KR20200044860A - Electroplating solution for iron-nickel alloys with low coefficient of thermal expansion and electroplating method using the same - Google Patents
Electroplating solution for iron-nickel alloys with low coefficient of thermal expansion and electroplating method using the same Download PDFInfo
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- KR20200044860A KR20200044860A KR1020207008220A KR20207008220A KR20200044860A KR 20200044860 A KR20200044860 A KR 20200044860A KR 1020207008220 A KR1020207008220 A KR 1020207008220A KR 20207008220 A KR20207008220 A KR 20207008220A KR 20200044860 A KR20200044860 A KR 20200044860A
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- Prior art keywords
- iron
- nickel
- thermal expansion
- electroplating
- nickel alloy
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 135
- 238000009713 electroplating Methods 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000007747 plating Methods 0.000 claims abstract description 68
- -1 unsaturated sulfonic acid compound Chemical class 0.000 claims abstract description 25
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 73
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 229910052742 iron Inorganic materials 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 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 19
- 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 19
- 229940005574 sodium gluconate Drugs 0.000 claims description 19
- 239000000176 sodium gluconate Substances 0.000 claims description 19
- 235000012207 sodium gluconate Nutrition 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 239000001433 sodium tartrate Substances 0.000 claims description 11
- 229960002167 sodium tartrate Drugs 0.000 claims description 11
- 235000011004 sodium tartrates Nutrition 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 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 claims description 5
- 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 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 94
- 239000000203 mixture Substances 0.000 description 19
- 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
- 239000007788 liquid Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 7
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- DKVTWZYQQQULFN-UHFFFAOYSA-L O.O.O.O.O.[Fe++].NS([O-])(=O)=O.NS([O-])(=O)=O Chemical compound O.O.O.O.O.[Fe++].NS([O-])(=O)=O.NS([O-])(=O)=O DKVTWZYQQQULFN-UHFFFAOYSA-L 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
- 229910021585 Nickel(II) bromide Inorganic materials 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
- 239000008199 coating composition Substances 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
- 238000005516 engineering process Methods 0.000 description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 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
- 239000000872 buffer Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- IDAGXRIGDWCIET-SDFKWCIISA-L disodium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IDAGXRIGDWCIET-SDFKWCIISA-L 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
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 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
- VSRIZRHGMXKDIK-UHFFFAOYSA-N nickel sulfamic acid tetrahydrate Chemical compound O.O.O.O.[Ni].S(N)(O)(=O)=O VSRIZRHGMXKDIK-UHFFFAOYSA-N 0.000 description 2
- UQBLNFAAJGJKSC-UHFFFAOYSA-N nickel tetrahydrate Chemical compound O.O.O.O.[Ni] UQBLNFAAJGJKSC-UHFFFAOYSA-N 0.000 description 2
- DVWAOMBFCAJFPW-UHFFFAOYSA-L nickel(2+) disulfamate hydrate Chemical compound O.S(N)([O-])(=O)=O.[Ni+2].S(N)([O-])(=O)=O DVWAOMBFCAJFPW-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 150000004686 pentahydrates Chemical class 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229940092162 sodium tartrate dihydrate Drugs 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
- 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 description 1
- 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 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation 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
- 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
- 230000007423 decrease Effects 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
- 230000005611 electricity Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 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
- 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 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
- 230000001376 precipitating effect Effects 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
- 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
- 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
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
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 may be substituted, an alkylene group or a phenylene group, and Y represents an alkali metal.)
As an electroplating solution for an iron-nickel alloy containing an unsaturated sulfonic acid compound represented by,
Further, an electroplating solution for an iron-nickel alloy having a low coefficient of thermal expansion, characterized in that it contains two or more carboxylic acid compounds having one or more carboxyl groups, two or more hydroxy groups, and two or more carbon atoms, and the same. The electroplating method used provides a technique for obtaining an iron-nickel alloy with excellent performance over a wide temperature range by plating.
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 coefficient of thermal expansion 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 alloys have a low thermal expansion coefficient and high hardness when they have a specific composition (invar composition). Since the iron-nickel alloy of this invar composition does not change in size with temperature, it is used for photomasks, bimetals, and the like.
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.The iron-nickel alloy having such an invar composition is usually a solvent alloy, but if the iron-nickel alloy having an invar composition can be directly precipitated by plating, it is clear that the use is expanded.
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 iron-nickel alloy obtained by a solvent and the iron-nickel alloy obtained by a plating have different alloy phases, even if an iron-nickel alloy having the same composition as the invar composition is simply obtained by plating, the same properties as those of the solvent are obtained. Do not 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.As a technique for precipitating iron-nickel alloys having the same properties as invar compositions by plating, iron-nickel in which fine particles having an average particle diameter of 3 µm or less are dispersed in an aqueous solution containing a nickel salt, ferrous salt, complexing agent and buffer There has been reported a method of performing heat treatment at 400 ° C or higher after electroplating with an alloy plating solution (Patent Document 1, Non-Patent Document 1). An iron-nickel alloy having a low thermal expansion coefficient and a high hardness has been obtained by this technique.
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 technique, the process was complicated because it is essential to contain the fine particles in the plating solution, it is necessary to control the conditions of agitation, and furthermore, heat treatment is essential even after plating. For this reason, there has been a demand for a technique for more easily obtaining an iron-nickel alloy having the same properties as the invar composition by 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 applicant has solved the above problem with an electroplating solution for an iron-nickel alloy containing a specific unsaturated sulfonic acid compound, thereby obtaining an iron-nickel alloy having a low thermal expansion coefficient 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 the above-mentioned plating has a problem such as lack of glossiness or a problem in normal use, but cannot maintain performance in a wider temperature range.
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 earnestly studying the present invention to solve the above problems, the present inventors have provided two or more types of carboxylic acid compounds having a specific structure in an electroplating solution for an iron-nickel alloy containing a conventionally known unsaturated sulfonic acid compound. By electroplating with, it was found that an iron-nickel alloy having a glossiness, a uniform composition, and a low thermal expansion coefficient at a wide temperature range was obtained, thereby completing the present invention.
즉, 본 발명은 이하의 일반식 (1)That is, the present invention is 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 may be substituted, an alkylene group or a phenylene group, and Y represents an alkali metal.)
로 나타내는 불포화 술폰산 화합물을 함유하는 철-니켈 합금용 전기 도금액으로서,As an electroplating solution for an 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.Further, it is an electric plating solution for an iron-nickel alloy having a low coefficient of thermal expansion, characterized in that it contains two or more 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.In addition, the present invention is an electroplating method of an iron-nickel alloy having a low thermal expansion coefficient, characterized in that the plated object is electroplated with the electroplating solution for an iron-nickel alloy having the 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.In addition, the present invention is an iron-nickel alloy plated coating product having a low thermal expansion coefficient obtained by electroplating an object to be plated with an electroplating solution for an 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 low coefficient of thermal expansion at a wider temperature range than the iron-nickel alloy of an invar composition obtained with a solvent can be obtained by electroplating only.
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 application as the iron-nickel alloy having an invar composition made of a solvent, and it can 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 having one or more carboxyl groups and two or more hydroxy groups, and having two or more carbon atoms, used in a plating solution for an iron-nickel alloy having a low thermal expansion coefficient of the present invention (hereinafter referred to as "the present invention plating solution") The acid compound is not particularly limited, and examples thereof include carboxylic acids such as gluconic acid, galactonic acid, mannonic acid and tartaric acid, and alkali metal salts of the carboxylic acids such as sodium tartrate and sodium gluconate. . Among these carboxylic acid compounds, sodium tartrate and sodium gluconate are preferred. In addition, in the said carboxylic acid compound, when calculating the number of a carboxyl group or a hydroxyl group, the hydroxyl group in a carboxyl group is not included in the number of hydroxyl groups. Therefore, malonic acid and malic acid are not included in the said carboxylic acid compound. It is necessary to contain 2 or more types of these carboxylic acid compounds in the plating solution of the present invention, preferably 2 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.Although the content of the carboxylic acid compound in the plating solution of the present invention is not particularly limited, for example, as a total amount of two types, 30 to 260 g / L, preferably 55 to 200 g / L, particularly preferably Is 80 to 160 g / L. When two types of sodium gluconate and sodium tartrate are used as the carboxylic acid compound in the plating solution of the present invention, the sodium gluconate is 20 to 180 g / L, preferably 40 to 140 g / L, particularly preferably Preferably, it is 60 to 120 g / L, and sodium tartrate is 10 to 80 g / L, preferably 15 to 60 g / L, particularly preferably 20 to 40 g / L. The concentration ratio of sodium gluconate / sodium tartrate is 10-1.25 by mass, preferably 6.5-1.5, particularly preferably 5-2.5.
본 발명 도금액에 사용되는 일반식 (1)General formula (1) used in the present invention plating solution
[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, the unsaturated sulfonic acid compound represented by R is a vinyl group or an ethynyl group, and preferably a vinyl group. Moreover, X is an alkylene group or phenylene group which may be substituted, Preferably it is an unsubstituted alkylene group or a phenylene group, More preferably, it is an unsubstituted alkylene group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a halogen group, a hydroxyl group, and the like, and an alkylene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 3 carbon atoms. Can be lifted. Further, Y is an alkali metal, preferably lithium, sodium, 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.As a more specific unsaturated sulfonic acid compound, sodium allyl sulfonate, sodium vinyl sulfonate, sodium propinsulfonate, etc. are mentioned, Preferably it is sodium allyl sulfonate. You may use these unsaturated sulfonic acid compounds in combination of 1 type or 2 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 alloys used as the base of the plating solution of the present invention is not particularly limited, but, for example, it is known in the prior art containing complexing agents such as iron ions, nickel ions, gluconic acid, and buffers such as boric acid and acetic acid. It can be mentioned. Examples of the electroplating solution for a more specific iron-nickel alloy include a chloride solution, a sulfate solution, a sulfate-chloride solution, a cyan solution, a citric acid solution, a pyrrolic acid solution, a watt solution, and a sulfamic acid solution. Among these, a wat liquid and a sulfamic acid liquid 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.Moreover, the electroplating solution for iron-nickel alloys may further contain cobalt, molybdenum, and tungsten in the plating solution of the present invention. 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. Moreover, cobalt sulfate, cobalt sulfamate, sodium molybdate, sodium tungstate, etc. are mentioned as a cobalt source.
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, in the plating solution of the present invention, in the above-mentioned electric plating solution for iron-nickel alloy, iron is 5 to 20 g / L, preferably 7.5 to 17.5 g / L, particularly preferably 10 to 15 g / L, It is preferable to use nickel containing 30 to 70 g / L, preferably 40 to 60 g / L.
이하에, 본 발명 도금액의 바람직한 양태로서, 와트액, 술팜산액의 조성을 기재한다.Below, as a preferable aspect of the plating liquid of this invention, the composition of a wattage liquid and a sulfamic acid liquid is described.
＜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 to 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: 20-180 g / L, preferably 40-140 g / L, particularly preferably 60-120 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 saccharate: 1 to 5 g / ℓ, preferably 2 to 4 g / ℓ
알릴술폰산나트륨 : 1.5 ∼ 10 g/ℓ, 바람직하게는 3.5 ∼ 8.5 g/ℓSodium allyl sulfonate: 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 to 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/ℓIron 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: 20-180 g / L, preferably 40-140 g / L, particularly preferably 60-120 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 saccharate: 1 to 5 g / ℓ, preferably 2 to 4 g / ℓ
알릴술폰산나트륨 : 1.5 ∼ 10 g/ℓ, 바람직하게는 3.5 ∼ 8.5 g/ℓSodium allyl sulfonate: 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 on an object to be plated using the plating solution of the present invention is not particularly limited, and for example, after subjecting the object to be plated to pretreatment such as alkali degreasing and acid activity, the method is immersed in the plating solution of the present invention. And the like.
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 the electroplating are not particularly limited, and the conditions of electroplating of a conventional iron-nickel alloy may be used. For example, at a liquid temperature of 20 to 60 ° C, iron and nickel are used in combination with the anode, and the cathode current density It may be carried out at 0.5 to 3 A / dm 2 . Moreover, it is preferable to stir with a paddle or the like during electroplating.
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 for electroplating, the higher the temperature of the plating solution, the lower the proportion of iron in the obtained iron-nickel alloy, and the faster the stirring rate, the higher the proportion of iron, and the relative concentration of iron in the plating solution. Since the ratio of iron decreases when it is lowered, the skilled person can control the ratio of iron and 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 plated object which can be electroplated with the plating solution of the present invention is not particularly limited, and examples thereof include a surface formed of a metal such as copper, nickel, stainless steel, a resin such as ABS, polyimide, or the like. .
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 coating product obtained by electroplating the plated object as described above has a low thermal expansion coefficient and high hardness. Specifically, the ratio of iron and nickel is set to 100% of both, and iron is 55 to 70% and nickel is 30 to 45%, preferably iron is 56 to 64% and nickel is 36 to 44%, the thermal expansion coefficient measured in the range of 25 ~ 400 ℃ 4.5 × 10 -6 / ℃ or less, preferably 4.0 × 10 -6 / ℃, particularly preferably at most 3.0 × 10 -6 / ℃ or less, 0.05 × 10 - 6 / ℃ or higher. Moreover, it is preferable that a coefficient of thermal expansion is measured under 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.The iron-nickel alloy plated coated product having such properties can be used for metal masks, power electronics wiring boards, etc. because of its uniform composition and low coefficient of thermal expansion.
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 with reference to 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, sulfamic acid nickel 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, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36%) 16 mL / L were added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.8, and the contents of nickel and iron 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, 270 g / l of nickel sulfamate / hydrate, 30 g / l of boric acid, 7 g / l of nickel bromide, 92 g / l of iron sulfamate / pentahydrate, 100 g / l of sodium gluconate, 15 g / s of sodium tartrate ℓ, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36%) 16 mL / L were added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.8, and the contents of nickel and iron 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, 270 g / l of nickel sulfamate hydrate, 30 g / l of boric acid, 7 g / l of nickel bromide, 87 g / l of iron sulfamate pentahydrate, 100 g / l of sodium gluconate, 60 g / s of sodium tartrate ℓ, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36%) 16 mL / L were added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.8, and the contents of nickel and iron 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, sulfamic acid nickel tetrahydrate 156 g / L, boric acid 30 g / L, nickel bromide 7 g / L, sulfamic acid sulfate pentahydrate 47 g / L, sodium gluconate 60 g / L, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36%) 16 ml / L were added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.8, and the contents of nickel and iron 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, 270 g / L of nickel sulfamate hydrate, 30 g / L of boric acid, 7 g / L of nickel bromide, 87 g / L of iron sulfamate pentahydrate, 100 g / L of sodium gluconate, 25 g of disodium malonate / L, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36%) 16 mL / L were added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.8, and the contents of nickel and iron 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, 270 g / l of nickel sulfamate tetrahydrate, 30 g / l of boric acid, 7 g / l of nickel bromide, 87 g / l of iron sulfamate pentahydrate, 100 g / l of sodium gluconate, 15 g / s of sodium malate ℓ, sodium saccharin 3.2 g / L and sodium allyl sulfonate (36%) 16 mL / L were added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.8, and the contents of nickel and iron 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 by using the electroplating solutions for iron-nickel alloys 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.Electricity for iron-nickel alloys prepared in Examples 1 to 3 and Comparative Examples 1 to 3 after alkali degreasing (55 ° C., 10 minutes) and acid activity (room temperature, 30 seconds) were performed on a copper plate (60 × 80 mm). The plating solution was immersed under the following conditions to perform electroplating with a target film thickness of 10 mu m to obtain an iron-nickel alloy electroplating film. In addition, with respect to the electroplating solution for iron-nickel alloy prepared in Comparative Example 2, in the above conditions, the liquid temperature was set to 40 ° C., and electroplating was performed by stirring instead of paddle stirring (6 m / min), and electroplating the iron-nickel alloy. A film was obtained.
＜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 :Measurement of physical properties:
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.The plated films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were visually evaluated for appearance, and then the thermal expansion coefficient was measured under a nitrogen atmosphere in the range shown in Table 1 in the range of Table 1 (SII, Nano It was measured using technology: TMA / SS 6100: load 50 mN: heating rate 5 ° C / min). Moreover, the uniformity of the film composition was investigated by XRF and evaluated by the following evaluation criteria. Table 1 shows these results. In addition, as a result of finding the mass ratio of iron-nickel in the coating by a fluorescence X-ray analysis method, the mass ratio of iron-nickel was 64:36 (the number of decimal places is rounded off). In addition, the same measurement was performed also for the metallurgical invar alloy (the mass ratio of iron-nickel is 64:36) as a comparison.
＜피막 조성의 균일성의 평가 기준＞<Evaluation criteria for uniformity of coating composition>
평가 내용Evaluation contents
○ : 5 개 지점 측정하고, 편차가 평균값으로부터 ±3 ％ 이내○: 5 points were measured, and the deviation was within ± 3% from the average value.
× : 5 개 지점 측정하고, 편차가 평균값으로부터 ±3 ％ 이상×: 5 points were measured, and the deviation was ± 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 were mixed, a coating of 64% iron in the coating had a glossy appearance, good composition uniformity, and exhibited low thermal expansion in 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.In the electroplating solution for iron-nickel alloys of Example 1, an electroplating solution for iron-nickel alloys was prepared in the same manner except that nickel sulfamate / tetrahydrate was 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.In the electroplating solution for iron-nickel alloys of Example 1, the electroplating solution for iron-nickel alloys was prepared in the same manner except that nickel sulfamate / tetrahydrate was 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.In the electroplating solution for iron-nickel alloy of Example 1, the electroplating solution for iron-nickel alloy was prepared in the same manner except that the pH was 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.In the electroplating solution for iron-nickel alloy of Example 1, the electroplating solution for iron-nickel alloy was prepared in the same manner except that the pH was 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 alloys prepared in Examples 5 to 8. Further, using the electroplating solution for the iron-nickel alloy prepared in Example 1, the solution temperature was 35 ° C (Example 10), 55 ° C (Example 11) or stirring was performed by paddle stirring (6 m / min) (Example 12) Electroplating was carried out in the same manner as in Example 5 except for being used. The iron-nickel mass ratio and the uniformity of the coating composition were evaluated in the same manner as in Example 5. Table 2 shows the results.
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 mass ratio of iron-nickel can be adjusted by adjusting the nickel concentration, pH, liquid temperature, and stirring speed in the plating solution.
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 of nickel sulfamate, 30 g / l of boric acid, 7 g / l of nickel bromide, 50 g / l of iron sulfamate, 60 g / l of sodium gluconate, 3.2 g / l of sodium saccharinate and sodium allylsulfonate ( 36%) 16 ml / L was added and mixed to prepare an electric plating solution for an iron-nickel alloy. The pH of this plating solution was 3.8, and the contents of nickel and iron 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, 75 g / L of nickel sulfate, 55 g / L of nickel chloride, 40 g / L of boric acid, 40 g / L of ferrous sulfate, 60 g / L of sodium gluconate, 3.2 g / L of sodium saccharin, and sodium allylsulfonate (36%) 16 ml / L was added and mixed to prepare an electric plating solution for iron-nickel alloys. The pH of this plating solution was 3.0, and the contents of nickel and iron 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 performing alkali degreasing (40 ° C., 10 minutes) and acid activity (room temperature, 30 seconds) on a polyimide substrate (10 × 40 mm), the electric plating solution for iron-nickel alloy prepared in Reference Example 1 was as follows. It was immersed under the conditions, and electroplated to a target film thickness of 10 mu m 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 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 the stirring was 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.The electroplating solution for iron-nickel alloy prepared in Reference Example 2 was used, and electroplating was performed in the same manner as in Reference Example 3, except that the temperature was 40 ° C, to obtain an iron-nickel alloy electroplating film.
참고 시험예 1Reference Test Example 1
물성 측정 :Measurement of physical properties:
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.For the plated films obtained in Reference Examples 3 to 6, after visually evaluating the appearance, stress using a spiral stress meter (manufactured by Yamamoto Plating Test Co., Ltd .: spiral plating stress meter), micrometer (Mitsu Co., Ltd.) Hardness was measured using a soft, micro Vickers hardness meter (manufactured by Akashi Co., Ltd .: load 0.25 N) as Toyo Corporation. In addition, the thermal expansion coefficient was measured using a thermal, stress and strain measuring device (SII and Nano Technology: TMA / SS 6100: load 50 mN: heating rate 5 ° C / min) in a nitrogen atmosphere in a range of 25 to 200 ° C. Did. In addition, the mass ratio of iron-nickel in the film was determined by fluorescence X-ray analysis. Table 3 shows the results.
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 coefficient of thermal expansion and high hardness was obtained even if the plating solution was not subjected to heat treatment only by electroplating. Moreover, it was found that the composition of the iron-nickel alloy from which the low thermal expansion coefficient is obtained is in the vicinity of 58% of iron and 42% of 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.An electric plating solution for an iron-nickel alloy was prepared in the same manner as in Reference Example 2, except that it did not contain sodium allyl sulfonate (36%), and this was used to obtain an iron-nickel alloy electroplating film under the same conditions as in Reference Example 6. . Further, the appearance of the coating was not uniform. The obtained film was measured in the same manner as in Test Example 1, and the mass ratio of iron-nickel in the film and the coefficient of thermal expansion (/ ° C) were measured. As a result, the mass ratio of iron-nickel was 64% iron and 36% nickel, and the coefficient of thermal expansion (/ ° C) of 25 to 200 ° C was 8.6 x 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.An electric plating solution for an iron-nickel alloy was prepared in the same manner as in Reference Example 2, except that sodium allyl sulfonate (36%) was used as vinyl sulfonic acid, and using this, an iron-nickel alloy electroplating coating was applied under the same conditions as in Reference Example 6. Got. A uniform coating appearance was obtained, and the iron-nickel mass ratio was 55% for iron and 45% for 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.An electroplating solution for an iron-nickel alloy was prepared in the same manner as in Reference Example 2, except that sodium allyl sulfonate (36%) was used as propinsulphonic acid, and this was used to apply an iron-nickel alloy electroplating film under the same conditions as in Reference Example 6. Got The iron-nickel mass ratio of 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, 270 g / L of nickel sulfamate, 30 g / L of boric acid, 7 g / L of nickel bromide, 87 g / L of iron sulfamate, 100 g / L of sodium gluconate, 3.2 g / L of sodium saccharinate and sodium allylsulfonate ( 36%) 16 ml / L was added and mixed to prepare an electric plating solution for an iron-nickel alloy. The pH of this plating solution was 3.8, and the contents of nickel and iron 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 alkali degreasing (55 ° C., 10 minutes) and acid activity (room temperature, 30 seconds) on a copper plate (60 × 80 mm), immersed in the electric plating solution for iron-nickel alloy prepared in Reference Example 9 under the following conditions: Electroplating was performed with 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, 270 g / L of nickel sulfamate, 30 g / L of boric acid, 7 g / L of nickel bromide, 76.5 g / L of iron sulfamate, 100 g / L of sodium gluconate, 3.2 g / L of sodium saccharinate, and sodium allylsulfonate ( 36%) 16 ml / L was added and mixed to prepare an electric plating solution for an iron-nickel alloy. The pH of this plating solution was 3.8, and the contents of nickel and iron 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 alkali degreasing (55 ° C., 10 minutes) and acid activity (room temperature, 30 seconds) on a copper plate (60 × 80 mm), immersed in the electric plating solution for iron-nickel alloy prepared in Reference Example 9 under the following conditions: Electroplating was performed with 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 :Measurement of physical properties:
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 plated films obtained in Reference Examples 9 and 11, after visually evaluating the appearance, the thermal expansion coefficient was measured under a nitrogen atmosphere in the range shown in Table 4 in the range of the heat, stress, and strain measurement apparatus (manufactured by SII and Nanotechnology: TMA / SS) 6100: load 50 mN: temperature increase rate was measured using 5 ℃ / min). Moreover, the uniformity of the coating composition was investigated by XRF, and evaluated by the same evaluation criteria as before. Table 4 shows these results.
산업상 이용가능성Industrial availability
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 application as the iron-nickel alloy having an invar composition made of a solvent, and can 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 함유하는 철-니켈 합금용 전기 도금액으로서,
추가로, 카르복실기를 1 개 이상, 하이드록시기를 2 이상 갖고, 탄소수가 2 개 이상인 카르복실산 화합물을 2 종 이상 함유하는 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 may be substituted, an alkylene group or a phenylene group, and Y represents an alkali metal.)
As an electroplating solution for an iron-nickel alloy containing an unsaturated sulfonic acid compound represented by,
Further, an electroplating solution for an iron-nickel alloy having a low coefficient of thermal expansion, characterized in that it contains at least two carboxylic acid compounds having at least one carboxyl group, at least two hydroxy groups, and two or more carbon atoms.
카르복실산 화합물이, 타르타르산나트륨 및 글루콘산나트륨인 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.According to claim 1,
An electroplating solution for an 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 coefficient of thermal expansion that contains 10 to 80 g / l sodium tartrate.
불포화 술폰산 화합물이, 알릴술폰산나트륨, 비닐술폰산나트륨 및 프로핀술폰산나트륨으로 이루어지는 군에서 선택되는 1 종 또는 2 종 이상인 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 in which the unsaturated sulfonic acid compound has a low thermal expansion coefficient of at least one selected from the group consisting of sodium allyl sulfonate, sodium vinyl sulfonate and sodium propinsulfonate.
철을 5 ∼ 20 g/ℓ 및 니켈을 30 ∼ 70 g/ℓ 함유하는 것인 저열팽창 계수를 갖는 철-니켈 합금용 전기 도금액.The method according to any one of claims 1 to 4,
An electroplating solution for an iron-nickel alloy having a low coefficient of thermal expansion that contains 5 to 20 g / L of iron and 30 to 70 g / L of nickel.
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 5,
An electroplating solution for iron-nickel alloys having a low coefficient of thermal expansion, wherein the electroplating solution for iron-nickel alloys is wattage or sulfamic acid.
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 6,
In the iron-nickel alloy having a low coefficient of thermal expansion, the ratio of both iron and nickel is 100 mass%, and iron is 55 to 70 mass% and nickel is 30 to 45 mass%, and is in the range of 25 to 400 ° C. An electroplating solution for iron-nickel alloys having a low coefficient of thermal expansion with a measured coefficient of thermal expansion of 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.The method of claim 8,
An electroplating method of an iron-nickel alloy having a low coefficient of thermal expansion by stirring the electroplating, and using iron and nickel in combination with an anode at a bath temperature of 20 to 60 ° C, with a cathode current density of 0.5 to 3 A / dm 2 .
(단, R 은 비닐기 또는 에티닐기, X 는 치환되어 있어도 되는, 알킬렌기 또는 페닐렌기, Y 는 알칼리 금속을 나타낸다)
로 나타내는 불포화 술폰산 화합물을 함유시킨 것을 특징으로 하는 저열팽창 계수 및 고경도를 갖는 철-니켈 합금용 전기 도금욕.In addition to the electroplating bath for iron-nickel alloys, the following general formula (1)
(However, R represents a vinyl group or ethynyl group, X may be substituted, an alkylene group or a phenylene group, and Y represents an alkali metal.)
An electroplating bath for an iron-nickel alloy having a low thermal expansion coefficient and a high hardness, characterized by containing an unsaturated sulfonic acid compound represented by.
불포화 술폰산 화합물이, 알릴술폰산나트륨, 비닐술폰산나트륨 및 프로핀술폰산나트륨으로 이루어지는 군에서 선택되는 1 종 또는 2 종 이상인 저열팽창 계수 및 고경도를 갖는 철-니켈 합금용 전기 도금욕.The method of claim 11,
An electroplating bath for an iron-nickel alloy having a low thermal expansion coefficient and high hardness of at least one selected from the group consisting of sodium allyl sulfonate, sodium vinyl sulfonate and sodium propinsulfonate.
철을 4 ∼ 20 g/ℓ 및 니켈을 20 ∼ 70 g/ℓ 함유하는 것인 저열팽창 계수 및 고경도를 갖는 철-니켈 합금용 전기 도금욕.The method of claim 11 or 12,
An electroplating bath for iron-nickel alloys having low thermal expansion coefficient and high hardness, containing 4 to 20 g / L of iron and 20 to 70 g / L of nickel.
철-니켈 합금용 전기 도금욕이, 와트욕 또는 술팜산욕인 저열팽창 계수 및 고경도를 갖는 철-니켈 합금용 전기 도금욕.The method according to any one of claims 11 to 13,
An electroplating bath for an iron-nickel alloy having a low thermal expansion coefficient and a high hardness, wherein the electroplating bath for an iron-nickel alloy is a watt bath or a sulfamic acid bath.
저열팽창 계수 및 고경도를 갖는 철-니켈 합금이, 철과 니켈의 비율이 양자의 합계량을 100 질량％ 로 하여, 철이 55 ∼ 64 질량％ 및 니켈이 36 ∼ 45 질량％ 이고, 열팽창 계수가 9.0 × 10-6/℃ 이하이고, 비커스 경도가 200 HV 이상인 저열팽창 계수 및 고경도를 갖는 철-니켈 합금용 전기 도금욕.The method according to any one of claims 11 to 14,
The iron-nickel alloy having a low thermal expansion coefficient and a high hardness, the ratio of both iron and nickel is 100 mass%, the iron is 55 to 64 mass%, the nickel is 36 to 45 mass%, and the thermal expansion coefficient is 9.0. An electroplating bath for iron-nickel alloys having a low thermal expansion coefficient and a high hardness of x 10 -6 / ° C. or less and a Vickers hardness of 200 HV or more.
전기 도금 후에, 열처리를 실시하지 않는 저열팽창 계수 및 고경도를 갖는 철-니켈 합금의 전기 도금 방법.The method of claim 16,
An electroplating method of an iron-nickel alloy having a low thermal expansion coefficient and a high hardness that does not undergo heat treatment after electroplating.
전기 도금 후에, 열처리를 실시하지 않는 저열팽창 계수 및 고경도를 갖는 철-니켈 합금 도금 피복 제품.The method of claim 18,
An iron-nickel alloy plated coating product having a low thermal expansion coefficient and high hardness that does not undergo heat treatment after electroplating.
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| JP2011168831A (en) | 2010-02-18 | 2011-09-01 | Kyoto Ichi | Method for manufacturing iron-nickel alloy plating film having high hardness and low thermal expansion coefficient |
| JP2014500404A (en) * | 2010-12-23 | 2014-01-09 | コヴェンツィア ソチエタ ペル アツィオーニ | SUBSTRATE HAVING CORROSION-RESISTANT COATING AND METHOD FOR PRODUCING THE SAME |
| JP6084899B2 (en) * | 2013-06-07 | 2017-02-22 | 株式会社Ｊｃｕ | Electroplating bath for iron-nickel alloy having low thermal expansion coefficient and high hardness, and electroplating method using the same |
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| US9828686B2 (en) * | 2012-04-19 | 2017-11-28 | Dipsol Chemicals Co., Ltd. | Copper-nickel alloy electroplating bath and plating method |
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| JP2011168831A (en) | 2010-02-18 | 2011-09-01 | Kyoto Ichi | Method for manufacturing iron-nickel alloy plating film having high hardness and low thermal expansion coefficient |
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