is essential even after plating, so the process is complicated. It was. Therefore, there has been a demand for a technique for easily obtaining an iron-nickel alloy having the same properties as the Invar composition by plating.
本発明は上記課題を解決するために鋭意研究した結果、本発明者らは従来公知の鉄−ニッケル合金電気メッキ液に更に分子末端にビニル基やエチニル基のような不飽和結合を持つ基を有するスルホン酸の化合物を含有させたメッキ液で電気メッキをすることにより、電気メッキ後に熱処理をすることなく、低熱膨張係数および高硬度を有する鉄−ニッケル合金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 further added a group having an unsaturated bond such as a vinyl group or an ethynyl group at the molecular end to a conventionally known iron-nickel alloy electroplating solution. The present inventors have found that an iron-nickel alloy having a low coefficient of thermal expansion and high hardness can be obtained without performing a heat treatment after electroplating by electroplating with a plating solution containing a sulfonic acid compound having the present invention. Completed.
すなわち、本発明は鉄−ニッケル合金用電気メッキ浴に、更に、以下の一般式（１）
で表される不飽和スルホン酸化合物を含有させたことを特徴とする低熱膨張係数および高硬度を有する鉄−ニッケル合金用電気メッキ浴である。
That is, the present invention relates to an electroplating bath for iron-nickel alloy, and the following general formula (1):
An electroplating bath for an iron-nickel alloy having a low thermal expansion coefficient and high hardness, characterized by containing an unsaturated sulfonic acid compound represented by the formula:
また、本発明は、被メッキ物を、上記低熱膨張係数および高硬度を有する鉄−ニッケル合金用電気メッキ浴で処理することを特徴とする低熱膨張係数および高硬度を有する鉄−ニッケル合金の電気メッキ方法である。 The present invention also relates to an iron-nickel alloy having a low thermal expansion coefficient and high hardness, characterized in that an object to be plated is treated with the above-described electroplating bath for iron-nickel alloy having a low thermal expansion coefficient and high hardness. It is a plating method.
更に、本発明は、被メッキ物を、上記低熱膨張係数および高硬度を有する鉄−ニッケル合金用電気メッキ浴で処理することにより得られる低熱膨張係数および高硬度を有する鉄−ニッケル合金被覆製品である。 Furthermore, the present invention provides an iron-nickel alloy-coated product having a low thermal expansion coefficient and high hardness obtained by treating an object to be plated with an electroplating bath for iron-nickel alloy having the above low thermal expansion coefficient and high hardness. is there.
本発明によれば溶製で得られるインバー組成の鉄−ニッケル合金と同様の性質を有する鉄−ニッケル合金を、電気メッキのみで得ることができ、従来のように、メッキの条件も複雑でなはなく、微粒子の含有が不必要で、更にメッキ後の熱処理も必要ない。 According to the present invention, an iron-nickel alloy having the same properties as an iron-nickel alloy having an invar composition obtained by melting can be obtained only by electroplating, and the plating conditions are complicated as in the prior art. There is no need to contain fine particles, and no heat treatment after plating is required.
そのため、本発明は、溶製で製造されるインバー組成の鉄−ニッケル合金と同様な用途に用いることができるのは勿論のこと、更に、溶製で製造される鉄−ニッケル合金よりも容易に薄く広い面積でも、あるいは微細な物でも均一に被メッキ部材に被覆できるため、新たな用途への応用が期待できる。 Therefore, the present invention can be used for the same application as an iron-nickel alloy having an invar composition manufactured by melting, and more easily than an iron-nickel alloy manufactured by melting. Even a thin, wide area or even a fine object can be uniformly coated on a member to be plated, so that application to a new application can be expected.
本発明の低熱膨張係数および高硬度を有する鉄−ニッケル合金用メッキ浴（以下、「本発明メッキ浴」という）は、従来公知の鉄−ニッケル合金用電気メッキ浴に、更に、以下の一般式（１）
上記不飽和スルホン酸化合物において、Ｒはビニル基またはエチニル基であり、好ましくはビニル基である。また、Ｘは置換されていてもよい、アルキレン基またはフェニレン基であり、好ましくは置換されていないアルキレン基またはフェニレン基であり、より好ましくは置換されていないアルキレン基である。置換基としては炭素数１〜３のアルキル基、ハロゲン、ヒドロキシル基等が挙げられ、アルキレン基としては炭素数１〜１０のもの、好ましくは炭素数１〜３のもの、より好ましくは炭素数１のものが挙げられる。更に、Ｙはアルカリ金属であり、好ましくはリチウム、ナトリウム、カリウムであり、より好ましくはナトリウムである。 In the unsaturated sulfonic acid compound, R is a vinyl group or an ethynyl group, preferably a vinyl group. X is an optionally substituted alkylene group or phenylene group, preferably an unsubstituted alkylene group or phenylene group, and more preferably an unsubstituted alkylene group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a halogen, and a hydroxyl group. The alkylene group has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 carbon atom. Can be mentioned. Furthermore, Y is an alkali metal, preferably lithium, sodium or potassium, more preferably sodium.
より具体的な不飽和スルホン酸化合物としては、アリルスルホン酸ナトリウム、ビニルスルホン酸ナトリウム、プロピンスルホン酸ナトリウム等が挙げられ、好ましくはアリルスルホン酸ナトリウムである。これらの不飽和スルホン酸化合物は、１種または２種以上を組み合わせて用いても良い。 More specific examples of the unsaturated sulfonic acid compound include sodium allyl sulfonate, sodium vinyl sulfonate, sodium propyne sulfonate, and the like, preferably sodium allyl sulfonate. These unsaturated sulfonic acid compounds may be used alone or in combination of two or more.
本発明メッキ浴における、不飽和スルホン酸化合物の含有量は１〜１０質量％（以下、単に「％」という）、好ましくは４〜８％である。 The content of the unsaturated sulfonic acid compound in the plating bath of the present invention is 1 to 10% by mass (hereinafter simply referred to as “%”), preferably 4 to 8%.
本発明メッキ浴のベースとなる従来公知の鉄−ニッケル合金用電気メッキ浴としては、特に限定されないが、例えば、鉄イオン、ニッケルイオン、リンゴ酸、クエン酸等の錯化剤、ホウ酸、酢酸等の緩衝剤を含有するものが挙げられる。より具体的な鉄−ニッケル合金用電気メッキ浴としては、塩化物浴、硫酸塩浴、硫酸塩−塩化物浴、シアン浴、クエン酸浴、ピロリン酸浴、ワット浴、スルファミン酸浴等が挙げられる。これらの中でもワット浴、スルファミン酸浴が好ましい。 Although it does not specifically limit as a conventionally well-known electroplating bath for iron-nickel alloys used as the base of this invention plating bath, For example, complexing agents, such as iron ion, nickel ion, malic acid, a citric acid, boric acid, acetic acid And those containing a buffering agent. More specific examples of the electroplating bath for iron-nickel alloy include chloride bath, sulfate bath, sulfate-chloride bath, cyan bath, citric acid bath, pyrophosphate bath, watt bath, sulfamic acid bath, and the like. It is done. Among these, Watt bath and sulfamic acid bath are preferable.
また、本発明メッキ浴には、上記従来公知の鉄−ニッケル合金用電気メッキ浴に、更にコバルトを含有させてもよい。この場合、この場合のコバルトの添加量は特に限定されず、例えば１〜１００ｇ／Ｌ、好ましくは１〜５０ｇ／Ｌである。また、コバルト源としては、硫酸コバルト等が挙げられる。 Further, the plating bath of the present invention may further contain cobalt in the above-described conventionally known electroplating bath for iron-nickel alloy. In this case, the addition amount of cobalt in this case is not specifically limited, For example, it is 1-100 g / L, Preferably it is 1-50 g / L. Moreover, cobalt sulfate etc. are mentioned as a cobalt source.
なお、本発明メッキ浴には、上記した従来公知の鉄−ニッケル合金用電気メッキ浴において、特に鉄を４〜１２ｇ／ｌ、好ましくは６〜１０ｇ／ｌ、ニッケルを２０〜５０ｇ／ｌ、好ましくは２５〜４０ｇ／ｌ含有させたものを用いることが好ましい。 In the plating bath of the present invention, in the above-described conventional electroplating bath for iron-nickel alloy, iron is particularly 4 to 12 g / l, preferably 6 to 10 g / l, nickel is 20 to 50 g / l, preferably It is preferable to use those containing 25 to 40 g / l.
以下に、本発明メッキ浴の好ましい態様として、ワット浴、スルファミン酸浴の組成を記載する。 Below, the composition of a watt bath and a sulfamic acid bath is described as a preferred embodiment of the plating bath of the present invention.
＜ワット浴＞
硫酸ニッケル：５０〜１２５ｇ／Ｌ、好ましくは６０〜１００ｇ／Ｌ
塩化ニッケル：４０〜８０ｇ／Ｌ、好ましくは５０〜７０ｇ／Ｌ
ホウ酸：３０〜６０ｇ／Ｌ
硫酸第一鉄：２０〜６０ｇ／Ｌ、好ましくは３５〜５０ｇ／Ｌ
グルコン酸ナトリウム：２０〜８０ｇ／Ｌ、好ましくは５０〜６０ｇ／Ｌ
サッカリンナトリウム：１〜５ｇ／Ｌ、好ましくは２〜４ｇ／Ｌ
アリルスルホン酸ナトリウム：１.５〜１０ｇ／Ｌ、好ましくは３.５〜８.５ｇ／Ｌ
<Watt bath>
Nickel sulfate: 50 to 125 g / L, preferably 60 to 100 g / L
Nickel chloride: 40-80 g / L, preferably 50-70 g / L
Boric acid: 30-60 g / L
Ferrous sulfate: 20-60 g / L, preferably 35-50 g / L
Sodium gluconate: 20-80 g / L, preferably 50-60 g / L
Saccharin sodium: 1 to 5 g / L, preferably 2 to 4 g / L
Sodium allyl sulfonate: 1.5-10 g / L, preferably 3.5-8.5 g / L
＜スルファミン酸浴＞
スルファミン酸ニッケル：９０〜２５０ｇ／Ｌ、好ましくは１４０〜１９０ｇ／Ｌ
ホウ酸：３０〜６０ｇ／Ｌ
臭化ニッケル：５〜１５ｇ／Ｌ、好ましくは６〜１０ｇ／Ｌ
スルファミン酸鉄：２５〜７５ｇ／Ｌ、好ましくは４０〜６０ｇ／Ｌ
グルコン酸ナトリウム：２０〜８０ｇ／Ｌ、好ましくは５０〜６０ｇ／Ｌ
サッカリンナトリウム：１〜５ｇ／Ｌ、好ましくは２〜４ｇ／Ｌ
アリルスルホン酸ナトリウム：１.５〜１０ｇ／Ｌ、好ましくは３.５〜８.５ｇ／Ｌ
<Sulphamic acid bath>
Nickel sulfamate: 90 to 250 g / L, preferably 140 to 190 g / L
Boric acid: 30-60 g / L
Nickel bromide: 5 to 15 g / L, preferably 6 to 10 g / L
Iron sulfamate: 25-75 g / L, preferably 40-60 g / L
Sodium gluconate: 20-80 g / L, preferably 50-60 g / L
Saccharin sodium: 1 to 5 g / L, preferably 2 to 4 g / L
Sodium allyl sulfonate: 1.5-10 g / L, preferably 3.5-8.5 g / L
本発明メッキ浴を用いて被メッキ物に電気メッキする方法は、特に限定されず、例えば、被メッキ物に、アルカリ脱脂、酸活性等の前処理を行った後、これを本発明メッキ浴に浸漬する方法等が挙げられる。 The method of electroplating an object to be plated using the plating bath of the present invention is not particularly limited. For example, after subjecting the object to be plated to pretreatment such as alkaline degreasing and acid activity, this is applied to the plating bath of the present invention. Examples include a dipping method.
電気メッキの条件は、特に限定されず、通常の鉄−ニッケル合金の電気メッキの条件を用いればよく、例えば、浴温４０〜６０℃で、アノードに鉄、ニッケルを併用し、陰極電流密度１〜３Ａ／ｄｍ２で行えばよい。また、電気メッキの際にはパドル等で撹拌することが好ましい。 Electroplating conditions are not particularly limited, and normal electroplating conditions of iron-nickel alloy may be used. For example, the bath temperature is 40 to 60 ° C., iron and nickel are used in combination with the anode, and the cathode current density is 1 it may be carried out by ~3A / dm 2. Moreover, it is preferable to stir with a paddle or the like during electroplating.
なお、電気メッキの条件として、メッキ浴の温度を高くすれば得られる鉄−ニッケル合金における鉄の比率が低くなり、また、撹拌速度を早くすれば鉄の比率は高くなり、更に、メッキ浴の鉄濃度を相対的に下げれば鉄の比率が低くなる傾向がわかっているため、当業者であればこれらの条件の調整により鉄−ニッケル合金における鉄とニッケルの比率を制御することもできる。 As the electroplating conditions, if the temperature of the plating bath is increased, the iron ratio in the obtained iron-nickel alloy is decreased, and if the stirring speed is increased, the iron ratio is increased. Since it is known that the iron ratio tends to decrease when the iron concentration is relatively lowered, those skilled in the art can control the ratio of iron to nickel in the iron-nickel alloy by adjusting these conditions.
本発明メッキ浴で電気メッキすることができる被メッキ物は特に限定されず、例えば、表面が、銅、ニッケル、ステンレス等の金属、ＡＢＳ、ポリイミド等の樹脂等で形成されたもの等が挙げられる。 The object to be plated that can be electroplated in the plating bath of the present invention is not particularly limited, and examples thereof include those whose surface is formed of a metal such as copper, nickel or stainless steel, a resin such as ABS or polyimide, and the like. .
上記のようにして被メッキ物に電気メッキして得られる鉄−ニッケル合金メッキ被覆製品は、低熱膨張係数および高硬度を有する。具体的には、鉄とニッケルの比率が、両者の合計量を１００％として、鉄が５５〜６４％およびニッケルが３６〜４５％、好ましくは鉄が５７〜５８％およびニッケルが４３〜４２％であり、熱膨張係数が９.０×１０−６／℃以下、好ましくは７.０×１０−６／℃以下であり、ビッカース硬度が２００ＨＶ以上、好ましくは３００〜３８０ＨＶである。 The iron-nickel alloy plating-coated product obtained by electroplating an object to be plated as described above has a low thermal expansion coefficient and high hardness. Specifically, the ratio of iron and nickel is such that the total amount of both is 100%, iron is 55 to 64% and nickel is 36 to 45%, preferably iron is 57 to 58% and nickel is 43 to 42%. The thermal expansion coefficient is 9.0 × 10 −6 / ° C. or less, preferably 7.0 × 10 −6 / ° C. or less, and the Vickers hardness is 200 HV or more, preferably 300 to 380 HV.
このような性質を有する鉄−ニッケル合金メッキ被覆製品は、低熱膨張係数および高硬度を有するためフォトマスク、バイメタル、金型電鋳等に利用することができる。 Since the iron-nickel alloy plated product having such properties has a low thermal expansion coefficient and high hardness, it can be used for photomasks, bimetals, die electroforming, and the like.
以下、本発明を実施例を挙げて詳細に説明するが、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 in detail, this invention is not limited to these Examples at all.
実 施 例 １
鉄−ニッケル合金用電気メッキ浴の調製：
水に、スルファミン酸ニッケル１５６ｇ／Ｌ、ホウ酸３０ｇ／Ｌ、臭化ニッケル７ｇ／Ｌ、スルファミン酸鉄５０ｇ／Ｌ、グルコン酸ナトリウム６０ｇ／Ｌ、サッカリンナトリウム３.２ｇ／Ｌおよびアリルスルホン酸ナトリウム（３６％）１６ｍｌ／Ｌを添加、混合し、鉄−ニッケル合金用電気メッキ浴を調製した。このメッキ浴のｐＨは３.８であり、ニッケルと鉄の含有量はそれぞれ３０ｇ／Ｌおよび８ｇ／Ｌであった。
Example 1
Preparation of electroplating bath for iron-nickel alloy:
In water, nickel sulfamate 156 g / L, boric acid 30 g / L, nickel bromide 7 g / L, iron sulfamate 50 g / L, sodium gluconate 60 g / L, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36 %) 16 ml / L was added and mixed to prepare an electroplating bath for iron-nickel alloy. The pH of this plating bath was 3.8, and the contents of nickel and iron were 30 g / L and 8 g / L, respectively.
実 施 例 ２
鉄−ニッケル合金用電気メッキ浴の調製：
水に、硫酸ニッケル７５ｇ／Ｌ、塩化ニッケル５５ｇ／Ｌ、ホウ酸４０ｇ／Ｌ、硫酸第一鉄４０ｇ／Ｌ、グルコン酸ナトリウム６０ｇ／Ｌ、サッカリンナトリウム３.２ｇ／Ｌおよびアリルスルホン酸ナトリウム（３６％）１６ｍｌ／Ｌを添加、混合し、鉄−ニッケル合金用電気メッキ浴を調製した。このメッキ浴のｐＨは３.０であり、ニッケルと鉄の含有量はそれぞれ３０ｇ／Ｌおよび８ｇ／Ｌであった。
Example 2
Preparation of electroplating bath for iron-nickel alloy:
In water, nickel sulfate 75 g / L, nickel chloride 55 g / L, boric acid 40 g / L, ferrous sulfate 40 g / L, sodium gluconate 60 g / L, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36% 16 ml / L was added and mixed to prepare an electroplating bath for iron-nickel alloy. The pH of this plating bath was 3.0, and the contents of nickel and iron were 30 g / L and 8 g / L, respectively.
実 施 例 ３
鉄−ニッケル合金電気メッキ皮膜の形成：
ポリイミド製の基板（１０×４０ｍｍ）に、アルカリ脱脂（４０℃、１０分）および酸活性（室温、３０秒）を行った後、実施例１で調製した鉄−ニッケル合金用電気メッキ浴に以下の条件で浸漬して目標膜厚１０μｍで電気メッキをして鉄−ニッケル合金電気メッキ皮膜を得た。
Example 3
Formation of iron-nickel alloy electroplating film:
After performing alkaline degreasing (40 ° C., 10 minutes) and acid activity (room temperature, 30 seconds) on a polyimide substrate (10 × 40 mm), the following is applied to the iron-nickel alloy electroplating bath prepared in Example 1. The film was immersed in the above conditions and electroplated with a target film thickness of 10 μm to obtain an iron-nickel alloy electroplated film.
＜メッキ条件＞
メッキ時間：３０分
液温：５０℃
アノード：鉄、ニッケル
陰極電流密度：２Ａ／ｄｍ２
撹拌：パドル撹拌（３ｍ／ｍｉｎ）
<Plating conditions>
Plating time: 30 minutes Liquid temperature: 50 ° C
Anode: Iron, nickel Cathode current density: 2 A / dm 2
Stirring: Paddle stirring (3m / min)
実 施 例 ４
鉄−ニッケル合金電気メッキ皮膜の形成：
温度を４０℃とする以外は実施例３と同様にして電気メッキをして鉄−ニッケル合金電気メッキ皮膜を得た。
Example 4
Formation of iron-nickel alloy electroplating film:
Except that the temperature was 40 ° C., electroplating was performed in the same manner as in Example 3 to obtain an iron-nickel alloy electroplating film.
実 施 例 ５
鉄−ニッケル合金電気メッキ皮膜の形成：
撹拌を６ｍ／ｍｉｎ、温度を４０℃とする以外は実施例３と同様にして電気メッキをして鉄−ニッケル合金電気メッキ皮膜を得た。
Example 5
Formation of iron-nickel alloy electroplating film:
An iron-nickel alloy electroplating film was obtained by electroplating in the same manner as in Example 3 except that the stirring was 6 m / min and the temperature was 40 ° C.
実 施 例 ６
鉄−ニッケル合金電気メッキ皮膜の形成：
実施例２で調製した鉄−ニッケル合金用電気メッキ浴を用い、温度を４０℃とする以外は実施例３と同様にして電気メッキをして鉄−ニッケル合金電気メッキ皮膜を得た。
Example 6
Formation of iron-nickel alloy electroplating film:
An iron-nickel alloy electroplating film was obtained by electroplating in the same manner as in Example 3 except that the temperature was set to 40 ° C. using the electroplating bath for iron-nickel alloy prepared in Example 2.
試 験 例 １
物性測定：
実施例３〜６で得られたメッキ皮膜について、外観を目視で評価した後、スパイラル応力計（（株）山本鍍金試験器社製：スパイラル鍍金応力計）を用いて応力、マイクロメータ（（株）ミツトヨ社製）で延展性、マイクロビッカース硬度計（（株）明石製作所社製：荷重０.２５Ｎ）を用いて硬度を測定した。また、熱膨張係数を窒素雰囲気下、２５〜２００℃の範囲で熱・応力・歪測定装置（エスアイアイ・ナノテクノロジー製：ＴＭＡ／ＳＳ ６１００：荷重５０ｍＮ：昇温速度５℃／ｍｉｎ）を用いて測定した。更に、皮膜中の鉄−ニッケルの質量比を蛍光Ｘ線分析法で求めた。これらの結果を表１に示した。
Test example 1
Physical property measurement:
About the plating film obtained in Examples 3-6, after visually evaluating the appearance, the stress was measured using a spiral stress meter (manufactured by Yamamoto Metal Tester Co., Ltd .: Spiral Metal Stress Tester), micrometer ((Co., Ltd.). The hardness was measured by using a micro Vickers hardness meter (manufactured by Akashi Seisakusho Co., Ltd .: load 0.25N). Further, a thermal / stress / strain measuring device (manufactured by SII Nanotechnology: TMA / SS 6100: load 50 mN: temperature rising rate 5 ° C./min) is used in a nitrogen atmosphere in a range of 25 to 200 ° C. in a nitrogen atmosphere. Measured. Furthermore, the mass ratio of iron-nickel in the film was determined by fluorescent X-ray analysis. These results are shown in Table 1.
以上の結果より、本発明メッキ浴により、電気メッキだけで熱処理を行わなくても低熱膨張係数および高硬度を有する鉄−ニッケル合金皮膜が得られることがわかった。また、低熱膨張係数が得られる鉄−ニッケル合金の組成は鉄５８％およびニッケル４２％付近にあることがわかった。 From the above results, it was found that an iron-nickel alloy film having a low thermal expansion coefficient and high hardness can be obtained by the plating bath of the present invention without performing heat treatment only by electroplating. It was also found that the composition of the iron-nickel alloy capable of obtaining a low thermal expansion coefficient was in the vicinity of 58% iron and 42% nickel.
比 較 例 １
比較メッキ：
アリルスルホン酸ナトリウム（３６％）を含まない以外は、実施例２と同様に鉄−ニッケル合金用電気メッキ浴を調製し、これを用いて実施例６と同様の条件で鉄−ニッケル合金電気メッキ皮膜を得た。なお、皮膜の外観は均一ではなかった。得られた皮膜について試験例１と同様にして皮膜中の鉄−ニッケルの質量比と、熱膨張係数（／℃）を測定した。その結果、鉄−ニッケルの質量比は鉄６４％およびニッケル３６％であり、熱膨張係数（／℃）は８.６×１０−６／℃であった。
Comparative Example 1
Comparative plating:
An iron-nickel alloy electroplating bath was prepared in the same manner as in Example 2 except that sodium allyl sulfonate (36%) was not contained, and this was used to perform iron-nickel alloy electroplating under the same conditions as in Example 6. A film was obtained. The appearance of the film was not uniform. About the obtained film | membrane, it carried out similarly to Test Example 1, and measured the mass ratio of iron-nickel in a film | membrane, and a thermal expansion coefficient (/ degreeC). As a result, the mass ratio of iron-nickel was iron 64% and nickel 36%, and the thermal expansion coefficient (/ ° C.) was 8.6 × 10 −6 / ° C.
実 施 例 ７
鉄−ニッケル合金電気メッキ皮膜の形成：
アリルスルホン酸ナトリウム（３６％）をビニルスルホン酸とする以外は、実施例２と同様に鉄−ニッケル合金用電気メッキ浴を調製し、これを用いて実施例６と同様の条件で鉄−ニッケル合金電気メッキ皮膜を得た。均一な皮膜外観が得られ、鉄−ニッケルの質量比は鉄５５およびニッケル４５％であった。この皮膜は低熱膨張係数および高硬度を有する。
Example 7
Formation of iron-nickel alloy electroplating film:
An electroplating bath for iron-nickel alloy was prepared in the same manner as in Example 2 except that sodium allyl sulfonate (36%) was changed to vinyl sulfonic acid, and iron-nickel was used under the same conditions as in Example 6 using this. An alloy electroplating film was obtained. A uniform film appearance was obtained and the mass ratio of iron-nickel was iron 55 and nickel 45%. This coating has a low coefficient of thermal expansion and a high hardness.
実 施 例 ８
鉄−ニッケル合金電気メッキ皮膜の形成：
アリルスルホン酸ナトリウム（３６％）をプロピンスルホン酸とする以外は、実施例２と同様に鉄−ニッケル合金用電気メッキ浴を調製し、これを用いて実施例６と同様の条件で鉄−ニッケル合金電気メッキ皮膜を得た。得られた皮膜の鉄−ニッケルの質量比は鉄６２％およびニッケル３８％であった。この皮膜は低熱膨張係数および高硬度を有する。
Example 8
Formation of iron-nickel alloy electroplating film:
An iron-nickel alloy electroplating bath was prepared in the same manner as in Example 2 except that sodium allyl sulfonate (36%) was used as propyne sulfonic acid. A nickel alloy electroplating film was obtained. The obtained coating had an iron-nickel mass ratio of 62% iron and 38% nickel. This coating has a low coefficient of thermal expansion and a high hardness.
本発明は、溶製で製造されるインバー組成の鉄−ニッケル合金と同様な用途に用いることができるのは勿論のこと、更に、溶製で製造される鉄−ニッケル合金よりも容易に薄く広い面積でも均一に被メッキ部材に被覆できるので新たな用途への応用が期待できる。
以 上
The present invention can be used for the same application as an iron-nickel alloy having an invar composition manufactured by melting, and more easily and wider than an iron-nickel alloy manufactured by melting. Since it is possible to uniformly coat the member to be plated even in the area, application to new applications can be expected.
that's all
Claims (3)
で表される不飽和スルホン酸化合物を含有させた鉄−ニッケル合金用電気メッキ浴（ただし、平均粒径３μｍ以下の微粒子を含むものを除く）を用い、撹拌して浴温４０〜６０℃でアノードに鉄、ニッケルを併用し、陰極電流密度１〜３Ａ／ｄｍ２で電気メッキし、電気メッキ後に、熱処理を行わないことを特徴とする鉄とニッケルの比率が両者の合計量を１００質量％として、鉄が５５〜６４質量％およびニッケルが３６〜４５質量％であり、窒素雰囲気下、２５〜２００℃の範囲で測定される熱膨張係数が７.０×１０−６／℃以下であり、ビッカース硬度が２００ＨＶ以上である鉄−ニッケル合金の電気メッキ方法。 An object to be plated is applied to an electroplating bath for iron-nickel alloy containing 4 to 12 g / l of iron and 20 to 50 g / l of nickel, and the following general formula (1)
An electroplating bath for an iron-nickel alloy containing an unsaturated sulfonic acid compound represented by the above (excluding those containing fine particles having an average particle size of 3 μm or less) and stirring at a bath temperature of 40 to 60 ° C. Iron and nickel are used in combination with the anode, electroplating is performed at a cathode current density of 1 to 3 A / dm 2 , and heat treatment is not performed after electroplating. The ratio of iron and nickel is 100% by mass. As described above, iron is 55 to 64% by mass and nickel is 36 to 45% by mass, and the thermal expansion coefficient measured in the range of 25 to 200 ° C. in a nitrogen atmosphere is 7.0 × 10 −6 / ° C. or less. Electroplating method of iron-nickel alloy whose Vickers hardness is 200HV or more.
The method of electroplating an iron-nickel alloy according to claim 1 or 2, wherein the electroplating bath for the iron-nickel alloy is a watt bath or a sulfamic acid bath.
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| WO2019044383A1 (en) * | 2017-09-01 | 2019-03-07 | 株式会社Ｊｃｕ | Electroplating liquid for iron-nickel alloy having low coefficient of thermal expansion, and electroplating method using the electroplating liquid |
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| CA1024930A (en) * | 1972-07-03 | 1978-01-24 | Richard J. Clauss | Electrodeposition of bright nickel iron deposits |
| JPS5187437A (en) * | 1975-01-29 | 1976-07-31 | Permalite Chem Ltd | Nitsukeru tetsugokinnodenkaimetsukyodenkaishitsuyoeki |
| US3974044A (en) * | 1975-03-31 | 1976-08-10 | Oxy Metal Industries Corporation | Bath and method for the electrodeposition of bright nickel-iron deposits |
| BE891722A (en) * | 1981-01-13 | 1982-07-07 | Hooker Chemicals Plastics Corp | BATH AND METHOD FOR ELECTRODEPOSITION OF A BRILLIANT NICKEL-IRON ALLOY |
| SE8505725L (en) * | 1985-12-04 | 1987-06-05 | Perstorp Ab | INVARFOLIE |
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| JPH07233494A (en) * | 1994-02-24 | 1995-09-05 | Osaka City | Iron-group alloy electroplating bath |
| KR100505002B1 (en) * | 2003-04-24 | 2005-08-01 | 주식회사 나노인바 | Nani invar alloyes and the process of producing the same |
| JP5478292B2 (en) * | 2010-02-18 | 2014-04-23 | 京都市 | Method for producing iron-nickel alloy plating film having high hardness and low thermal expansion coefficient |
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| WO2019044383A1 (en) * | 2017-09-01 | 2019-03-07 | 株式会社Ｊｃｕ | Electroplating liquid for iron-nickel alloy having low coefficient of thermal expansion, and electroplating method using the electroplating liquid |
| KR20200044860A (en) * | 2017-09-01 | 2020-04-29 | 가부시끼가이샤 제이씨유 | Electroplating solution for iron-nickel alloys with low coefficient of thermal expansion and electroplating method using the same |
| CN111094633A (en) * | 2017-09-01 | 2020-05-01 | 株式会社杰希优 | Electroplating solution for iron-nickel alloy having low thermal expansion coefficient and electroplating method using the same |
| TWI763907B (en) * | 2017-09-01 | 2022-05-11 | 日商傑希優股份有限公司 | Electroplating solution for iron-nickel alloy with low coefficient of thermal expansion and electroplating method using the same |
| CN111094633B (en) * | 2017-09-01 | 2023-03-07 | 株式会社杰希优 | Electroplating solution for iron-nickel alloy having low thermal expansion coefficient and electroplating method using the same |
| KR102591174B1 (en) * | 2017-09-01 | 2023-10-18 | 가부시끼가이샤 제이씨유 | Electroplating solution for iron-nickel alloy with low thermal expansion coefficient and electroplating method using the same |
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