JPH0319309B2 - - Google Patents
Info
- Publication number
- JPH0319309B2 JPH0319309B2 JP305886A JP305886A JPH0319309B2 JP H0319309 B2 JPH0319309 B2 JP H0319309B2 JP 305886 A JP305886 A JP 305886A JP 305886 A JP305886 A JP 305886A JP H0319309 B2 JPH0319309 B2 JP H0319309B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- nickel
- electroplating solution
- salt
- current density
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 39
- 150000003839 salts Chemical class 0.000 claims description 32
- 238000009713 electroplating Methods 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 16
- -1 amine borane compound Chemical class 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000006172 buffering agent Substances 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating Methods 0.000 description 73
- 238000004070 electrodeposition Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 13
- 239000000956 alloy Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 241000080590 Niso Species 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 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
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- BQFFOAXUGJJYNZ-UHFFFAOYSA-N dichloromethane;sulfuric acid Chemical compound ClCCl.OS(O)(=O)=O BQFFOAXUGJJYNZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- SQZYOZWYVFYNFV-UHFFFAOYSA-L iron(2+);disulfamate Chemical compound [Fe+2].NS([O-])(=O)=O.NS([O-])(=O)=O SQZYOZWYVFYNFV-UHFFFAOYSA-L 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- RHZZVWTVJHZKAH-UHFFFAOYSA-K trisodium;naphthalene-1,2,3-trisulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(S([O-])(=O)=O)=C(S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC2=C1 RHZZVWTVJHZKAH-UHFFFAOYSA-K 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Description
産業上の利用分野
本発明はニツケル、コバルト、鉄あるいはこれ
らの合金の均一電着性に優れためつき被膜を与え
ることができる電気めつき液に関する。
従来の技術及び発明が解決しようとする問題点
従来、ニツケル及びニツケル合金電気めつき液
として、ワツト浴、ワイズベルグ浴、高硫酸ニツ
ケル浴、高塩化物浴、スルフアミン酸ニツケル浴
などが知られているが、これらの浴はいずれも均
一電着性の点で問題があり、低電流密度部分の膜
厚不足による耐食性、光沢・レベリングの低下、
逆に低電流密度部分の膜厚を確保するために生じ
るめつき時間の増大や高電流密度部分への過剰電
析によるめつき製品の寸法精度の低下、めつき金
属の無駄な消費などの問題が起こる。特に最近に
おいては、プリント基板のエツチングレジスト用
めつき、端子めつき、IC、LSIの配線、リードフ
レーム等への金めつき下地などにニツケルメツキ
やニツケル−コバルト合金めつきが広く使用され
ているが、これらのめつきに用いる場合は、上述
したように均一電着性に劣り、低電流密度部分の
被覆力が乏しいので、ボンデイング、半田付け不
良、耐食性不良が生じたり、これを防止するため
低電流密度部分のめつき厚さを厚くすると、高電
流密度部分のめつき厚さが増大し、応力が上昇し
て密着不良が生じるなどの欠点があり、IC、LSI
等の製造上大きな問題となつていた。更に、プラ
スチツクや亜鉛ダイキヤスト製品にめつきした
り、EMI（電磁波障害）防止用パツケージにめつ
きしたりする場合は、これら製品は複雑な形状の
ものが多いので、低電流密度部分の光沢不良、
EMI防止能の低下などの問題があつた。
この場合、めつき厚さを均一にするには化学め
つき法を採用することが考えられるが、化学めつ
き法はめつき速度が遅い上、金属イオンの還元剤
を必要とすることからめつきコストが増大し、ま
た現在化学めつき可能な金属、合金の種類が限ら
れ、しかも通常は金属イオンが錯化されているの
で排水処理に手間を要するなどの問題がある。
従つて、従来よりニツケル、コバルト、鉄、こ
れらの合金電気めつき液として均一電着性に優れ
たものが望まれていた。
本発明は上記事情に鑑みなされたもので、均一
電着性が優れたニツケル、コバルト、鉄又はこれ
らの合金めつき被膜が得られる電気めつき液を提
供することを目的とする。
問題点を解決するための手段
即ち、本発明者は、ニツケル、ニツケル合金等
のめつき被膜の均一電着性を改良することにつき
鋭意研究を重ねた結果、ニツケル、コバルト及び
鉄から選ばれる金属の水溶性塩をめつきすべき金
属のイオン源としためつき液中にアルカリ金属、
アルカリ土類金属及びアルミニウムから選ばれる
金属の水溶性硫酸塩及びスルフアミン酸塩の少な
くとも１種を150ｇ／以上、より好ましくは200
ｇ／以上の高濃度で含有させ、かつ、緩衝剤と
してホウ酸を添加した場合、均一電着性が著しく
増大することを知見した。この場合、例えば、ワ
ツト浴はNiSO4・6H2Oを300ｇ／程度含有し、
通常のスルフアミン酸ニツケル浴はスルフアミン
酸ニツケルを300ｇ／以上含有し、また、従来
より高塩化ニツケル浴としてNiCl2・6H2Oを300
ｇ／含有するめつき液は知られているが、これ
らは上述したように均一電着性に劣る。ところ
が、硫酸イオン、ハロゲンイオン又はスルフアミ
ン酸イオンをNi，Co，Fe等の硫酸塩、ハロゲン
化物として与えるのではなく、アルカリ金属、ア
ルカリ土類金属、或いはアルミニウムの硫酸塩、
ハロゲン化物又はスルフアミン酸塩として高濃度
で与え、かつ緩衝剤としてホウ酸を添加する場合
は、均一電着性が顕著に増大することを見出し、
更に硫酸や塩酸を添加した場合はより均一電着性
が増大すること、また、アミンボラン化合物、ヒ
ドラジン化合物、亜リン酸、次亜リン酸又はこれ
らの塩を添加すると高硬度のめつき被膜が得られ
るなどの特長が付与されることを知見し、本発明
をなすに至つたものである。
以下、本発明につき更に詳しく説明する。
本発明に係るメツキ液は、ニツケル、コバルト
及び鉄から選ばれる金属の水溶性塩を含有すると
共に、導電性塩としてアルカリ金属、アルカリ土
類金属及びアルミニウムから選ばれる金属の水溶
性硫酸塩及びスルフアミン酸塩の少なくとも１種
を150〜800ｇ／含有しているものである。
ここで、上記水溶性金属塩としてはNi，Fe，
Coの水溶性塩であれば特に制限はなく、例えば、
Ni，Fe，Coの硫酸塩、スルフアミン酸塩、ハロ
ゲン化物等、具体的には硫酸ニツケル、硫酸第１
鉄、硫酸コバルト、臭化ニツケル、塩化ニツケ
ル、塩化第１鉄、塩化コバルト、スルフアミン酸
ニツケル、スルフアミン酸第１鉄、スルフアミン
酸コバルトなどが挙げられ、これらの金属塩は10
〜400ｇ／、特に10〜200ｇ／、より好適には
10〜100ｇ／の濃度で使用することができる。
この場合、これら金属塩の濃度が低くても本発明
によればこげが生じがたく、しかも均一電着性の
向上を計ることができる。合金めつき被膜を得る
場合には、上記水溶性金属塩の２種以上、あるい
は上記水溶性金属塩を主成分とし、これにタング
ステン酸及びその塩、モリブデン酸及びその塩、
硫酸亜鉛、塩化亜鉛などの亜鉛金属塩、硫酸銅、
塩化銅などの銅金属塩、硫酸錫、塩化錫などの錫
金属塩など、Ni，Fe，Coと合金化すべき所望の
金属の水溶性塩を選択して使用することができ
る。また、これら合金化すべき金属塩の濃度は合
金組成において適宜選定されるが、通常１〜100
ｇ／、特に１〜50ｇ／の範囲とすることがで
きる。
本発明においては、上記水溶性金属塩をめつき
すべき金属のイオン源とするめつき液中に導電性
塩としてアルカリ金属、アルカリ土類金属、アル
ミニウムから選ばれる金属の硫酸塩及びスルフア
ミン酸塩の１種又は２種以上添加する。具体的に
は硫酸リチウム、硫酸ナトリウム、硫酸カリウ
ム、硫酸アルミニウム、スルフアミン酸ナトリウ
ム、スルフアミン酸カリウムなどが例示される。
これらの導電性塩の使用量は150〜800ｇ／と
することが必要であり、これら導電性塩を150
ｇ／以上の高濃度で使用することにより高均一
電着性が達成される。これに対し、その配合量が
150ｇ／より少ない場合は均一電着性の向上に
対する効果が乏しく、本発明の目的を達成し得な
い。なお、前記導電性塩のより好ましい使用量は
200〜500ｇ／である。
本発明のめつき液には、上記成分に加えて更に
緩衝剤としてホウ酸を添加するものであり、その
添加量は緩衝剤として有効に作用する量であれば
よく、特に制限されないが、20〜60ｇ／とし、
また、前記Ni，Fe，Coイオンと緩衝剤としての
ホウ酸との比率は重量比として１：１〜１：５と
することが均一電着性をより高める点から好まし
い。
また、本発明のめつき液にはハロゲンイオンを
陽極の溶解のために加えることが望ましい。その
添加量は、ハロゲン化塩として５〜100ｇ／で
あることが望ましい。ハロゲン化塩は、例えば塩
化ニツケル、塩化鉄、塩化コバルト、塩化ナトリ
ウム、塩化カリウム、臭化ニツケル、臭化ナトリ
ウム、臭化カリウム等であることが望ましい。
更に本発明のめつき液には、塩酸又は硫酸を添
加することができ、これにより均一電着性を改良
することができる。その使用量は0.1〜30ｇ／、
特に１〜３ｇ／とすることが好ましい。なおこ
の場合、前記Ni，Fe，Coの水溶性塩の濃度を10
〜100ｇ／の低濃度とすることが高均一電着性
のめつき被膜を得ることから好ましい。
本発明のめつき液には、次亜リン酸、亜リン
酸、及びこれらの塩やアミンボラン化合物、ヒド
ラジン化合物を１〜100ｇ／程度添加すること
ができ、これによりリン含有又はホウ素含有めつ
き被膜を得ることができる。このようなリン又は
ホウ素含有めつき被膜は、マイクロビツカース硬
度Hv500〜800の硬質被膜となり、化学ニツケル
めつき被膜と同様に加熱処理により更に高硬度の
被膜を得ることができる。また、ホウ素含有合金
めつき被膜は、優れた半田付け性、ボンデイング
性、耐熱性、耐摩耗性を発揮するようになる。
なおまた、本発明の電気めつき液には、光沢
剤、レベリング剤などの添加剤として通常用いら
れる添加剤、例えばサツカリン、ナフタレンジス
ルホン酸ナトリウム、ナフタレントリスルホン酸
ナトリウム、アリルスルホン酸ナトリウム、プロ
パギルスルホン酸ナトリウム、ブチンジオール、
プロパギルアルコール、クマリン、ホルマリンな
どを適量添加することができる。
本発明のめつき液のPHは１〜12、特に１〜10が
好適であり、酸性浴、中性浴、アルカリ性浴のい
ずれであつてもよいが、とりわけ酸性めつきにお
いて本発明の効果を有効に発揮する。
本発明のめつき液を用いてめつきする場合のめ
つき条件は公知のNi，Fe，Coあるいはこれらの
合金めつきと同様の条件を採用し得、例えばめつ
き温度は10〜70℃、陰極電流密度0.01〜50A／ｄ
m2の条件が採用され得る。また、必要に応じ、空
気撹拌、カソードロツキング、ポンプ等による液
循環、プロペラ撹拌などの方法で撹拌を行なうこ
とができる。アノードはそのめつき液の種類に応
じ選定され、例えば電気ニツケル、硫黄含有ニツ
ケル、カーボナイズドニツケル、鉄、コバルト、
合金アノード等の可溶性陽極が用いられ、また場
合によつては白金、カーボン等の不溶性陽極を使
用することもできる。
なお、本発明のめつき液を用いてめつきする場
合、電流効率は60〜100％になるようにすること
が高均一電着性を達成し、低電流密度部分のめつ
き膜厚を厚くし得る点から好ましい。
本発明のめつき液を用いてめつきする製品の材
質に制限はなく、電気めつき可能な材質であれば
いずれのものもめつきし得、例えば金属や導電化
されたプラスチツク、セラミツク等がめつきされ
る。これらは公知の前処理を施し、所望の下地め
つきを施した後、本発明のめつき液を用いてめつ
きすることができ、また本発明のめつき液による
めつき後、その上にクロムめつき、金めつき、そ
の他所望のめつきを施すなどの公知の後処理を施
すことができる。
発明の効果
本発明に係る電気めつき液は、ニツケル、コバ
ルト及び鉄から選ばれる金属の水溶性塩を含有
し、アルカリ金属、アルカリ土類金属及びアルミ
ニウムから選ばれる金属の水溶性ハロゲン化物、
硫酸塩及びスルフアミン酸塩の少なくとも１種を
150〜800ｇ／を含有し、更に緩衝剤としてホウ
酸を含有したことにより、均一電着性に優れ、高
電流密度部分と低電流密度部分との膜厚差の少な
いめつき被膜が得られる。このため、本発明めつ
き液は、電子部品（プリント基板のエツチングレ
ジスト用めつき、端子めつき、IC、LSIの配線、
リードフレーム等）、金型、プリント配線基板、
摺動部品、電鋳品へのめつき、バレルめつきや複
雑な形状を有するプラスチツク、電磁波障害防止
用パツケージ、多孔性素材への金属被膜、アルマ
イト染色めつきなどに好適に用いられる。
以下に実施例を示して本発明を具体的に説明す
るが、本発明の範囲はこれに限定されるものでは
ない。
実施例 １
NiCl24・6H2O 50ｇ／
Na2SO4 300 〃
H3BO3 45 〃
PH 4.0
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行なつたところ、ワツト浴から得られるめつき
によく似た外観を有するNiめつき被膜が得られ
た。
実施例 ２
実施例１の電気めつき液にサツカリンナトリウ
ム１ｇ／とブチンジオール0.1ｇ／とを添加
した電気めつき液を用いて、温度55℃、陰極電流
密度2A／ｄm2において空気撹拌下でめつきを行
なつたところ、黒みのある光沢状の柔軟性のある
Niめつき被膜が得られた。
実施例 ３
NiBr2 70ｇ／
K2SO4 150 〃
H3BC3 45 〃
PH 4.2
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行なつたところ、黒みのある無光沢の低応力で
柔軟性のあるNiめつき被膜が得られた。
実施例 ４
実施例１の電気めつき液にジメチルアミンボラ
ン１ｇ／を添加した電気めつき液を用いて、温
度55℃、陰極電流密度2A／ｄm2において空気撹
拌下でめつきを行なつたところ、完全光沢のNi
−Ｂめつき被膜が得られた。
実施例 ５
実施例１の電気めつき液に亜リン酸50ｇ／と
濃硫酸1.5ml／とを加えてPHを２に調整した電
気めつき液を用いて、温度55℃、陰極電流密度
2A／ｄm2において空気撹拌下でめつきを行なつ
たところ、完全光沢のNi−Ｐ合金めつきが得ら
れた。
実施例 ６
CoSO4・7H2O 50ｇ／
Na2SO4 250 〃
H3BO3 40 〃
PH 4.2
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行なつたところ、無光沢で柔軟性のあるCoめ
つきが得られた。
実施例 ７
FeSO4・7H2O 60ｇ／
K2SO4 240 〃
H3BO3 40 〃
PH 3.5
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行なつたところ、無光沢で柔軟性のあるFeめ
つきが得られた。
実施例 ８
NiSO4・6H2O 60ｇ／
KCl 25 〃
スルフアミン酸ナトリウム 500 〃
H3BO3 45 〃
PH 4.2
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行なつたところ、白みある無光沢で柔軟性のあ
るNiめつき被膜が得られた。
比較例 １
NiSO4・6H2O 280ｇ／
NiCl2・6H2O 45 〃
H3BO3 40 〃
PH 4.4
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行ない、Niめつき被膜を得た。
比較例 ２
スルフアミン酸Ni 300ｇ／
NiCl2・6H2O 30 〃
H3BO3 40 〃
PH 4.4
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行ない、Niめつき被膜を得た。
比較例 ３
NiSO4・6H2O 280ｇ／
NiCl2・6H2O 40 〃
CoSO4・7H2O 35 〃
ギ酸ナトリウム 25 〃
H3BO3 40 〃
PH 4.2
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行ない、Ni−Co合金めつき被膜を得た。
比較例 ４
NiCl2・6H2O 300ｇ／
H3BO3 35 〃
PH 4.2
上記の電気めつき液を用いて、温度55℃、陰極
電流密度2A／ｄm2において空気撹拌下でめつき
を行ない、Niめつき被膜を得た。
また、上記実施例１〜11及び比較例１〜４の電
気めつき液につき、めつき試験器として山本鍍金
試験器社製改良型ハーリングセルを用いて均一電
着性を調べた。この場合、陽極には電気ニツケル
板、陰極にはそれぞれ裏面にテープコーテイング
を施した61×100×0.3mmサイズの銅板２枚を用
い、距離比１：５にて、電気めつき液を液温55℃
に保ち、ゆるい空気撹拌を行ないながら総電流
2Aにて30分間通電した。得られためつきの均一
電着性（Ｔ（％））は、陰極に析出しためつき被膜
重量を秤量し、下記の式に従い算出した。
Ｔ（％）＝Ｐ−Ｍ／Ｐ＋Ｍ−２×100
但し、Ｔ：均一電着性
Ｐ：距離比（本実験では５）
Ｍ：陰極に析出しためつき被膜重量比
〔M1／M2：M1は陽極に近い方の陰極重量
増加、M2は陽極に遠い方の陰極重量増加〕
INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to an electroplating solution that can provide a glazed film with excellent uniform electrodeposition properties of nickel, cobalt, iron, or alloys thereof. Conventional techniques and problems to be solved by the invention Conventionally, as nickel and nickel alloy electroplating solutions, Watt bath, Weisberg bath, high nickel sulfate bath, high chloride bath, nickel sulfamic acid bath, etc. have been known. However, all of these baths have problems in terms of uniform electrodeposition, and corrosion resistance, gloss and leveling decrease due to insufficient film thickness in low current density areas.
On the other hand, there are problems such as increased plating time to ensure film thickness in low current density areas, decreased dimensional accuracy of plated products due to excessive electrodeposition in high current density areas, and wasteful consumption of plated metal. happens. Particularly recently, nickel plating and nickel-cobalt alloy plating have been widely used for etching resist plating on printed circuit boards, terminal plating, IC and LSI wiring, gold plating bases for lead frames, etc. When used for these platings, as mentioned above, the uniform electrodeposition is poor and the coverage of low current density areas is poor, resulting in poor bonding, poor soldering, and poor corrosion resistance. If the plating thickness is increased in the current density area, the plating thickness will increase in the high current density area, which increases stress and causes poor adhesion.
This has become a major problem in manufacturing. Furthermore, when plating plastics, zinc die-cast products, or EMI (electromagnetic interference) prevention packages, many of these products have complex shapes, so poor gloss in low current density areas,
There were problems such as a decline in EMI prevention ability. In this case, chemical plating may be used to make the plating thickness uniform, but chemical plating has a slow plating speed and requires a metal ion reducing agent, which increases the plating cost. In addition, the types of metals and alloys that can be chemically plated are currently limited, and since metal ions are usually complexed, wastewater treatment requires time and effort. Therefore, there has been a desire for electroplating solutions for nickel, cobalt, iron, and alloys thereof that have excellent uniform electrodeposition properties. The present invention was made in view of the above circumstances, and an object of the present invention is to provide an electroplating solution capable of producing a nickel, cobalt, iron, or alloy plating film having excellent uniform electrodeposition properties. Means for Solving the Problems Namely, as a result of extensive research into improving the uniform electrodepositivity of plating films made of nickel, nickel alloys, etc., the present inventor has developed a metal selected from nickel, cobalt, and iron. The water-soluble salt of the alkali metal,
150 g or more, more preferably 200 g of at least one water-soluble sulfate or sulfamate of a metal selected from alkaline earth metals and aluminum.
It has been found that when boric acid is contained at a high concentration of g/g/g or more and boric acid is added as a buffer, uniform electrodeposition properties are significantly increased. In this case, for example, the Watts bath contains about 300 g/NiSO 4 6H 2 O,
A normal nickel sulfamate bath contains 300 g or more of nickel sulfamate, and conventionally, a high chloride bath contains 300 g of nickel sulfamate.
Although plating solutions containing g/g/g are known, these have poor uniform electrodeposition properties as described above. However, instead of providing sulfate ions, halogen ions, or sulfamate ions as sulfates or halides of Ni, Co, Fe, etc., sulfates of alkali metals, alkaline earth metals, or aluminum,
It has been found that when a halide or sulfamate is provided at a high concentration and boric acid is added as a buffer, uniform electrodeposition is significantly increased,
Furthermore, if sulfuric acid or hydrochloric acid is added, the uniform electrodeposition property will be increased, and if an amine borane compound, hydrazine compound, phosphorous acid, hypophosphorous acid, or a salt thereof is added, a highly hard plated film can be obtained. The present invention was based on the discovery that the present invention has the following characteristics. The present invention will be explained in more detail below. The plating solution according to the present invention contains a water-soluble salt of a metal selected from nickel, cobalt, and iron, and a water-soluble sulfate of a metal selected from alkali metals, alkaline earth metals, and aluminum as a conductive salt, and sulfamine. It contains 150 to 800 g of at least one acid salt. Here, the water-soluble metal salts include Ni, Fe,
There is no particular restriction as long as it is a water-soluble salt of Co. For example,
Ni, Fe, Co sulfates, sulfamates, halides, etc., specifically nickel sulfate, dichloromethane sulfate, etc.
These metal salts include iron, cobalt sulfate, nickel bromide, nickel chloride, ferrous chloride, cobalt chloride, nickel sulfamate, ferrous sulfamate, and cobalt sulfamate.
~400g/, especially 10-200g/, more preferably
It can be used at a concentration of 10-100g/.
In this case, even if the concentration of these metal salts is low, according to the present invention, scorching is unlikely to occur and uniform electrodeposition can be improved. When obtaining an alloy plating film, two or more of the above water-soluble metal salts or the above water-soluble metal salts are used as the main component, and tungstic acid and its salts, molybdic acid and its salts,
Zinc metal salts such as zinc sulfate and zinc chloride, copper sulfate,
Water-soluble salts of desired metals to be alloyed with Ni, Fe, and Co can be selected and used, such as copper metal salts such as copper chloride, tin metal salts such as tin sulfate, and tin chloride. In addition, the concentration of these metal salts to be alloyed is selected appropriately depending on the alloy composition, but is usually 1 to 100%.
g/, especially in the range from 1 to 50 g/. In the present invention, a sulfate or sulfamate of a metal selected from alkali metals, alkaline earth metals, and aluminum is added as a conductive salt to a plating solution in which the water-soluble metal salt is used as an ion source for the metal to be plated. Add one or more types. Specific examples include lithium sulfate, sodium sulfate, potassium sulfate, aluminum sulfate, sodium sulfamate, and potassium sulfamate. The amount of these conductive salts used must be 150 to 800 g/
High uniformity of electrodeposition can be achieved by using it at a high concentration of more than g/g/g. On the other hand, the amount of
If the amount is less than 150 g/l, the effect of improving uniform electrodeposition is poor and the object of the present invention cannot be achieved. In addition, the more preferable usage amount of the conductive salt is
It is 200-500g/. In addition to the above-mentioned components, boric acid is added to the plating solution of the present invention as a buffering agent, and the amount of boric acid added is not particularly limited as long as it acts effectively as a buffering agent. ~60g/and
Further, it is preferable that the ratio of the Ni, Fe, and Co ions to the boric acid as a buffering agent is 1:1 to 1:5 in terms of weight ratio from the viewpoint of further improving uniform electrodeposition. Further, it is desirable to add halogen ions to the plating solution of the present invention in order to dissolve the anode. The amount added is preferably 5 to 100 g/halide salt. Desirably, the halide salt is, for example, nickel chloride, iron chloride, cobalt chloride, sodium chloride, potassium chloride, nickel bromide, sodium bromide, potassium bromide, or the like. Furthermore, hydrochloric acid or sulfuric acid can be added to the plating solution of the present invention, thereby improving uniform electrodeposition. The amount used is 0.1~30g/,
In particular, it is preferably 1 to 3 g/. In this case, the concentration of the water-soluble salts of Ni, Fe, and Co is 10
It is preferable to use a low concentration of ~100 g/l because a plated film with high uniformity of electrodeposition can be obtained. Approximately 1 to 100 g of hypophosphorous acid, phosphorous acid, salts thereof, amine borane compounds, and hydrazine compounds can be added to the plating solution of the present invention, thereby forming a phosphorus-containing or boron-containing plating film. can be obtained. Such a phosphorus- or boron-containing plating film becomes a hard film with a micro-Vickers hardness of Hv500 to 800, and a film with even higher hardness can be obtained by heat treatment in the same way as a chemical nickel plating film. In addition, the boron-containing alloy plating film exhibits excellent solderability, bonding properties, heat resistance, and wear resistance. Furthermore, the electroplating solution of the present invention contains additives commonly used as additives such as brightening agents and leveling agents, such as saccharin, sodium naphthalene disulfonate, sodium naphthalene trisulfonate, sodium allylsulfonate, and propargyl. Sodium sulfonate, butynediol,
Appropriate amounts of propargyl alcohol, coumarin, formalin, etc. can be added. The pH of the plating solution of the present invention is preferably 1 to 12, particularly 1 to 10, and may be an acidic bath, a neutral bath, or an alkaline bath. Demonstrate effectively. The plating conditions for plating using the plating solution of the present invention may be the same as those for known Ni, Fe, Co, or alloy plating, such as a plating temperature of 10 to 70°C, Cathode current density 0.01~50A/d
m 2 conditions may be adopted. Further, if necessary, stirring can be performed by methods such as air stirring, cathode locking, liquid circulation using a pump, etc., and propeller stirring. The anode is selected depending on the type of plating liquid, such as electric nickel, sulfur-containing nickel, carbonized nickel, iron, cobalt,
A soluble anode such as an alloy anode is used, and in some cases an insoluble anode such as platinum or carbon may also be used. In addition, when plating using the plating solution of the present invention, the current efficiency should be set to 60 to 100% to achieve high uniformity of electrodeposition and increase the thickness of the plating film in low current density areas. It is preferable because it can be done. There is no restriction on the material of the product to be plated using the plating solution of the present invention, and any material that can be electroplated can be plated.For example, metals, conductive plastics, ceramics, etc. can be plated. be done. These can be plated using the plating solution of the present invention after performing a known pretreatment and a desired base plating, or after plating with the plating solution of the present invention, Known post-treatments such as chrome plating, gold plating, and other desired plating can be performed. Effects of the Invention The electroplating solution according to the present invention contains a water-soluble salt of a metal selected from nickel, cobalt, and iron, and a water-soluble halide of a metal selected from alkali metals, alkaline earth metals, and aluminum;
At least one of sulfate and sulfamate
By containing 150 to 800 g/ and further containing boric acid as a buffering agent, a plated film with excellent uniform electrodeposition and little difference in film thickness between the high current density portion and the low current density portion can be obtained. For this reason, the plating liquid of the present invention is suitable for electronic components (printed circuit board etching resist plating, terminal plating, IC, LSI wiring,
lead frames, etc.), molds, printed wiring boards,
Suitable for plating sliding parts, electroformed products, barrel plating, plastics with complex shapes, packages for preventing electromagnetic interference, metal coatings on porous materials, dyed alumite plating, etc. The present invention will be specifically explained below with reference to Examples, but the scope of the present invention is not limited thereto. Example 1 NiCl 24・6H 2 O 50 g / Na 2 SO 4 300 〃 H 3 BO 3 45 〃 PH 4.0 Using the above electroplating solution, the temperature was 55°C and the cathode current density was 2 A/dm 2 under air stirring. When plating was carried out, a Ni-plated film with an appearance very similar to the plating obtained from Watt bath was obtained. Example 2 An electroplating solution prepared by adding 1 g of saccharin sodium and 0.1 g of butynediol to the electroplating solution of Example 1 was used at a temperature of 55°C and a cathode current density of 2 A/dm 2 under air stirring. When I did the plating, it turned out to be a blackish glossy and flexible product.
A Ni-plated film was obtained. Example 3 NiBr 2 70g / K 2 SO 4 150 〃 H 3 BC 3 45 〃 PH 4.2 Using the above electroplating solution, plating was carried out at a temperature of 55°C and a cathode current density of 2A/dm 2 with air stirring. As a result, a dark, matte, low-stress, flexible Ni-plated film was obtained. Example 4 Using an electroplating solution prepared by adding 1 g of dimethylamine borane to the electroplating solution of Example 1, plating was carried out at a temperature of 55° C. and a cathode current density of 2 A/dm 2 under air agitation. However, completely glossy Ni
-B plating film was obtained. Example 5 Using an electroplating solution prepared by adding 50 g of phosphorous acid and 1.5 ml of concentrated sulfuric acid to the electroplating solution of Example 1 to adjust the pH to 2, the temperature was 55°C and the cathode current density was
When plating was carried out under air agitation at 2 A/dm 2 , a completely glossy Ni-P alloy plating was obtained. Example 6 CoSO 4・7H 2 O 50g / Na 2 SO 4 250 〃 H 3 BO 3 40 〃 PH 4.2 Using the above electroplating solution, the temperature was 55°C and the cathode current density was 2A/dm 2 under air stirring. When plating was carried out, a matte and flexible coating was obtained. Example 7 FeSO 4・7H 2 O 60 g / K 2 SO 4 240 〃 H 3 BO 3 40 〃 PH 3.5 Using the above electroplating solution, the temperature was 55°C and the cathode current density was 2 A/dm 2 under air stirring. When plating was carried out, a matte and flexible Fe plating was obtained. Example 8 NiSO 4 6H 2 O 60g / KCl 25 〃 Sodium sulfamate 500 〃 H 3 BO 3 45 〃 PH 4.2 Using the above electroplating solution, air was applied at a temperature of 55°C and a cathode current density of 2A/dm 2 When plating was carried out under stirring, a white, matte and flexible Ni-plated film was obtained. Comparative Example 1 NiSO 4・6H 2 O 280g/ NiCl 2・6H 2 O 45 〃 H 3 BO 3 40 〃 PH 4.4 Using the above electroplating solution, air was applied at a temperature of 55℃ and a cathode current density of 2A/dm 2. Plating was performed under stirring to obtain a Ni-plated film. Comparative Example 2 Ni sulfamic acid 300g/NiCl 2・6H 2 O 30 〃 H 3 BO 3 40 〃 PH 4.4 Using the above electroplating solution, plating was carried out at a temperature of 55°C and a cathode current density of 2A/dm 2 under air stirring. Plating was performed to obtain a Ni-plated film. Comparative example 3 NiSO 4・6H 2 O 280g/ NiCl 2・6H 2 O 40 〃 CoSO 4・7H 2 O 35 〃 Sodium formate 25 〃 H 3 BO 3 40 〃 PH 4.2 Using the above electroplating solution, the temperature Plating was carried out at 55° C. and with air stirring at a cathode current density of 2 A/dm 2 to obtain a Ni--Co alloy plated film. Comparative Example 4 NiCl 2 6H 2 O 300g / H 3 BO 3 35 〃 PH 4.2 Using the above electroplating solution, plating was carried out at a temperature of 55°C and a cathode current density of 2A/dm 2 with air stirring, A Ni-plated film was obtained. Further, the electroplating solutions of Examples 1 to 11 and Comparative Examples 1 to 4 were examined for uniform electrodeposition using an improved Harling cell manufactured by Yamamoto Plating Test Instruments Co., Ltd. as a plating tester. In this case, an electric nickel plate was used as the anode, and two copper plates with a size of 61 x 100 x 0.3 mm each with tape coating on the back were used as the cathode, and the electroplating solution was heated at a distance of 1:5. 55℃
the total current with gentle air agitation.
Electricity was applied at 2A for 30 minutes. The uniform electrodepositability (T (%)) of the obtained tampon was calculated by weighing the weight of the tamping film deposited on the cathode and according to the following formula. T (%) = P-M/P+M-2×100 However, T: Uniform electrodeposition P: Distance ratio (5 in this experiment) M: Weight ratio of the deposited film on the cathode [M 1 /M 2 : M 1 is the increase in the weight of the cathode closer to the anode, M 2 is the increase in the weight of the cathode farther from the anode]
【表】
上記の結果より、本発明に係る導電性塩を150
〜800ｇ／、並びにホウ酸を含有する電気めつ
き液（実施例）は、これらの導電性塩を含まず、
従つて本発明に係る導電性塩とホウ酸とを共に含
有していない電気めつき液（比較例）に比し、め
つき被膜の均一電着性がはるかに優れていること
が確認された。[Table] From the above results, the conductive salt according to the present invention
~800g/, and the electroplating solution (example) containing boric acid does not contain these conductive salts,
Therefore, it was confirmed that the uniform electrodeposition of the plating film was far superior to that of the electroplating solution (comparative example) that did not contain both the conductive salt and boric acid according to the present invention. .
Claims (1)
の水溶性塩を含有すると共に、導電性塩としてア
ルカリ金属、アルカリ土類金属及びアルミニウム
から選ばれる金属の水溶性硫酸塩及びスルフアミ
ン酸塩の少なくとも１種を150〜800ｇ／含有
し、かつ緩衝剤としてホウ酸を含有してなること
を特徴とする電気めつき液。 ２ H2SO4及び／又はHClを0.1〜30ｇ／添加
した特許請求の範囲第１項記載の電気めつき液。 ３ アミンボラン化合物、ヒドラジン化合物、亜
リン酸、次亜リン酸又はこれらの塩を添加した特
許請求の範囲第１項又は第２項記載の電気めつき
液。[Claims] 1. Contains a water-soluble salt of a metal selected from nickel, cobalt and iron, and as a conductive salt, a water-soluble sulfate and sulfamic acid of a metal selected from alkali metals, alkaline earth metals and aluminum. 1. An electroplating solution containing 150 to 800 g/at least one salt and boric acid as a buffering agent. 2. The electroplating solution according to claim 1, wherein 0.1 to 30 g of H 2 SO 4 and/or HCl are added. 3. The electroplating solution according to claim 1 or 2, to which an amine borane compound, a hydrazine compound, phosphorous acid, hypophosphorous acid, or a salt thereof is added.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60-167014 | 1985-07-29 | ||
| JP16701485 | 1985-07-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62109991A JPS62109991A (en) | 1987-05-21 |
| JPH0319309B2 true JPH0319309B2 (en) | 1991-03-14 |
Family
ID=15841785
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP305886A Granted JPS62109991A (en) | 1985-07-29 | 1986-01-10 | Electroplating solution |
| JP305786A Granted JPS62103387A (en) | 1985-07-29 | 1986-01-10 | Electroplating liquid |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP305786A Granted JPS62103387A (en) | 1985-07-29 | 1986-01-10 | Electroplating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPS62109991A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010131714A1 (en) | 2009-05-13 | 2010-11-18 | リズム時計工業株式会社 | Detection system, signal processing method of detection system, and smoke sensor |
| KR20160028244A (en) * | 2014-09-03 | 2016-03-11 | 연세대학교 산학협력단 | Object extraction method and apparatus using IR light |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH049492A (en) * | 1990-04-26 | 1992-01-14 | Nippon Kagaku Sangyo Kk | Hard nickel alloy plating bath |
| JPH04116191A (en) * | 1990-09-04 | 1992-04-16 | C Uyemura & Co Ltd | Electroplating method |
| JPH05331677A (en) * | 1992-05-27 | 1993-12-14 | Sumitomo Metal Mining Co Ltd | Iron electroplating liquid |
| JPH05331676A (en) * | 1992-05-27 | 1993-12-14 | Sumitomo Metal Mining Co Ltd | Iron electroplating liquid |
| JP4737790B2 (en) * | 1999-10-01 | 2011-08-03 | 株式会社シミズ | Nickel plating bath without boric acid |
| JP4740528B2 (en) * | 2003-09-08 | 2011-08-03 | 大阪府 | Nickel-molybdenum alloy plating solution, plating film and plated article |
| US7494578B2 (en) * | 2004-03-01 | 2009-02-24 | Atotech Deutschland Gmbh | Iron-phosphorus electroplating bath and method |
| JP2007262430A (en) * | 2006-03-27 | 2007-10-11 | C Uyemura & Co Ltd | Electroplating method |
| JP5201315B2 (en) * | 2007-09-26 | 2013-06-05 | 上村工業株式会社 | Electroplating method |
| JP5631775B2 (en) | 2011-02-24 | 2014-11-26 | 新光電気工業株式会社 | Composite plating solution |
| JP2014227570A (en) * | 2013-05-22 | 2014-12-08 | 日東電工株式会社 | Electroless plating method, multilayer base material manufacturing method, multilayer base material, and input device |
| JP5758557B1 (en) * | 2013-10-25 | 2015-08-05 | オーエム産業株式会社 | Manufacturing method of plated products |
| CN108468072B (en) * | 2018-03-13 | 2020-05-05 | 阿德文泰克全球有限公司 | Iron-nickel alloy shadow mask and preparation method thereof |
| CN111771016B (en) * | 2018-03-20 | 2023-05-23 | 阿文尼公司 | Method for electrodeposition of cobalt |
| FR3079242B1 (en) | 2018-03-20 | 2020-04-10 | Aveni | COBALT ELECTRODEPOSITION PROCESS |
| EP3781728A2 (en) | 2018-04-19 | 2021-02-24 | Basf Se | Composition for cobalt or cobalt alloy electroplating |
-
1986
- 1986-01-10 JP JP305886A patent/JPS62109991A/en active Granted
- 1986-01-10 JP JP305786A patent/JPS62103387A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010131714A1 (en) | 2009-05-13 | 2010-11-18 | リズム時計工業株式会社 | Detection system, signal processing method of detection system, and smoke sensor |
| KR20160028244A (en) * | 2014-09-03 | 2016-03-11 | 연세대학교 산학협력단 | Object extraction method and apparatus using IR light |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62103387A (en) | 1987-05-13 |
| JPH0319308B2 (en) | 1991-03-14 |
| JPS62109991A (en) | 1987-05-21 |
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