KR102591174B1 - Electroplating solution for iron-nickel alloy with low thermal expansion coefficient and electroplating method using the same - Google Patents
Electroplating solution for iron-nickel alloy with low thermal expansion coefficient and electroplating method using the same Download PDFInfo
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- KR102591174B1 KR102591174B1 KR1020207008220A KR20207008220A KR102591174B1 KR 102591174 B1 KR102591174 B1 KR 102591174B1 KR 1020207008220 A KR1020207008220 A KR 1020207008220A KR 20207008220 A KR20207008220 A KR 20207008220A KR 102591174 B1 KR102591174 B1 KR 102591174B1
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- South Korea
- Prior art keywords
- iron
- nickel
- nickel alloy
- electroplating
- thermal expansion
- Prior art date
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 114
- 238000009713 electroplating Methods 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 13
- -1 unsaturated sulfonic acid compound Chemical class 0.000 claims abstract description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 125000005156 substituted alkylene group Chemical group 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 229910052742 iron Inorganic materials 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 31
- 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 claims description 20
- 229940005574 sodium gluconate Drugs 0.000 claims description 20
- 239000000176 sodium gluconate Substances 0.000 claims description 20
- 235000012207 sodium gluconate Nutrition 0.000 claims description 20
- 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 18
- 238000003756 stirring Methods 0.000 claims description 18
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 12
- 239000001433 sodium tartrate Substances 0.000 claims description 12
- 229960002167 sodium tartrate Drugs 0.000 claims description 12
- 235000011004 sodium tartrates Nutrition 0.000 claims description 12
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- 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
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- RGHNJXZEOKUKBD-MGCNEYSASA-N D-galactonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-MGCNEYSASA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-MBMOQRBOSA-N D-mannonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O RGHNJXZEOKUKBD-MBMOQRBOSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 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
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229960001367 tartaric acid Drugs 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 55
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 97
- 239000000203 mixture Substances 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 13
- 239000004327 boric acid Substances 0.000 description 13
- 229910001374 Invar Inorganic materials 0.000 description 12
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 9
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 9
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 9
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- UQBLNFAAJGJKSC-UHFFFAOYSA-N nickel tetrahydrate Chemical compound O.O.O.O.[Ni] UQBLNFAAJGJKSC-UHFFFAOYSA-N 0.000 description 6
- 150000004686 pentahydrates Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- TXRHHNYLWVQULI-UHFFFAOYSA-L nickel(2+);disulfamate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O TXRHHNYLWVQULI-UHFFFAOYSA-L 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- FGJLAJMGHXGFDE-UHFFFAOYSA-L disodium;2,3-dihydroxybutanedioate;dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C(O)C(O)C([O-])=O FGJLAJMGHXGFDE-UHFFFAOYSA-L 0.000 description 2
- 239000010419 fine particle 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229940092162 sodium tartrate dihydrate Drugs 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 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
- WLQXLCXXAPYDIU-UHFFFAOYSA-L cobalt(2+);disulfamate Chemical compound [Co+2].NS([O-])(=O)=O.NS([O-])(=O)=O WLQXLCXXAPYDIU-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 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 group CC#CS(O)(=O)=O FYHLDUXIKXBAAT-UHFFFAOYSA-N 0.000 description 1
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 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
- 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 group OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Abstract
이하의 일반식 (1)
(단, R 은 비닐기 또는 에티닐기, X 는 치환되어 있어도 되는, 알킬렌기 또는 페닐렌기, Y 는 알칼리 금속을 나타낸다)
로 나타내는 불포화 술폰산 화합물을 함유하는 철-니켈 합금용 전기 도금액으로서,
추가로, 카르복실기를 1 개 이상, 하이드록시기를 2 개 이상 갖고, 탄소수가 2 개 이상인 카르복실산 화합물을 2 종 이상 함유하는 것을 특징으로 하는 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액 및 이것을 사용한 전기 도금 방법에 의해, 폭넓은 온도대에서 성능이 우수한 철-니켈 합금을 도금으로 얻는 기술을 제공한다.The following general formula (1)
(However, R represents a vinyl group or ethynyl group, X represents an optionally substituted alkylene group or phenylene group, and Y represents an alkali metal)
An electroplating solution for iron-nickel alloy containing an unsaturated sulfonic acid compound represented by,
Additionally, an electroplating solution for iron-nickel alloys having a low coefficient of thermal expansion, characterized in that it contains two or more types of carboxylic acid compounds having one or more carboxyl groups, two or more hydroxy groups, and two or more carbon atoms, and the same. We provide a technology to obtain an iron-nickel alloy with excellent performance over a wide temperature range by plating, using the electroplating method used.
Description
본 발명은, 저열팽창 계수를 갖는 철-니켈 합금을 형성시키기 위한 전기 도금액 및 이것을 사용한 전기 도금 방법에 관한 것이다.The present invention relates to an electroplating solution for forming an iron-nickel alloy having a low thermal expansion coefficient and an electroplating method using the same.
철-니켈 합금은, 특정한 조성 (인바 조성) 이 되면 저열팽창 계수 및 고경도가 되는 것이 알려져 있다. 이 인바 조성의 철-니켈 합금은 온도에 의해 치수가 변화하지 않기 때문에, 포토마스크, 바이메탈 등에 이용되고 있다.It is known that iron-nickel alloy has a low coefficient of thermal expansion and high hardness when it has a specific composition (Invar composition). Since the dimensions of this iron-nickel alloy of Invar composition do not change with temperature, it is used in photomasks, bimetals, etc.
이와 같은 인바 조성의 철-니켈 합금은, 통상적으로 용제 합금이지만, 도금에 의해 인바 조성의 철-니켈 합금을 직접 석출시킬 수 있으면, 용도가 확대되는 것은 분명하다.Such an iron-nickel alloy with an invar composition is usually a solvent alloy, but if the iron-nickel alloy with an invar composition can be directly precipitated by plating, it is clear that its uses will expand.
그러나, 용제로 얻어지는 철-니켈 합금과, 도금으로 얻어지는 철-니켈 합금은 합금상이 상이하기 때문에, 단순히 인바 조성과 동일한 조성이 되는 철-니켈 합금을 도금으로 얻어도, 용제의 것과 동일한 성질은 얻어지지 않는다.However, since the alloy phases of the iron-nickel alloy obtained by solvent and the iron-nickel alloy obtained by plating are different, even if an iron-nickel alloy with the same composition as the invar composition is simply obtained by plating, the same properties as those of the solvent are not obtained. I don't lose.
지금까지 도금으로 인바 조성과 동일한 성질의 철-니켈 합금을 석출시키는 기술로는, 니켈염, 제1철염, 착화제 및 완충제를 함유하는 수용액 중에 평균 입경 3 ㎛ 이하의 미립자를 분산시킨 철-니켈 합금 도금액으로 전기 도금을 실시한 후, 400 ℃ 이상의 열처리를 실시하는 방법이 보고되어 있다 (특허문헌 1, 비특허문헌 1). 이 기술에 의해 저열팽창 계수 및 고경도를 갖는 철-니켈 합금이 얻어지고 있다.Until now, the technology to precipitate an iron-nickel alloy with the same properties as the Invar composition by plating has been to disperse fine particles with an average particle size of 3 ㎛ or less in an aqueous solution containing a nickel salt, a ferrous salt, a complexing agent, and a buffering agent. A method of performing electroplating with an alloy plating solution and then performing heat treatment at 400°C or higher has been reported (Patent Document 1, Non-Patent Document 1). Through this technology, an iron-nickel alloy with a low coefficient of thermal expansion and high hardness is obtained.
그러나, 상기 기술에서는, 도금액에 미립자를 함유시키는 것이 필수이거나, 교반의 조건을 제어하는 것이 필수이거나, 나아가서는 도금 후에도 열처리가 필수이기 때문에, 공정이 번잡하였다. 그 때문에, 보다 간편하게 인바 조성과 동일한 성질의 철-니켈 합금을 도금으로 얻는 기술이 요구되고 있었다.However, in the above technology, the process was complicated because it was essential to include fine particles in the plating solution, it was essential to control the conditions of stirring, and further, heat treatment was essential even after plating. Therefore, there has been a demand for a technology to more simply obtain an iron-nickel alloy with the same properties as the Invar composition through plating.
본 출원인은, 특정한 불포화 술폰산 화합물을 함유하는 철-니켈 합금용 전기 도금액에 의해 상기 문제를 해결하여, 저열팽창 계수 및 고경도를 갖는 철-니켈 합금을 얻고 있다 (특허문헌 2).The present applicant has solved the above problem by using an electroplating solution for iron-nickel alloy containing a specific unsaturated sulfonic acid compound, and has obtained an iron-nickel alloy having a low coefficient of thermal expansion and high hardness (Patent Document 2).
상기와 같은 도금으로 얻어지는 인바 조성의 철-니켈 합금은 광택성이 부족하거나, 또, 통상적인 사용에서는 문제는 없지만, 더욱 폭넓은 온도대에서 성능을 유지할 수 없는 등의 과제가 있었다.The iron-nickel alloy of the Invar composition obtained by plating as described above had problems such as insufficient glossiness and the inability to maintain performance over a wider temperature range, although this was not a problem in normal use.
본 발명은 상기 과제를 해결하기 위해 예의 연구한 결과, 본 발명자들은 종래 공지된 불포화 술폰산 화합물을 함유하는 철-니켈 합금용 전기 도금액에, 특정한 구조를 갖는 카르복실산 화합물을 2 종 이상 함유시킨 도금액으로 전기 도금을 함으로써, 광택성을 갖고, 조성이 균일하고, 폭넓은 온도대에서 저열팽창 계수를 갖는 철-니켈 합금이 얻어지는 것을 알아내어, 본 발명을 완성시켰다.As a result of intensive research to solve the above problems, the present inventors have developed a plating solution in which two or more types of carboxylic acid compounds having a specific structure are contained in an electroplating solution for iron-nickel alloy containing a conventionally known unsaturated sulfonic acid compound. It was found that by electroplating, an iron-nickel alloy with gloss, uniform composition, and low thermal expansion coefficient over a wide temperature range was obtained, and the present invention was completed.
즉, 본 발명은 이하의 일반식 (1)That is, the present invention has the following general formula (1)
[화학식 1][Formula 1]
(단, R 은 비닐기 또는 에티닐기, X 는 치환되어 있어도 되는, 알킬렌기 또는 페닐렌기, Y 는 알칼리 금속을 나타낸다)(However, R represents a vinyl group or ethynyl group, X represents an optionally substituted alkylene group or phenylene group, and Y represents an alkali metal)
로 나타내는 불포화 술폰산 화합물을 함유하는 철-니켈 합금용 전기 도금액으로서,An electroplating solution for iron-nickel alloy containing an unsaturated sulfonic acid compound represented by,
추가로, 카르복실기를 1 개 이상, 하이드록시기를 2 개 이상 갖고, 탄소수가 2 개 이상인 카르복실산 화합물을 2 종 이상 함유하는 것을 특징으로 하는 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액이다.Additionally, it is an electroplating solution for iron-nickel alloys with a low thermal expansion coefficient, characterized in that it contains two or more types of carboxylic acid compounds having one or more carboxyl groups, two or more hydroxy groups, and two or more carbon atoms.
또, 본 발명은, 피도금물을, 상기 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액으로 전기 도금하는 것을 특징으로 하는 저열팽창 계수를 갖는 철-니켈 합금의 전기 도금 방법이다.Additionally, the present invention is an electroplating method for an iron-nickel alloy having a low thermal expansion coefficient, characterized in that the object to be plated is electroplated with the electroplating solution for an iron-nickel alloy having a low thermal expansion coefficient.
또한, 본 발명은, 피도금물을, 상기 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액으로 전기 도금함으로써 얻어지는 저열팽창 계수를 갖는 철-니켈 합금 도금 피복 제품이다.Furthermore, the present invention is an iron-nickel alloy plating coating product having a low thermal expansion coefficient obtained by electroplating a plated object with the electroplating solution for iron-nickel alloy having the low thermal expansion coefficient.
본 발명에 의하면 용제로 얻어지는 인바 조성의 철-니켈 합금보다 폭넓은 온도대에서 저열팽창 계수를 갖는 철-니켈 합금을, 전기 도금만으로 얻을 수 있다.According to the present invention, an iron-nickel alloy having a lower thermal expansion coefficient in a wider temperature range than an iron-nickel alloy of Invar composition obtained by solvent can be obtained only by electroplating.
그 때문에, 본 발명은, 용제로 제조되는 인바 조성의 철-니켈 합금과 동일한 용도에 사용할 수 있는 것은 물론, 파워 일렉트로닉스 등의 새로운 용도로의 응용을 기대할 수 있다.Therefore, the present invention can be used for the same applications as the iron-nickel alloy of the Invar composition manufactured with a solvent, and can also be expected to be applied to new applications such as power electronics.
본 발명의 저열팽창 계수를 갖는 철-니켈 합금용 도금액 (이하,「본 발명 도금액」이라고 한다) 에 사용되는, 카르복실기를 1 개 이상, 하이드록시기를 2 개 이상 갖고, 탄소수가 2 개 이상인 카르복실산 화합물은, 특별히 한정되지 않지만, 예를 들어, 글루콘산, 갈락톤산, 만논산, 타르타르산 등의 카르복실산이나, 타르타르산나트륨, 글루콘산나트륨 등의 상기 카르복실산의 알칼리 금속염 등을 들 수 있다. 이들 카르복실산 화합물 중에서도 타르타르산나트륨, 글루콘산나트륨이 바람직하다. 또한, 상기 카르복실산 화합물에 있어서, 카르복실기나 하이드록시기의 수를 계산하는 경우, 카르복실기 중의 하이드록시기는, 하이드록시기의 수에는 넣지 않는다. 그 때문에, 말론산이나 말산은 상기 카르복실산 화합물에는 포함되지 않는다. 이들 카르복실산 화합물은 본 발명 도금액에 2 종 이상, 바람직하게는 2 종 함유시킬 필요가 있다.A carboxyl group having one or more carboxyl groups, two or more hydroxy groups, and having two or more carbon atoms, used in a plating solution for iron-nickel alloys having a low thermal expansion coefficient of the present invention (hereinafter referred to as “plating solution of the present invention”) The acid compound is not particularly limited, but examples include carboxylic acids such as gluconic acid, galactonic acid, mannonic acid, and tartaric acid, and alkali metal salts of these carboxylic acids such as sodium tartrate and sodium gluconate. . Among these carboxylic acid compounds, sodium tartrate and sodium gluconate are preferable. In addition, when calculating the number of carboxyl groups or hydroxy groups in the above carboxylic acid compound, the hydroxy groups in the carboxyl groups are not included in the number of hydroxy groups. Therefore, malonic acid and malic acid are not included in the carboxylic acid compounds. These carboxylic acid compounds need to be contained in the plating solution of the present invention at least two types, preferably two types.
본 발명 도금액에 있어서의, 카르복실산 화합물의 함유량은, 특별히 한정되지 않지만, 예를 들어, 2 종류의 합계량으로서, 30 ∼ 260 g/ℓ, 바람직하게는 55 ∼ 200 g/ℓ, 특히 바람직하게는 80 ∼ 160 g/ℓ 이다. 본 발명 도금액에, 카르복실산 화합물로서, 글루콘산나트륨과 타르타르산나트륨의 2 종을 사용하는 경우에는, 글루콘산나트륨은, 20 ∼ 180 g/ℓ, 바람직하게는 40 ∼ 140 g/ℓ, 특히 바람직하게는 60 ∼ 120 g/ℓ 이고, 타르타르산나트륨은, 10 ∼ 80 g/ℓ, 바람직하게는 15 ∼ 60 g/ℓ, 특히 바람직하게는 20 ∼ 40 g/ℓ 이다. 또 글루콘산나트륨/타르타르산나트륨의 농도비는 질량비로 10 ∼ 1.25, 바람직하게는 6.5 ∼ 1.5, 특히 바람직하게는 5 ∼ 2.5 이다.The content of the carboxylic acid compound in the plating solution of the present invention is not particularly limited, but for example, the total amount of the two types is 30 to 260 g/l, preferably 55 to 200 g/l, especially preferably is 80 to 160 g/l. In the case where two types of carboxylic acid compounds, sodium gluconate and sodium tartrate, are used in the plating solution of the present invention, the sodium gluconate content is 20 to 180 g/l, preferably 40 to 140 g/l, especially preferred. Typically, it is 60 to 120 g/l, and the sodium tartrate content is 10 to 80 g/l, preferably 15 to 60 g/l, and particularly preferably 20 to 40 g/l. Moreover, the concentration ratio of sodium gluconate/sodium tartrate is 10 to 1.25, preferably 6.5 to 1.5, and particularly preferably 5 to 2.5 in mass ratio.
본 발명 도금액에 사용되는 일반식 (1)General formula (1) used in the plating solution of the present invention
[화학식 2][Formula 2]
로 나타내는 불포화 술폰산 화합물은, 상기 식에 있어서, R 은 비닐기 또는 에티닐기이고, 바람직하게는 비닐기이다. 또, X 는 치환되어 있어도 되는, 알킬렌기 또는 페닐렌기이고, 바람직하게는 치환되어 있지 않은 알킬렌기 또는 페닐렌기이고, 보다 바람직하게는 치환되어 있지 않은 알킬렌기이다. 치환기로는 탄소수 1 ∼ 3 의 알킬기, 할로겐, 하이드록실기 등을 들 수 있고, 알킬렌기로는 탄소수 1 ∼ 10 의 것, 바람직하게는 탄소수 1 ∼ 3 의 것, 보다 바람직하게는 탄소수 1 의 것을 들 수 있다. 또한, Y 는 알칼리 금속이고, 바람직하게는 리튬, 나트륨, 칼륨이고, 보다 바람직하게는 나트륨이다.In the above formula, R is a vinyl group or an ethynyl group, and is preferably a vinyl group. In addition, Substituents include alkyl groups, halogens, and hydroxyl groups having 1 to 3 carbon atoms, and alkylene groups include those having 1 to 10 carbon atoms, preferably those with 1 to 3 carbon atoms, and more preferably 1 carbon atoms. I can hear it. Additionally, Y is an alkali metal, preferably lithium, sodium, or potassium, and more preferably sodium.
보다 구체적인 불포화 술폰산 화합물로는, 알릴술폰산나트륨, 비닐술폰산나트륨, 프로핀술폰산나트륨 등을 들 수 있고, 바람직하게는 알릴술폰산나트륨이다. 이들 불포화 술폰산 화합물은, 1 종 또는 2 종 이상을 조합하여 사용해도 된다.More specific unsaturated sulfonic acid compounds include sodium allylsulfonate, sodium vinylsulfonate, and sodium propynesulfonate, and sodium allylsulfonate is preferred. These unsaturated sulfonic acid compounds may be used singly or in combination of two or more types.
본 발명 도금액에 있어서의, 불포화 술폰산 화합물의 함유량은 1 ∼ 10 질량％ (이하, 간단히「％」라고 한다), 바람직하게는 4 ∼ 8 ％ 이다.The content of the unsaturated sulfonic acid compound in the plating solution of the present invention is 1 to 10% by mass (hereinafter simply referred to as “%”), preferably 4 to 8%.
본 발명 도금액의 베이스가 되는 철-니켈 합금용 전기 도금액으로는, 특별히 한정되지 않지만, 예를 들어, 철 이온, 니켈 이온, 글루콘산 등의 착화제, 붕산, 아세트산 등의 완충제를 함유하는 종래 공지된 것을 들 수 있다. 보다 구체적인 철-니켈 합금용 전기 도금액으로는, 염화물액, 황산염액, 황산염-염화물액, 시안액, 시트르산액, 피롤린산액, 와트액, 술팜산액 등을 들 수 있다. 이들 중에서도 와트액, 술팜산액이 바람직하다.The electroplating solution for iron-nickel alloy that serves as the base of the plating solution of the present invention is not particularly limited, but includes, for example, a conventionally known solution containing complexing agents such as iron ions, nickel ions, and gluconic acid, and buffering agents such as boric acid and acetic acid. You can hear what happened. More specific electroplating solutions for iron-nickel alloy include chloride solution, sulfate solution, sulfate-chloride solution, cyanide solution, citric acid solution, pyrrolic acid solution, Watts solution, and sulfamic acid solution. Among these, Watt's solution and sulfamic acid solution are preferable.
또, 본 발명 도금액에는, 상기한 철-니켈 합금용 전기 도금액에, 추가로 코발트, 몰리브덴, 텅스텐을 함유시켜도 된다. 이 경우의 코발트, 몰리브덴, 텅스텐의 첨가량은 특별히 한정되지 않고, 예를 들어 0.1 ∼ 100 g/ℓ, 바람직하게는 0.5 ∼ 50 g/ℓ 이다. 또, 코발트원으로는, 황산코발트, 술팜산코발트, 몰리브덴산나트륨, 텅스텐산나트륨 등을 들 수 있다.Additionally, the plating solution of the present invention may contain cobalt, molybdenum, and tungsten in addition to the electroplating solution for iron-nickel alloy described above. The amount of cobalt, molybdenum, and tungsten added in this case is not particularly limited, and is, for example, 0.1 to 100 g/l, preferably 0.5 to 50 g/l. In addition, cobalt sources include cobalt sulfate, cobalt sulfamate, sodium molybdate, and sodium tungstate.
또한, 본 발명 도금액에는, 상기한 철-니켈 합금용 전기 도금액에 있어서, 특히 철을 5 ∼ 20 g/ℓ, 바람직하게는 7.5 ∼ 17.5 g/ℓ, 특히 바람직하게는 10 ∼ 15 g/ℓ, 니켈을 30 ∼ 70 g/ℓ, 바람직하게는 40 ∼ 60 g/ℓ 함유시킨 것을 사용하는 것이 바람직하다.In addition, the plating solution of the present invention contains iron in an amount of 5 to 20 g/l, preferably 7.5 to 17.5 g/l, particularly preferably 10 to 15 g/l, in the electroplating solution for iron-nickel alloy described above. It is preferable to use one containing 30 to 70 g/l of nickel, preferably 40 to 60 g/l.
이하에, 본 발명 도금액의 바람직한 양태로서, 와트액, 술팜산액의 조성을 기재한다.Below, the compositions of Watt's solution and sulfamic acid solution are described as preferred embodiments of the plating solution of the present invention.
＜와트액＞＜Watt amount＞
황산니켈 6수화물 : 80 ∼ 230 g/ℓ, 바람직하게는 110 ∼ 200 g/ℓNickel sulfate hexahydrate: 80 to 230 g/l, preferably 110 to 200 g/l.
염화니켈 6수화물 : 40 ∼ 80 g/ℓ, 바람직하게는 50 ∼ 70 g/ℓNickel chloride hexahydrate: 40 to 80 g/l, preferably 50 to 70 g/l
붕산 : 30 ∼ 60 g/ℓBoric acid: 30 ~ 60 g/ℓ
황산제1철 7수화물 : 25 ∼ 100 g/ℓ, 바람직하게는 37.5 ∼ 75 g/ℓFerrous sulfate heptahydrate: 25 to 100 g/l, preferably 37.5 to 75 g/l.
글루콘산나트륨 : 20 ∼ 180 g/ℓ, 바람직하게는 40 ∼ 140 g/ℓ, 특히 바람직하게는 60 ∼ 120 g/ℓSodium gluconate: 20 to 180 g/l, preferably 40 to 140 g/l, particularly preferably 60 to 120 g/l.
타르타르산나트륨 2수화물 : 10 ∼ 80 g/ℓ, 바람직하게는 15 ∼ 60 g/ℓ, 특히 바람직하게는 20 ∼ 40 g/ℓSodium tartrate dihydrate: 10 to 80 g/l, preferably 15 to 60 g/l, particularly preferably 20 to 40 g/l.
사카린산나트륨 : 1 ∼ 5 g/ℓ, 바람직하게는 2 ∼ 4 g/ℓSodium saccharinate: 1 to 5 g/l, preferably 2 to 4 g/l
알릴술폰산나트륨 : 1.5 ∼ 10 g/ℓ, 바람직하게는 3.5 ∼ 8.5 g/ℓSodium allylsulfonate: 1.5 to 10 g/l, preferably 3.5 to 8.5 g/l.
＜술팜산액＞＜Sulfame acid solution＞
술팜산니켈 4수화물 : 160 ∼ 370 g/ℓ, 바람직하게는 210 ∼ 320 g/ℓNickel sulfamate tetrahydrate: 160 to 370 g/l, preferably 210 to 320 g/l.
붕산 : 30 ∼ 60 g/ℓBoric acid: 30 ~ 60 g/ℓ
브롬화니켈 : 5 ∼ 15 g/ℓ, 바람직하게는 6 ∼ 10 g/ℓNickel bromide: 5 to 15 g/l, preferably 6 to 10 g/l
술팜산철 5수화물 : 30 ∼ 125 g/ℓ, 바람직하게는 45 ∼ 95 g/ℓFerrous sulfamate pentahydrate: 30 to 125 g/l, preferably 45 to 95 g/l.
글루콘산나트륨 : 20 ∼ 180 g/ℓ, 바람직하게는 40 ∼ 140 g/ℓ, 특히 바람직하게는 60 ∼ 120 g/ℓSodium gluconate: 20 to 180 g/l, preferably 40 to 140 g/l, particularly preferably 60 to 120 g/l.
타르타르산나트륨 2수화물 : 10 ∼ 80 g/ℓ, 바람직하게는 15 ∼ 60 g/ℓ, 특히 바람직하게는 20 ∼ 40 g/ℓSodium tartrate dihydrate: 10 to 80 g/l, preferably 15 to 60 g/l, particularly preferably 20 to 40 g/l.
사카린산나트륨 : 1 ∼ 5 g/ℓ, 바람직하게는 2 ∼ 4 g/ℓSodium saccharinate: 1 to 5 g/l, preferably 2 to 4 g/l
알릴술폰산나트륨 : 1.5 ∼ 10 g/ℓ, 바람직하게는 3.5 ∼ 8.5 g/ℓSodium allylsulfonate: 1.5 to 10 g/l, preferably 3.5 to 8.5 g/l.
본 발명 도금액을 사용하여 피도금물에 전기 도금하는 방법은, 특별히 한정되지 않고, 예를 들어, 피도금물에, 알칼리 탈지, 산 활성 등의 전처리를 실시한 후, 이것을 본 발명 도금액에 침지하는 방법 등을 들 수 있다.The method of electroplating the object to be plated using the plating solution of the present invention is not particularly limited, and for example, a method of subjecting the object to be plated to pretreatment such as alkaline degreasing and acid activation, and then immersing it in the plating solution of the present invention. etc. can be mentioned.
전기 도금의 조건은, 특별히 한정되지 않고, 통상적인 철-니켈 합금의 전기 도금의 조건을 사용하면 되고, 예를 들어, 액온 20 ∼ 60 ℃ 에서, 애노드에 철, 니켈을 병용하여, 음극 전류 밀도 0.5 ∼ 3 A/dm2 으로 실시하면 된다. 또, 전기 도금시에는 패들 등으로 교반하는 것이 바람직하다.The conditions of electroplating are not particularly limited, and the conditions for electroplating of a normal iron-nickel alloy can be used. For example, iron and nickel are used together for the anode at a liquid temperature of 20 to 60 ° C, and the cathode current density is It can be carried out at 0.5 to 3 A/dm 2 . Additionally, during electroplating, it is preferable to stir with a paddle or the like.
또한, 전기 도금의 조건으로서, 도금액의 온도를 높게 하면 얻어지는 철-니켈 합금에 있어서의 철의 비율이 낮아지고, 또, 교반 속도를 빠르게 하면 철의 비율은 높아지고, 또한, 도금액의 철 농도를 상대적으로 내리면 철의 비율이 낮아지는 경향을 알고 있기 때문에, 당업자라면 이들 조건의 조정에 의해 철-니켈 합금에 있어서의 철과 니켈의 비율을 제어할 수도 있다.In addition, as a condition of electroplating, if the temperature of the plating solution is raised, the ratio of iron in the resulting iron-nickel alloy decreases, and if the stirring speed is increased, the ratio of iron increases, and the iron concentration of the plating solution is increased relative to the other. Since it is known that the ratio of iron tends to decrease when lowered to , a person skilled in the art can control the ratio of iron to nickel in the iron-nickel alloy by adjusting these conditions.
본 발명 도금액으로 전기 도금할 수 있는 피도금물은 특별히 한정되지 않고, 예를 들어, 표면이, 구리, 니켈, 스테인리스 등의 금속, ABS, 폴리이미드 등의 수지 등으로 형성된 것 등을 들 수 있다.The object to be plated that can be electroplated with the plating solution of the present invention is not particularly limited, and examples include those whose surfaces are formed of metals such as copper, nickel, and stainless steel, and resins such as ABS and polyimide. .
상기와 같이 하여 피도금물에 전기 도금하여 얻어지는 철-니켈 합금 도금 피복 제품은, 저열팽창 계수 및 고경도를 갖는다. 구체적으로는, 철과 니켈의 비율이, 양자의 합계량을 100 ％ 로 하여, 철이 55 ∼ 70 ％ 및 니켈이 30 ∼ 45 ％, 바람직하게는 철이 56 ∼ 64 ％ 및 니켈이 36 ∼ 44 ％ 이고, 25 ∼ 400 ℃ 의 범위에서 측정되는 열팽창 계수가 4.5 × 10-6/℃ 이하, 바람직하게는 4.0 × 10-6/℃ 이하, 특히 바람직하게는 3.0 × 10-6/℃ 이하, 0.05 × 10-6/℃ 이상이다. 또한, 열팽창 계수는, 예를 들어, 질소 분위기하에서 측정되는 것이 바람직하다.The iron-nickel alloy plated coated product obtained by electroplating the object to be plated as described above has a low coefficient of thermal expansion and high hardness. Specifically, the ratio of iron and nickel is 55 to 70% iron and 30 to 45% nickel, preferably 56 to 64% iron and 36 to 44% nickel, with the total amount of both being 100%. The thermal expansion coefficient measured in the range of 25 to 400°C is 4.5 × 10 -6 /°C or less, preferably 4.0 × 10 -6 /°C or less, particularly preferably 3.0 × 10 -6 /°C or less, 0.05 × 10 - It is above 6 /℃. Additionally, the thermal expansion coefficient is preferably measured under a nitrogen atmosphere, for example.
이와 같은 성질을 갖는 철-니켈 합금 도금 피복 제품은, 조성이 균일하고, 저열팽창 계수를 갖기 때문에 메탈 마스크, 파워 일렉트로닉스 분야의 배선 기판 등에 이용할 수 있다.Iron-nickel alloy plated coated products with these properties have a uniform composition and a low thermal expansion coefficient, so they can be used for metal masks, wiring boards in the power electronics field, etc.
실시예Example
이하, 본 발명을 실시예를 들어 상세하게 설명하지만, 본 발명은 이들 실시예에 전혀 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples at all.
실시예 1Example 1
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈·4수화물 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철·5수화물 87 g/ℓ, 글루콘산나트륨 100 g/ℓ, 타르타르산나트륨 25 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 13.7 g/ℓ 였다.In water, nickel sulfamate/tetrahydrate 270 g/l, boric acid 30 g/l, nickel bromide 7 g/l, iron sulfamate/pentahydrate 87 g/l, sodium gluconate 100 g/l, sodium tartrate 25 g/ ℓ, 3.2 g/L of sodium saccharin and 16 mL/L of sodium allylsulfonate (36%) were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 13.7 g/l, respectively.
실시예 2Example 2
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈·4수화물 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철·5수화물 92 g/ℓ, 글루콘산나트륨 100 g/ℓ, 타르타르산나트륨 15 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 14.5 g/ℓ 였다.In water, nickel sulfamate/tetrahydrate 270 g/l, boric acid 30 g/l, nickel bromide 7 g/l, iron sulfamate/pentahydrate 92 g/l, sodium gluconate 100 g/l, sodium tartrate 15 g/ ℓ, 3.2 g/L of sodium saccharin and 16 mL/L of sodium allylsulfonate (36%) were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 14.5 g/l, respectively.
실시예 3Example 3
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈·4수화물 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철·5수화물 87 g/ℓ, 글루콘산나트륨 100 g/ℓ, 타르타르산나트륨 60 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 13.7 g/ℓ 였다.In water, nickel sulfamate/tetrahydrate 270 g/l, boric acid 30 g/l, nickel bromide 7 g/l, iron sulfamate/pentahydrate 87 g/l, sodium gluconate 100 g/l, sodium tartrate 60 g/ ℓ, 3.2 g/L of sodium saccharin and 16 mL/L of sodium allylsulfonate (36%) were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 13.7 g/l, respectively.
비교예 1Comparative Example 1
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈·4수화물 156 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철·5수화물 47 g/ℓ, 글루콘산나트륨 60 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 30 g/ℓ 및 7.5 g/ℓ 였다.In water, nickel sulfamate/tetrahydrate 156 g/l, boric acid 30 g/l, nickel bromide 7 g/l, iron sulfamate/pentahydrate 47 g/l, sodium gluconate 60 g/l, sodium saccharin 3.2 g/ ℓ and 16 mL/L of sodium allylsulfonate (36%) were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 30 g/l and 7.5 g/l, respectively.
비교예 2Comparative Example 2
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈·4수화물 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철·5수화물 87 g/ℓ, 글루콘산나트륨 100 g/ℓ, 말론산이나트륨 25 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 13.7 g/ℓ 였다.In water, nickel sulfamate/tetrahydrate 270 g/l, boric acid 30 g/l, nickel bromide 7 g/l, iron sulfamate/pentahydrate 87 g/l, sodium gluconate 100 g/l, disodium malonate 25 g. /L, 3.2 g/L of sodium saccharin and 16 mL/L of sodium allylsulfonate (36%) were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 13.7 g/l, respectively.
비교예 3Comparative Example 3
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈·4수화물 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철·5수화물 87 g/ℓ, 글루콘산나트륨 100 g/ℓ, 말산나트륨 15 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 13.7 g/ℓ 였다.In water, nickel sulfamate/tetrahydrate 270 g/l, boric acid 30 g/l, nickel bromide 7 g/l, iron sulfamate/pentahydrate 87 g/l, sodium gluconate 100 g/l, sodium malate 15 g/ ℓ, 3.2 g/L of sodium saccharin and 16 mL/L of sodium allylsulfonate (36%) were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 13.7 g/l, respectively.
실시예 4Example 4
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
이하의 방법으로, 실시예 1 ∼ 3, 비교예 1 ∼ 3 에서 조제한 철-니켈 합금용 전기 도금액을 사용하여, 전기 도금을 하였다.Electroplating was performed using the electroplating solution for iron-nickel alloy prepared in Examples 1 to 3 and Comparative Examples 1 to 3 by the following method.
구리판 (60 × 80 ㎜) 에, 알칼리 탈지 (55 ℃, 10 분) 및 산 활성 (실온, 30 초) 을 실시한 후, 실시예 1 ∼ 3, 비교예 1 ∼ 3 에서 조제한 철-니켈 합금용 전기 도금액에 이하의 조건에서 침지하여 목표 막 두께 10 ㎛ 로 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다. 또한, 비교예 2 에서 조제한 철-니켈 합금용 전기 도금액에 대해서는, 상기 조건 중, 액온을 40 ℃ 로, 교반을 패들 교반 (6 m/min) 을 대신하여 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.After alkaline degreasing (55°C, 10 minutes) and acid activation (room temperature, 30 seconds) were applied to a copper plate (60 It was immersed in a plating solution under the following conditions and electroplated to a target film thickness of 10 ㎛ to obtain an iron-nickel alloy electroplated film. In addition, with respect to the electroplating solution for iron-nickel alloy prepared in Comparative Example 2, among the above conditions, electroplating was performed with the solution temperature at 40°C and stirring instead of paddle stirring (6 m/min) to achieve iron-nickel alloy electroplating. obtained a film.
＜도금 조건＞＜Plating conditions＞
도금 시간 : 60 분Plating time: 60 minutes
액온 : 45 ℃Liquid temperature: 45℃
애노드 : 철, 니켈Anode: iron, nickel
음극 전류 밀도 : 1 A/dm2 Cathode current density: 1 A/dm 2
교반 : 패들 교반 (3 m/min)Stirring: Paddle stirring (3 m/min)
시험예 1Test example 1
물성 측정 :Physical property measurement:
실시예 1 ∼ 3 및 비교예 1 ∼ 3 에서 얻어진 도금 피막에 대해, 외관을 육안으로 평가한 후, 열팽창 계수를 질소 분위기하, 표 1 에 기재된 범위에서 열·응력·변형 측정 장치 (SII·나노테크놀로지 제조 : TMA/SS 6100 : 하중 50 mN : 승온 속도 5 ℃/min) 를 사용하여 측정하였다. 또, 피막 조성의 균일성을 XRF 로 조사하고, 이하의 평가 기준으로 평가하였다. 이들 결과를 표 1 에 나타내었다. 또한, 피막 중의 철-니켈의 질량비를 형광 X 선 분석법으로 구한 결과, 철-니켈의 질량비는, 모두 64 : 36 이었다 (소수점 한 자릿수를 사사오입). 또한, 비교로서 야금 인바 합금 (철-니켈의 질량비는, 64 : 36) 에 대해서도 동일한 측정을 실시하였다.For the plating films obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the appearance was evaluated visually, and the thermal expansion coefficient was measured in a nitrogen atmosphere in the range shown in Table 1 using a heat, stress, and strain measuring device (SII, Nano). Technology Manufacturing: TMA/SS 6100: Load 50 mN: Temperature increase rate 5°C/min). In addition, the uniformity of the film composition was investigated by XRF and evaluated based on the following evaluation criteria. These results are shown in Table 1. Additionally, as a result of determining the mass ratio of iron-nickel in the film using fluorescence X-ray analysis, the mass ratio of iron-nickel was found to be 64:36 (rounded to one decimal place). Additionally, as a comparison, the same measurement was performed on a metallurgical Invar alloy (mass ratio of iron-nickel was 64:36).
＜피막 조성의 균일성의 평가 기준＞＜Evaluation criteria for uniformity of film composition＞
평가 내용Evaluation contents
○ : 5 개 지점 측정하고, 편차가 평균값으로부터 ±3 ％ 이내○: Measurement at 5 points, deviation within ±3% from the average value
× : 5 개 지점 측정하고, 편차가 평균값으로부터 ±3 ％ 이상×: Measure at 5 points, and the deviation is ±3% or more from the average value
이 결과로부터 글루콘산나트륨과 타르타르산나트륨을 2 종 혼합하면, 피막 중의 철 64 ％ 의 피막에 있어서 광택 외관, 양호한 조성 균일성을 갖는 것 및 폭넓은 온도 영역에서 저열팽창률을 나타내는 것을 알 수 있었다.From these results, it was found that when two types of sodium gluconate and sodium tartrate are mixed, a film containing 64% iron in the film has a glossy appearance, good composition uniformity, and shows a low coefficient of thermal expansion over a wide temperature range.
실시예 5Example 5
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
실시예 1 의 철-니켈 합금용 전기 도금액에 있어서, 술팜산니켈·4수화물을 297 g/ℓ 로 하는 것 이외에는 동일하게 하여, 철-니켈 합금용 전기 도금액을 조제하였다.An electroplating solution for an iron-nickel alloy was prepared in the same manner as the electroplating solution for an iron-nickel alloy of Example 1, except that the content of nickel sulfamate tetrahydrate was adjusted to 297 g/l.
실시예 6Example 6
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
실시예 1 의 철-니켈 합금용 전기 도금액에 있어서, 술팜산니켈·4수화물을 315 g/ℓ 로 하는 것 이외에는 동일하게 하여, 철-니켈 합금용 전기 도금액을 조제하였다.An electroplating solution for an iron-nickel alloy was prepared in the same manner as the electroplating solution for an iron-nickel alloy of Example 1, except that the amount of nickel sulfamate tetrahydrate was adjusted to 315 g/l.
실시예 7Example 7
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
실시예 1 의 철-니켈 합금용 전기 도금액에 있어서, pH 를 3.4 로 하는 것 이외에는 동일하게 하여, 철-니켈 합금용 전기 도금액을 조제하였다.The electroplating solution for iron-nickel alloy of Example 1 was prepared in the same manner except that the pH was set to 3.4.
실시예 8Example 8
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
실시예 1 의 철-니켈 합금용 전기 도금액에 있어서, pH 를 4.2 로 하는 것 이외에는 동일하게 하여, 철-니켈 합금용 전기 도금액을 조제하였다.The electroplating solution for iron-nickel alloy of Example 1 was prepared in the same manner except that the pH was set to 4.2.
실시예 9Example 9
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
실시예 5 ∼ 8 에서 조제한 철-니켈 합금용 전기 도금액을 사용하여, 실시예 5 와 동일하게 하여, 전기 도금을 하였다. 또, 실시예 1 에서 조제한 철-니켈 합금용 전기 도금액을 사용하여 액온을 35 ℃ (실시예 10), 55 ℃ (실시예 11) 또는 교반을 패들 교반 (6 m/min) (실시예 12) 으로 하는 것 이외에는 실시예 5 와 동일하게 하여, 전기 도금을 하였다. 철-니켈의 질량비와 피막 조성의 균일성을 실시예 5 와 동일하게 하여 평가하였다. 그 결과를 표 2 에 나타내었다.Electroplating was performed in the same manner as in Example 5 using the electroplating solution for iron-nickel alloy prepared in Examples 5 to 8. In addition, using the electroplating solution for iron-nickel alloy prepared in Example 1, the liquid temperature was set to 35°C (Example 10), 55°C (Example 11), or stirring was done with paddle stirring (6 m/min) (Example 12). Electroplating was performed in the same manner as in Example 5 except that . The iron-nickel mass ratio and uniformity of film composition were evaluated in the same manner as in Example 5. The results are shown in Table 2.
이상의 결과로부터, 철-니켈의 질량비는, 도금액 중의 니켈 농도, pH, 액온, 교반 속도를 조정함으로써 조정 가능한 것을 알 수 있었다.From the above results, it was found that the iron-nickel mass ratio can be adjusted by adjusting the nickel concentration in the plating solution, pH, solution temperature, and stirring speed.
참고예 1Reference example 1
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈 156 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철 50 g/ℓ, 글루콘산나트륨 60 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 30 g/ℓ 및 8 g/ℓ 였다.In water, 156 g/l nickel sulfamate, 30 g/l boric acid, 7 g/l nickel bromide, 50 g/l iron sulfamate, 60 g/l sodium gluconate, 3.2 g/l sodium saccharin and sodium allylsulfonate ( 36%) 16 mL/L was added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 30 g/l and 8 g/l, respectively.
참고예 2Reference example 2
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 황산니켈 75 g/ℓ, 염화니켈 55 g/ℓ, 붕산 40 g/ℓ, 황산제1철 40 g/ℓ, 글루콘산나트륨 60 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.0 이고, 니켈과 철의 함유량은 각각 30 g/ℓ 및 8 g/ℓ 였다.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 allylsulfonate. (36%) 16 mL/L was added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.0, and the nickel and iron contents were 30 g/l and 8 g/l, respectively.
참고예 3Reference example 3
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
폴리이미드제의 기판 (10 × 40 ㎜) 에, 알칼리 탈지 (40 ℃, 10 분) 및 산 활성 (실온, 30 초) 을 실시한 후, 참고예 1 에서 조제한 철-니켈 합금용 전기 도금액에 이하의 조건에서 침지하여 목표 막 두께 10 ㎛ 로 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.After alkaline degreasing (40°C, 10 minutes) and acid activation (room temperature, 30 seconds) were applied to a polyimide substrate (10 Electroplating was performed to a target film thickness of 10 ㎛ by immersion under these conditions to obtain an iron-nickel alloy electroplating film.
＜도금 조건＞＜Plating conditions＞
도금 시간 : 30 분Plating time: 30 minutes
액온 : 50 ℃Liquid temperature: 50℃
애노드 : 철, 니켈Anode: iron, nickel
음극 전류 밀도 : 2 A/dm2 Cathode current density: 2 A/dm 2
교반 : 패들 교반 (3 m/min)Stirring: Paddle stirring (3 m/min)
참고예 4Reference example 4
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
온도를 40 ℃ 로 하는 것 이외에는 참고예 3 과 동일하게 하여 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.Electroplating was performed in the same manner as in Reference Example 3 except that the temperature was set to 40°C to obtain an iron-nickel alloy electroplating film.
참고예 5Reference example 5
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
교반을 6 m/min, 온도를 40 ℃ 로 하는 것 이외에는 참고예 3 과 동일하게 하여 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.Electroplating was performed in the same manner as in Reference Example 3 except that stirring was performed at 6 m/min and the temperature was 40°C to obtain an iron-nickel alloy electroplating film.
참고예 6Reference example 6
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
참고예 2 에서 조제한 철-니켈 합금용 전기 도금액을 사용하고, 온도를 40 ℃ 로 하는 것 이외에는 참고예 3 과 동일하게 하여 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.Using the electroplating solution for iron-nickel alloy prepared in Reference Example 2, electroplating was performed in the same manner as in Reference Example 3 except that the temperature was set to 40°C to obtain an iron-nickel alloy electroplating film.
참고 시험예 1Reference test example 1
물성 측정 :Physical property measurement:
참고예 3 ∼ 6 에서 얻어진 도금 피막에 대해, 외관을 육안으로 평가한 후, 스파이럴 응력계 ((주) 야마모토 도금 시험기사 제조 : 스파이럴 도금 응력계) 를 사용하여 응력, 마이크로미터 ((주) 미츠토요사 제조) 로 연전성, 마이크로 비커스 경도계 ((주) 아카시 제작소사 제조 : 하중 0.25 N) 를 사용하여 경도를 측정하였다. 또, 열팽창 계수를 질소 분위기하, 25 ∼ 200 ℃ 의 범위에서 열·응력·변형 측정 장치 (SII·나노테크놀로지 제조 : TMA/SS 6100 : 하중 50 mN : 승온 속도 5 ℃/min) 를 사용하여 측정하였다. 또한, 피막 중의 철-니켈의 질량비를 형광 X 선 분석법으로 구하였다. 이들 결과를 표 3 에 나타내었다.After visually evaluating the appearance of the plating films obtained in Reference Examples 3 to 6, the stress was measured using a spiral stress meter (spiral plating stress meter manufactured by Yamamoto Plating Testing Equipment Co., Ltd.) and a micrometer (Mitsu Co., Ltd.). Hardness was measured using a micro-Vickers hardness tester (manufactured by Toyo Corporation: load 0.25 N). In addition, the thermal expansion coefficient was measured in a nitrogen atmosphere in the range of 25 to 200 ℃ using a heat, stress, and strain measuring device (SII Nanotechnology Co., Ltd.: TMA/SS 6100: load 50 mN: temperature increase rate 5 ℃/min) did. Additionally, the mass ratio of iron-nickel in the film was determined by fluorescence X-ray analysis. These results are shown in Table 3.
이상의 결과로부터, 상기 도금액에 의해, 전기 도금만으로 열처리를 실시하지 않아도 저열팽창 계수 및 고경도를 갖는 철-니켈 합금 피막이 얻어지는 것을 알 수 있었다. 또, 저열팽창 계수가 얻어지는 철-니켈 합금의 조성은 철 58 ％ 및 니켈 42 ％ 부근에 있는 것을 알 수 있었다.From the above results, it was found that an iron-nickel alloy film having a low thermal expansion coefficient and high hardness was obtained with the above plating solution even without heat treatment by electroplating alone. In addition, it was found that the composition of the iron-nickel alloy that yields a low coefficient of thermal expansion is around 58% iron and 42% nickel.
참고 비교예 1Reference Comparative Example 1
비교 도금 :Comparative plating:
알릴술폰산나트륨 (36 ％) 을 함유하지 않는 것 이외에는, 참고예 2 와 동일하게 철-니켈 합금용 전기 도금액을 조제하고, 이것을 사용하여 참고예 6 과 동일한 조건에서 철-니켈 합금 전기 도금 피막을 얻었다. 또한, 피막의 외관은 균일하지 않았다. 얻어진 피막에 대해 시험예 1 과 동일하게 하여 피막 중의 철-니켈의 질량비와, 열팽창 계수 (/℃) 를 측정하였다. 그 결과, 철-니켈의 질량비는 철 64 ％ 및 니켈 36 ％ 이고, 25 ∼ 200 ℃ 의 열팽창 계수 (/℃) 는 8.6 × 10-6/℃ 였다.Except that it did not contain sodium allylsulfonate (36%), an electroplating solution for iron-nickel alloy was prepared in the same manner as in Reference Example 2, and an iron-nickel alloy electroplating film was obtained using this under the same conditions as in Reference Example 6. . Additionally, the appearance of the film was not uniform. For the obtained film, the mass ratio of iron-nickel in the film and the thermal expansion coefficient (/°C) were measured in the same manner as in Test Example 1. As a result, the iron-nickel mass ratio was 64% iron and 36% nickel, and the thermal expansion coefficient (/°C) from 25 to 200°C was 8.6 × 10 -6 /°C.
참고예 7Reference example 7
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
알릴술폰산나트륨 (36 ％) 을 비닐술폰산으로 하는 것 이외에는, 참고예 2 와 동일하게 철-니켈 합금용 전기 도금액을 조제하고, 이것을 사용하여 참고예 6 과 동일한 조건에서 철-니켈 합금 전기 도금 피막을 얻었다. 균일한 피막 외관이 얻어지고, 철-니켈의 질량비는 철 55 및 니켈 45 ％ 였다. 이 피막은 저열팽창 계수 및 고경도를 갖는다.Except that sodium allylsulfonate (36%) was replaced with vinylsulfonic acid, an electroplating solution for iron-nickel alloy was prepared in the same manner as in Reference Example 2, and an iron-nickel alloy electroplating film was formed using this under the same conditions as in Reference Example 6. got it A uniform film appearance was obtained, and the iron-nickel mass ratio was 55% iron and 45% nickel. This film has a low coefficient of thermal expansion and high hardness.
참고예 8Reference example 8
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
알릴술폰산나트륨 (36 ％) 을 프로핀술폰산으로 하는 것 이외에는, 참고예 2 와 동일하게 철-니켈 합금용 전기 도금액을 조제하고, 이것을 사용하여 참고예 6 과 동일한 조건에서 철-니켈 합금 전기 도금 피막을 얻었다. 얻어진 피막의 철-니켈의 질량비는 철 62 ％ 및 니켈 38 ％ 였다. 이 피막은 저열팽창 계수 및 고경도를 갖는다.Except that sodium allylsulfonate (36%) was replaced with propynesulfonic acid, an electroplating solution for iron-nickel alloy was prepared in the same manner as in Reference Example 2, and this was used to produce an iron-nickel alloy electroplating film under the same conditions as in Reference Example 6. got it The mass ratio of iron to nickel in the obtained film was 62% iron and 38% nickel. This film has a low coefficient of thermal expansion and high hardness.
참고예 9Reference example 9
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철 87 g/ℓ, 글루콘산나트륨 100 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 13.7 g/ℓ 였다.In water, nickel sulfamate 270 g/ℓ, boric acid 30 g/ℓ, nickel bromide 7 g/ℓ, iron sulfamate 87 g/ℓ, sodium gluconate 100 g/ℓ, sodium saccharin 3.2 g/ℓ and sodium allylsulfonate ( 36%) 16 mL/L was added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 13.7 g/l, respectively.
참고예 10Reference example 10
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
구리판 (60 × 80 ㎜) 에, 알칼리 탈지 (55 ℃, 10 분) 및 산 활성 (실온, 30 초) 을 실시한 후, 참고예 9 에서 조제한 철-니켈 합금용 전기 도금액에 이하의 조건에서 침지하여 목표 막 두께 10 ㎛ 로 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.After performing alkaline degreasing (55°C, 10 minutes) and acid activation (room temperature, 30 seconds) on a copper plate (60 Electroplating was performed to a target film thickness of 10 μm to obtain an iron-nickel alloy electroplating film.
＜도금 조건＞＜Plating conditions＞
도금 시간 : 60 분Plating time: 60 minutes
액온 : 45 ℃Liquid temperature: 45℃
애노드 : 철, 니켈Anode: iron, nickel
음극 전류 밀도 : 1 A/dm2 Cathode current density: 1 A/dm 2
교반 : 패들 교반 (3 m/min)Stirring: Paddle stirring (3 m/min)
참고예 11Reference example 11
철-니켈 합금용 전기 도금액의 조제 :Preparation of electroplating solution for iron-nickel alloy:
물에, 술팜산니켈 270 g/ℓ, 붕산 30 g/ℓ, 브롬화니켈 7 g/ℓ, 술팜산철 76.5 g/ℓ, 글루콘산나트륨 100 g/ℓ, 사카린나트륨 3.2 g/ℓ 및 알릴술폰산나트륨 (36 ％) 16 ㎖/ℓ 를 첨가, 혼합하여, 철-니켈 합금용 전기 도금액을 조제하였다. 이 도금액의 pH 는 3.8 이고, 니켈과 철의 함유량은 각각 50.7 g/ℓ 및 12.0 g/ℓ 였다.In water, nickel sulfamate 270 g/ℓ, boric acid 30 g/ℓ, nickel bromide 7 g/ℓ, iron sulfamate 76.5 g/ℓ, sodium gluconate 100 g/ℓ, sodium saccharin 3.2 g/ℓ and sodium allylsulfonate ( 36%) 16 mL/L was added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating solution was 3.8, and the nickel and iron contents were 50.7 g/l and 12.0 g/l, respectively.
참고예 12Reference example 12
철-니켈 합금 전기 도금 피막의 형성 :Formation of iron-nickel alloy electroplating film:
구리판 (60 × 80 ㎜) 에, 알칼리 탈지 (55 ℃, 10 분) 및 산 활성 (실온, 30 초) 을 실시한 후, 참고예 9 에서 조제한 철-니켈 합금용 전기 도금액에 이하의 조건에서 침지하여 목표 막 두께 10 ㎛ 로 전기 도금을 하여 철-니켈 합금 전기 도금 피막을 얻었다.After performing alkaline degreasing (55°C, 10 minutes) and acid activation (room temperature, 30 seconds) on a copper plate (60 Electroplating was performed to a target film thickness of 10 μm to obtain an iron-nickel alloy electroplating film.
＜도금 조건＞＜Plating conditions＞
도금 시간 : 60 분Plating time: 60 minutes
액온 : 30 ℃Liquid temperature: 30℃
애노드 : 철, 니켈Anode: iron, nickel
음극 전류 밀도 : 1 A/dm2 Cathode current density: 1 A/dm 2
교반 : 패들 교반 (3 m/min)Stirring: Paddle stirring (3 m/min)
참고 시험예 2Reference test example 2
물성 측정 :Physical property measurement:
참고예 9, 11 에서 얻어진 도금 피막에 대해, 외관을 육안으로 평가한 후, 열팽창 계수를 질소 분위기하, 표 4 에 기재된 범위에서 열·응력·변형 측정 장치 (SII·나노테크놀로지 제조 : TMA/SS 6100 : 하중 50 mN : 승온 속도 5 ℃/min) 를 사용하여 측정하였다. 또, 피막 조성의 균일성을 XRF 로 조사하고, 지금까지와 동일한 평가 기준으로 평가하였다. 이들 결과를 표 4 에 나타내었다.For the plating films obtained in Reference Examples 9 and 11, the appearance was evaluated with the naked eye, and the thermal expansion coefficient was determined in the range shown in Table 4 under a nitrogen atmosphere using a heat, stress, and strain measuring device (SII, Nanotechnology Co., Ltd.: TMA/SS) 6100: load 50 mN: temperature increase rate 5°C/min). Additionally, the uniformity of the film composition was investigated by XRF and evaluated using the same evaluation criteria as before. These results are shown in Table 4.
본 발명은, 용제로 제조되는 인바 조성의 철-니켈 합금과 동일한 용도에 사용할 수 있는 것은 물론, 파워 일렉트로닉스 등의 새로운 용도로의 응용을 기대할 수 있다.The present invention can be used for the same applications as the iron-nickel alloy of the Invar composition produced with a solvent, and can also be expected to be applied to new applications such as power electronics.
Claims (19)
(단, R 은 비닐기 또는 에티닐기, X 는 치환되어 있어도 되는, 알킬렌기 또는 페닐렌기, Y 는 알칼리 금속을 나타낸다)
로 나타내는 불포화 술폰산 화합물을 함유하고,
추가로, 카르복실기를 1 개 이상, 하이드록시기를 2 이상 갖고, 탄소수가 2 개 이상인 카르복실산 화합물을 2 종 이상 함유하는 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액으로서,
상기 불포화 술폰산 화합물이, 알릴술폰산나트륨, 비닐술폰산나트륨 및 프로핀술폰산나트륨으로 이루어지는 군에서 선택되는 1 종 또는 2 종 이상이고,
상기 카르복실기를 1 개 이상, 하이드록시기를 2 이상 갖고, 탄소수가 2 개 이상인 카르복실산 화합물이, 글루콘산, 갈락톤산, 만논산, 타르타르산, 타르타르산나트륨 및 글루콘산나트륨으로 이루어진 군에서 선택되고,
상기 전기 도금액 중, 상기 불포화 술폰산 화합물의 함유량이 1 ∼ 10 질량％ 이고, 상기 카르복실산 화합물의 함유량이, 합계량으로서, 30 ∼ 260 g/ℓ 이고, 철의 함유량이 5 ∼ 20 g/ℓ 이고, 니켈의 함유량이 30 ∼ 70 g/ℓ 인 것을 특징으로 하는 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.The following general formula (1)
(However, R represents a vinyl group or ethynyl group, X represents an optionally substituted alkylene group or phenylene group, and Y represents an alkali metal)
Contains an unsaturated sulfonic acid compound represented by,
Additionally, an electroplating solution for iron-nickel alloys having a low coefficient of thermal expansion containing at least one carboxylic group, at least two hydroxyl groups, and containing at least two carboxylic acid compounds having at least two carbon atoms,
The unsaturated sulfonic acid compound is one or two or more types selected from the group consisting of sodium allylsulfonate, sodium vinylsulfonate, and sodium propynesulfonate,
The carboxylic acid compound having one or more carboxyl groups, two or more hydroxy groups, and two or more carbon atoms is selected from the group consisting of gluconic acid, galactonic acid, mannonic acid, tartaric acid, sodium tartrate, and sodium gluconate,
In the electroplating solution, the content of the unsaturated sulfonic acid compound is 1 to 10% by mass, the content of the carboxylic acid compound is 30 to 260 g/l as a total amount, and the iron content is 5 to 20 g/l. , An electroplating solution for iron-nickel alloy having a low thermal expansion coefficient, characterized in that the nickel content is 30 to 70 g/l.
카르복실산 화합물이, 타르타르산나트륨 및 글루콘산나트륨인 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.According to claim 1,
An electroplating solution for iron-nickel alloy having a low coefficient of thermal expansion wherein the carboxylic acid compound is sodium tartrate and sodium gluconate.
타르타르산나트륨을 10 ∼ 80 g/ℓ 함유하는 것인 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.According to claim 2,
An electroplating solution for iron-nickel alloys having a low thermal expansion coefficient containing 10 to 80 g/l of sodium tartrate.
철-니켈 합금용 전기 도금액이, 와트액 또는 술팜산액인 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.The method according to any one of claims 1 to 3,
An electroplating solution for iron-nickel alloys having a low coefficient of thermal expansion, wherein the electroplating solution for iron-nickel alloys is Watts solution or sulfamic acid solution.
저열팽창 계수를 갖는 철-니켈 합금이, 철과 니켈의 비율이 양자의 합계량을 100 질량％ 로 하여, 철이 55 ∼ 70 질량％ 및 니켈이 30 ∼ 45 질량％ 이고, 25 ∼ 400 ℃ 의 범위에서 측정되는 열팽창 계수가 4.5 × 10-6/℃ 이하인 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.The method according to any one of claims 1 to 3,
An iron-nickel alloy with a low coefficient of thermal expansion has a ratio of iron and nickel with the total amount of both being 100% by mass, 55 to 70% by mass of iron and 30 to 45% by mass of nickel, and is heated in the range of 25 to 400 ° C. An electroplating solution for iron-nickel alloy having a low thermal expansion coefficient where the measured thermal expansion coefficient is 4.5 × 10 -6 /°C or less.
전기 도금을, 교반하여 욕온 20 ∼ 60 ℃ 에서 애노드에 철, 니켈을 병용하여, 음극 전류 밀도 0.5 ∼ 3 A/dm2 로 실시하는 저열팽창 계수를 갖는 철-니켈 합금의 전기 도금 방법.According to claim 6,
A method of electroplating for an iron-nickel alloy with a low coefficient of thermal expansion, wherein the electroplating is carried out with stirring at a bath temperature of 20 to 60°C, using a combination of iron and nickel as an anode, and at a cathode current density of 0.5 to 3 A/dm 2 .
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