EP2141261B1 - Elektrolytische Zinnbeschichtungslösung und elektrolytisches Zinnbeschichtungsverfahren - Google Patents
Elektrolytische Zinnbeschichtungslösung und elektrolytisches Zinnbeschichtungsverfahren Download PDFInfo
- Publication number
- EP2141261B1 EP2141261B1 EP09155197.8A EP09155197A EP2141261B1 EP 2141261 B1 EP2141261 B1 EP 2141261B1 EP 09155197 A EP09155197 A EP 09155197A EP 2141261 B1 EP2141261 B1 EP 2141261B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plating
- acid
- tin plating
- tin
- plating solution
- 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.)
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- 238000007747 plating Methods 0.000 title claims description 130
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 23
- 150000001412 amines Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- MVEOHWRUBFWKJY-UHFFFAOYSA-N 7-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(O)=CC=C21 MVEOHWRUBFWKJY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 4
- 150000008365 aromatic ketones Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 claims 1
- 239000011135 tin Substances 0.000 description 44
- 229910052718 tin Inorganic materials 0.000 description 43
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 10
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 7
- 229940098779 methanesulfonic acid Drugs 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 229910001432 tin ion Inorganic materials 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 4
- IVXSQYUPCUOMRV-UHFFFAOYSA-M sodium;7-sulfonaphthalen-2-olate Chemical compound [Na+].C1=CC(S([O-])(=O)=O)=CC2=CC(O)=CC=C21 IVXSQYUPCUOMRV-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 3
- 229930008407 benzylideneacetone Natural products 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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- VKDSBABHIXQFKH-UHFFFAOYSA-M potassium;4-hydroxy-3-sulfophenolate Chemical compound [K+].OC1=CC=C(O)C(S([O-])(=O)=O)=C1 VKDSBABHIXQFKH-UHFFFAOYSA-M 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 3
- KDKIWFRRJZZYRP-UHFFFAOYSA-N 1-hydroxypropane-2-sulfonic acid Chemical compound OCC(C)S(O)(=O)=O KDKIWFRRJZZYRP-UHFFFAOYSA-N 0.000 description 2
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical class [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- YYONSVDCBDKMPX-UHFFFAOYSA-F methanesulfonate tin(4+) Chemical compound [Sn+4].[Sn+4].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-].CS(=O)(=O)[O-] YYONSVDCBDKMPX-UHFFFAOYSA-F 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- -1 polyoxypropylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- IKQCSJBQLWJEPU-UHFFFAOYSA-N 2,5-dihydroxybenzenesulfonic acid Chemical compound OC1=CC=C(O)C(S(O)(=O)=O)=C1 IKQCSJBQLWJEPU-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- ADIJLGOTHNVIMK-UHFFFAOYSA-N 2-[hydroxy(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(O)CCO ADIJLGOTHNVIMK-UHFFFAOYSA-N 0.000 description 1
- VVPHSMHEYVOVLH-UHFFFAOYSA-N 6-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(O)=CC=C21 VVPHSMHEYVOVLH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ONNDSTQPCPIOBG-WEVVVXLNSA-N CCC(CC(C1C)/C1=C/C)N Chemical compound CCC(CC(C1C)/C1=C/C)N ONNDSTQPCPIOBG-WEVVVXLNSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/16—Apparatus for electrolytic coating of small objects in bulk
Definitions
- the present invention relates to a tin plating solution and an electrolytic tin plating method; and in further detail relates to an electrolytic tin plating solution and plating method for plating chip components such as ceramic capacitors.
- Chip components are metal plated with tin, copper, silver, gold, nickel, palladium, or an alloy thereof, or the like, using a plating method such as barrel plating, plating with a flow-through plater, or the like, depending on the shape of the chip and the construction of the regions to be plated.
- a plating method such as barrel plating, plating with a flow-through plater, or the like, depending on the shape of the chip and the construction of the regions to be plated.
- the purpose for tin plating is to provide solderability to the electrode parts of the chip component.
- the chip components will stick to each other (hereinafter also referred to as aggregation, sticking, and coupling). Chips that stick together become defective products, and reduce the yield of the product.
- the ratio of chip components that stick together from the total number of chip components is referred to as the coupling rate, and in severe cases, the coupling rate can exceed 90%.
- a tin plating bath with excellent solder wetting properties is important for tin plating to provide solderability to the chip components, or the like.
- the present inventors have previously improved on this point, and have discovered that specific naphthol compounds are useful as an additive for electrolytic tin plating that can form a tin film with uniform appearance, and the deposited tin film will have favorable solder wetting properties, and have also discovered that the solderability can be improved using specific naphthol compounds.
- an objective present invention is to provide a plating solution for chip components and a plating method for chip components, which does not use a complexing agent, and which provides favorable solder wetting properties and an extremely low coupling rate when electrolytic tin plating is performed, and particularly when electrolytic tin plating is performed using a barrel plating method.
- a smooth tin plating film with higher film surface hardness than a conventional film and which can minimize sticking between plated substrates can be achieved by using specific compounds in a strongly acidic (pH of 1 or lower) tin plating bath, and particularly in a barrel tin plating bath that does not contain a complexing agent.
- one aspect of the present invention provides an electrolytic tin plating solution for chip components, comprising (A) stannous ions; (B) acid; (C) N,N-dipolyoxy-alkylene-N-alkyl amine, amine oxide, or blend thereof; (D) an anti-sticking agent; (E) a plating uniformity Improver; (F) an acrylic acid or acrylic acid derivative; and (G) an antioxidant, wherein the pH is 1 or lower.
- the acrylic acid or acrylic acid derivative is compound expressed by the following General Formula (1)
- R represents a hydrogen atom or an alkyl group containing between 1 and 3 carbon atoms.
- N,N-dipolyoxyalkylene-N-alkyl amine is one or more compounds expressed by the following General Formula (2). RN[(CH 2 CH 2 CH 2 O) x (CH 2 CH 2 O) z H][(CH 2 CH 2 CH 2 O) y (CH 2 CH 2 O) w H] (2)
- R represents an alkyl group with between 6 and 28 carbon atoms
- w, x, y, and z each represent an integer between 0 and 30.
- the sum ofw, x, y, and z is not 0.
- one aspect of the present invention provides an electrolytic tin plating solution for chip components, wherein the aforementioned amine oxide is one or more compound expressed by the following General Formula (3).
- R represents an alkyl group, cycloalkyl group, or aryl group
- R' represents a hydrogen atom, alkyl group, or cycloalkyl group
- the aforementioned (D) anti-sticking agent is one or more compound selected from a group consisting of aromatic aldehydes and aromatic ketones.
- one aspect of the present invention provides a method of plating chip components, comprising electrolytically tin plating chip components using an electrolytic tin plating solution comprising (A) stannous ions; (B) acid; (C) N,N-dipolyoxyalkylene-N-alkyl amine, amine oxide, or blend thereof; (D) an anti-sticking agent; (E) a plating uniformity Improver; (F) an acrylic acid or acrylic acid derivative; and (G) an antioxidant, wherein the pH is 1 or lower.
- an electrolytic tin plating solution comprising (A) stannous ions; (B) acid; (C) N,N-dipolyoxyalkylene-N-alkyl amine, amine oxide, or blend thereof; (D) an anti-sticking agent; (E) a plating uniformity Improver; (F) an acrylic acid or acrylic acid derivative; and (G) an antioxidant, wherein the pH is 1 or lower.
- the plating solution of the present invention is very effective at preventing substrates from sticking together and can minimize plating defects so the product yield increases when a plurality of substrates such as chip components, or the like, are electrolytically tin plated, and particularly when electrolytically tin plated using a barrel plating method.
- making the tin plating film smooth can reduce the sticking phenomenon that occurs when substrates come in contact with each other, where substrates lock together and physically cannot be peeled apart, similar to mat plating.
- increasing the film surface hardness can prevent tin plating films from deforming when substrates come in mutual contact, caused by the film surface being soft such as with mat plating, and can minimize the occurrence of tin plating films sticking together.
- the plating solution of the present invention does not include a complexing agent, so wastewater treatment is easier than with a convention plating solution for barrel plating.
- the terms "plating solution” and “plating bath” used in this specification have exactly the same meaning and are used interchangeably.
- the electrolytic tin plating solution of the present invention is an electrolytic tin plating solution for chip components, containing: (A) stannous ions, (B) acid, (C) N,N-dipolyoxy-alkylene-N-alkyl amine, amine oxide, or blend thereof, (D) an anti-sticking agent, (E) a plating uniformity Improver, (F) an acrylic acid or acrylic acid derivative, and (G) an antioxidant; wherein the pH is 1 or lower.
- A stannous ions
- B acid
- C N,N-dipolyoxy-alkylene-N-alkyl amine, amine oxide, or blend thereof
- D an anti-sticking agent
- E a plating uniformity Improver
- F an acrylic acid or acrylic acid derivative
- G an antioxidant
- the plating bath of the present invention contains stannous ions as an essential component.
- Stannous ions are bivalent tin ions. Any compound that can provide stannous ions to the plating bath can be used. Generally, the tin salt of an inorganic acid or an organic acid is preferable.
- tin salts of inorganic acids include the stannous salt of sulfuric acid or hydrochloric acid
- examples of tin salts of organic acids include the stannous salt of substituted or unsubstituted alkanesulfonic acids or alkanolsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, and 1-hydroxypropane-2-sulfonic acid, and the like.
- Particularly preferable sources of stannous ions are stannous sulfate for salts of inorganic acids and stannous methanesulfonate for salts of organic acids.
- the compounds which can provide these ions can be used individually, or as a blend of 2 or more types.
- the amount of stannous ion added to the plating bath is, for example, between 1 g/L and 150 g/L, preferably between 5 g/L and 50 g/L, and more preferably between 8 g/L and 20 g/L.
- the acid can be any arbitrary acid that can adjust the pH to 1 or lower and can provide conductivity to the plating bath.
- the acid can be any inorganic or organic acid.
- organic acids include substituted or unsubstituted alkanesulfonic acids or alkanolsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid, and 1-hydroxypropane-2-sulfonic acid. Methanesulfonic acid is preferable.
- examples of inorganic acids include sulfuric acid and hydrochloric acid, and sulfuric acid is preferable. These acids that can adjust the pH to 1 or lower and can provide conductivity to the plating bath can be used individually, or as a blend of 2 or more types.
- the amount of acid in the plating bath solution is preferably at least stoichiometically equivalent to the amount of bivalent tin ions in the plating bath.
- the amount of free acid in the plating bath is, for example, between 10 g/L and 500 g/L, preferably between 30 g/L and 300 g/L, and more preferably between 50 g/L and 200 g/L.
- the plating bath of the present invention contains N,N-dipolyoxyalkylene-N-alkyl amine, amine oxide, or blend thereof as an essential component.
- the present inventors have evaluated various nonionic surfactants, and have discovered that uniform plating at the required plating film thickness can be achieved by using N,N-dipolyoxyalkylene-N-alkyl amine or amine oxides which are specific anionic surfactants.
- N,N-dipolyoxyalkylene-N-alkyl amine is a polyoxypropylene polyoxyethylenealkylamine expressed by the following General Formula (2). RN[(CH 2 CH 2 CH 2 O) x (CH 2 CH 2 O) z H][(CH 2 CH 2 CH 2 O) y (CH 2 CH 2 O) w H] (2)
- R represents a straight or branched alkyl group with between 6 and 26 carbon atoms, and w, x, y, and z each represent an integer between 0 and 30. However, the sum of w, x, y, and z is not 0. Preferably, R represents a straight chain alkyl group with between 8 and 18 carbon atoms, and the sum of w, x, y, and z is between 10 and 20.
- the amine oxide is one or more compound expressed by the following General Formula (4).
- R 1 , R 2 , and R 3 each represent an alkyl group, a cycloalkyl group, or an aryl group, which may have a substitution group. Examples include a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, phenyl group, tolyl group xylyl group and naphthyl group, and the like.
- the amine oxide of the present invention is preferably one or more amine oxides with a structure as expressed by General Formula (3).
- R represents an alkyl group, cycloalkyl group or aryl group
- R' represents an alkyl group or a cycloalkyl group
- N,N-dipolyoxyalkylene-N-alkyl amine or amine oxide can act as a film modifying agent in the plating bath of the present invention.
- smoothing the plating film with N,N-dipolyoxyalkylene-N-alkyl amine or amine oxide can minimize the sticking phenomenon where substrates lock together and physically cannot be peeled apart, similar to mat plating, which occurs when substrates come in contact with each other.
- the concentration of N,N-dipolyoxyalkylene-N-alkyl amine or amine oxide in the plating bath is suitably between 0.01 g/L and 100 g/L, preferably between 0.1 g/L and 50 g/L, and more preferably between 1 g/L and 25 g/L.
- the plating bath of the present invention contains an anti-sticking agent as an essential component.
- the anti-sticking agent acts to prevent the plated chip components from agglomerating (sticking) together in the plating bath of the present invention.
- the anti-sticking agent is useful for preventing the chip components from agglomerating together, or in other words, preventing the chip components from sticking together, particularly during barrel plating.
- the anti-sticking agent is selected from aromatic aldehydes and aromatic ketones. Examples of preferable anti-sticking agents include benzaldehyde and benzylidene acetone. These compounds act to increase the film surface hardness in particular. In other words, increasing the film surface hardness can prevent tin plating films from deforming when substrates come in mutual contact, which is caused by the film surface being soft such as with mat plating, and can minimize the occurrence of tin plating films sticking together.
- the aforementioned preferable anti-sticking agents are particular effective when used in combination with the aforementioned (C) N,N-dipolyoxyalkylene-N-alkyl amine or amine oxide.
- concentration of anti-sticking agent in the plating bath is suitably between 1 mg/L and 50 g/L, preferably between 5 mg/L and 10 g/L, and more preferably between 10 mg/L and 5 g/L.
- the plating bath of the present invention contains a plating uniformity improver.
- the plating uniformity improver of the present invention is a compound that improves the plating uniformity particularly in areas of low current density.
- barrel plating in particular, the object to be plated is placed in a barrel and electroplating is performed while rotating the barrel with the parts immersed in the plating solution, and therefore variation in the current density will occur, the current density range of the object to be plated will vary widely from a high current density region to a low current density region, and in the low current density region, there will be problems with lower plating uniformity, and therefore the plating film will have variation.
- the plating uniformity improver By adding a plating uniformity improver, the plating can be uniformly performed even in the low current density regions.
- the plating uniformity improver is 2-naphthol-7-sulfonic acid, which can be either in the form of a free acid or as a salt.
- Suitable salts of 2-naphthol-7-sulfonic acid include water soluble salts such as potassium, sodium, ammonium, and tin, or the like, but potassium and sodium salts are preferable, and sodium 2-naphthol-7-sulfonate is even more preferable. These salts can be used individually, or as a blend of two or more types.
- the amount of 2-naphthol-7-sulfonic acid or salt thereof added to the plating bath is between 0.01 g/L and 20 g/L, preferably between 0.1 g/L and 10 g/L, and more preferably between 0.2 g/L and 5 g/L.
- the plating bath of the present invention contains one or more acrylic acid or acrylic acid derivative expressed by the following General Formula (1).
- acrylic acid and methacrylic acid are preferable.
- R represents a hydrogen atom or an alkyl group containing between 1 and 3 carbon atoms.
- the methacrylic acid or acrylic acid is preferably added to the plating solution of the present invention as an auxiliary anti-sticking agent that supports the aforementioned (D) anti-sticking agent.
- the methacrylic acid or acrylic acid can further increase the component anti-sticking effect of the (D) anti-sticking agent, and in particular has the effect of increasing the film surface hardness, and can increase the sustainability of the anti-sticking effect, by being used in combination with the (D) anti-sticking agent.
- the amount of acrylic acid or acrylic acid derivative expressed by the aforementioned General Formula (1) in the plating solution is suitably such that the concentration is between 0.1 g/L and 100 g/L, preferably between 0.1 g/L and 50 g/L, more preferably between 0.5 g/L and 10 g/L.
- An antioxidant is used in the plating solution of the present invention.
- the antioxidant is used to prevent oxidation of the bivalent tin ions to tetravalent tin ions, and examples include hydroquinone, catechol, resorcin, phloroglucin, pyrogallol, hydroquinonesulfonic acid, and salts thereof.
- the concentration of antioxidant in the plating bath is suitably between 10 mg/L and 100 g/L, preferably between 100 mg/L and 50 g/L, more preferably between 0.5 g/L and 5 g/L.
- additives can be added to the plating bath of the present invention, if necessary, such as glossing agents, smoothing agents, conductivity agents, and anode dissolving agents, and the like.
- the order when adding the various components when making the plating bath is not restricted in particular, but from the perspective of safety, the acid is added after adding the water, and after sufficiently mixing, the tin salt is added, and after sufficiently mixing, the other required chemicals are added in order.
- Examples of the chip components that can be plated using the plating solution of the present invention include electronic components such as resistors, capacitors, inductors, variable resistors, variable capacitors, and other passive components, quartz oscillator, LC filter, ceramic filter, delay lines, SAW filters, and other functional components, switches, connectors, relay fuses, optical components, and other contact components.
- electronic components such as resistors, capacitors, inductors, variable resistors, variable capacitors, and other passive components, quartz oscillator, LC filter, ceramic filter, delay lines, SAW filters, and other functional components, switches, connectors, relay fuses, optical components, and other contact components.
- the electroplating method that is used with the plating solution of the present invention can be a commonly known plating method such as barrel plating, and plating using a flow-through plater, or the like.
- the concentration of the various components (A) through (G) in the plating solution can be arbitrarily selected based on the forgoing descriptions for each of the components.
- the electroplating method that is used with the plating solution of the present invention can be performed at a bath temperature between 10°C and 50°C, preferably between 15°C and 30°C.
- the cathode current density is suitably selected within a range between 0.01 and 5 A/dm 2 , preferably between 0.05 and 3 A/dm 2 .
- the plating bath may be left without stirring, or can be stirred using a stirrer, or the like, or re-circulated using a pump, or the like.
- a bath was formed using the tin plating solution with the following composition.
- B (A) Methanesulfonic acid (as free acid): 50 g/L
- C Amine oxide: oxirane, methyl-, polymer with oxirane, ether with 2,2'-(oxidoimino)bis[ethanol] (2:1) N-[3-(C9-11-isoalkyloxy)propyl] derives 10 g/L
- E Methacrylic acid: 2 g/L
- F Sodium 2-naphthol-7-sulfonate: 0.5 g/L
- G Potassium hydroquinonesulfonate: 2 g/L
- Distilled water balance
- Barrel tin plating was performed on chip resistors that had been nickel plated using a 1 L tin plating solution at the conditions shown below, and then various evaluations were performed. The results are shown in Table 1.
- the plating thickness on the front surface, back surface, and on the left and right sides was measured using a fluorescent light x-ray film thickness meter, and the thickness and the plating thickness various between each point were evaluated.
- the barrel-plated chip components were sorted into chips which were stuck together and chips that were not stuck together, and the coupling rate was calculated as a ratio (%) with the weight of chips that stuck together in the numerator and the weight of all of the chips in the denominator (stuck chips/(stuck chips + unstuck chips) x 100).
- the zero cross time was measured and a value of 3.0 seconds or less was considered a PASS.
- the pass rate was calculated as a percentage using the number of samples with a zero cross time of 3 seconds or less in the numerator, and the total number of samples measured (10 samples) in the denominator.
- Tin plating baths were created at the ratios shown in Table 1 and Table 2 in a similar manner to Example 1, and the various tests were performed similar to Example 1. The results are also shown in Table 1 and Table 2. Note, the symbols related to the evaluation of the plating thickness are as shown below.
- Plating thickness is uniform on the front surface, back surface, and on the left and right
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Claims (4)
- Eine elektrolytische Zinnplattierungslösung für Chipkomponenten, die Folgendes beinhaltet:(A) Zinn-(II)-Ionen;(B) Säure;(C) eine oder mehrere Verbindungen, ausgedrückt durch die folgende allgemeine Formel:
RN[(CH2CH2CH2O)x(CH2CH2O)zH][(CH2CH2CH2O)y(CH2CH2O)wH],
wobei R eine Alkylgruppe mit zwischen 6 und 28 Kohlenstoffatomen darstellt und w, x, y und z jeweils eine ganze Zahl zwischen 0 und 30 darstellen, wobei die Summe von w, x, y und z allerdings nicht 0, ein Aminoxid oder eine Mischung davon ist; und(D) ein Antihaftmittel, das ausgewählt ist aus der Gruppe, bestehend aus aromatischen Aldehyden und aromatischen Ketonen;(E) 2-Naphthol-7-sulfonsäure oder ein Alkalisalz davon;(F) eine oder mehrere Acrylsäuren oder ein oder mehrere Acrylsäurederivate, wie durch die folgende allgemeine Formel (1) ausgedrückt:(G) ein Antioxidationsmittel;
wobei der pH-Wert 1 oder niedriger ist. - Elektrolytische Zinnplattierungslösung für Chipkomponenten gemäß Anspruch 1, wobei das oben erwähnte Aminoxid eine oder mehrere Verbindungen, ausgedrückt durch die folgende allgemeine Formel (3), ist:
- Elektrolytische Zinnplattierungslösung für Chipkomponenten gemäß Anspruch 1, wobei das Antihaftmittel aus Benzaldehyd und Benzylidinaceton ausgewählt ist.
- Ein Verfahren zum Plattieren von Chipkomponenten, beinhaltend das elektrolytische Zinnplattieren von Chipkomponenten unter Verwendung einer elektrolytischen Zinnplattierungslösung, welche Folgendes beinhaltet:(A) Zinn-(II)-Ionen;(B) Säure;(C) eine oder mehrere Verbindungen, ausgedrückt durch die folgende allgemeine Formel:
RN[(CH2CH2CH2O)x(CH2CH2O)zH][(CH2CH2CH2O)y(CH2CH2O)wH],
wobei R eine Alkylgruppe mit zwischen 6 und 28 Kohlenstoffatomen darstellt und w, x, y und z jeweils eine ganze Zahl zwischen 0 und 30 darstellen, wobei die Summe von w, x, y und z allerdings nicht 0, Aminoxid oder eine Mischung davon ist;(D) ein Antihaftmittel, das ausgewählt ist aus der Gruppe, bestehend aus aromatischen Aldehyden und aromatischen Ketonen;(E) 2-Naphthol-7-sulfonsäure oder ein Alkalisalz davon;(F) eine oder mehrere Acrylsäuren oder ein oder mehrere Acrylsäurederivate, wie durch die folgende allgemeine Formel (1) ausgedrückt:(G) ein Antioxidationsmittel;
wobei der pH-Wert 1 oder weniger ist.
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EP (1) | EP2141261B1 (de) |
JP (1) | JP5583894B2 (de) |
KR (1) | KR101593475B1 (de) |
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WO2011013252A1 (ja) | 2009-07-31 | 2011-02-03 | 株式会社Mテック・ジャパン | スズ含有合金メッキ浴、これを用いた電解メッキ方法および該電解メッキが堆積された基体 |
US20110293961A1 (en) | 2009-02-06 | 2011-12-01 | M-Tech Japan Co., Ltd. | Silver-containing alloy plating bath and method for electrolytic plating using same |
JP2012021224A (ja) * | 2010-06-15 | 2012-02-02 | Mitsubishi Shindoh Co Ltd | 錫めっき液中のスラッジ発生防止方法 |
US8888984B2 (en) * | 2012-02-09 | 2014-11-18 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
EP2740820A1 (de) | 2012-12-04 | 2014-06-11 | Dr.Ing. Max Schlötter GmbH & Co. KG | Elektrolyt und Verfahren zur Abscheidung von lötbaren Schichten |
JP6133056B2 (ja) * | 2012-12-27 | 2017-05-24 | ローム・アンド・ハース電子材料株式会社 | スズまたはスズ合金めっき液 |
US20150122662A1 (en) * | 2013-11-05 | 2015-05-07 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
US20150122661A1 (en) * | 2013-11-05 | 2015-05-07 | Rohm And Haas Electronic Materials Llc | Plating bath and method |
JP2017504715A (ja) * | 2013-12-05 | 2017-02-09 | ハネウェル・インターナショナル・インコーポレーテッド | 調節されたpHを有するメタンスルホン酸第一スズ溶液 |
CN105755513A (zh) * | 2016-04-28 | 2016-07-13 | 四川昊吉科技有限公司 | 一种镀锡防腐剂 |
JP6818520B2 (ja) | 2016-11-11 | 2021-01-20 | ローム・アンド・ハース電子材料株式会社 | 中性スズめっき液を用いたバレルめっきまたは高速回転めっき方法 |
JP6620858B2 (ja) * | 2017-10-24 | 2019-12-18 | 三菱マテリアル株式会社 | 錫又は錫合金めっき堆積層の形成方法 |
WO2019082885A1 (ja) * | 2017-10-24 | 2019-05-02 | 三菱マテリアル株式会社 | 錫又は錫合金めっき液 |
WO2019121092A1 (en) | 2017-12-20 | 2019-06-27 | Basf Se | Composition for tin or tin alloy electroplating comprising suppressing agent |
US11242606B2 (en) | 2018-04-20 | 2022-02-08 | Basf Se | Composition for tin or tin alloy electroplating comprising suppressing agent |
CN109518233B (zh) * | 2018-11-27 | 2020-07-14 | 东莞美坚化工原料有限公司 | 一种防止微型电子元器件粘片的导电溶液及其制备方法 |
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BE553400A (de) * | 1956-01-16 | |||
US3616306A (en) * | 1969-11-19 | 1971-10-26 | Conversion Chem Corp | Tin plating bath and method |
US4000047A (en) * | 1972-11-17 | 1976-12-28 | Lea-Ronal, Inc. | Electrodeposition of tin, lead and tin-lead alloys |
US4135991A (en) * | 1977-08-12 | 1979-01-23 | R. O. Hull & Company, Inc. | Bath and method for electroplating tin and/or lead |
US4871429A (en) * | 1981-09-11 | 1989-10-03 | Learonal, Inc | Limiting tin sludge formation in tin or tin/lead electroplating solutions |
US4717460A (en) * | 1983-12-22 | 1988-01-05 | Learonal, Inc. | Tin lead electroplating solutions |
US4582576A (en) * | 1985-03-26 | 1986-04-15 | Mcgean-Rohco, Inc. | Plating bath and method for electroplating tin and/or lead |
US4885064A (en) * | 1989-05-22 | 1989-12-05 | Mcgean-Rohco, Inc. | Additive composition, plating bath and method for electroplating tin and/or lead |
JP2856857B2 (ja) * | 1990-07-27 | 1999-02-10 | 石原薬品株式会社 | 錫、鉛または錫―鉛合金めっき浴 |
JP2001040498A (ja) * | 1999-07-27 | 2001-02-13 | Ne Chemcat Corp | 錫−銅合金めっき皮膜で被覆された電子部品 |
JP2001234387A (ja) * | 2000-02-17 | 2001-08-31 | Yuken Industry Co Ltd | 錫系電気めっきのウィスカー発生防止剤および防止方法 |
EP1260614B1 (de) * | 2001-05-24 | 2008-04-23 | Shipley Co. L.L.C. | Zinn Platierung |
JP3910028B2 (ja) | 2001-09-13 | 2007-04-25 | 株式会社村田製作所 | チップ型セラミックス電子部品の電極形成法 |
JP4812365B2 (ja) * | 2005-08-19 | 2011-11-09 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | 錫電気めっき液および錫電気めっき方法 |
CN101360851B (zh) * | 2005-11-18 | 2011-09-21 | 莱里斯奥鲁斯集团 | 一种主电极及其制备方法 |
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- 2009-06-11 US US12/456,077 patent/US20100000873A1/en not_active Abandoned
- 2009-06-11 KR KR1020090051978A patent/KR101593475B1/ko active IP Right Grant
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US20100000873A1 (en) | 2010-01-07 |
EP2141261A2 (de) | 2010-01-06 |
CN101619470B (zh) | 2012-03-28 |
JP5583894B2 (ja) | 2014-09-03 |
EP2141261A3 (de) | 2010-07-28 |
JP2009299123A (ja) | 2009-12-24 |
CN101619470A (zh) | 2010-01-06 |
TW201006966A (en) | 2010-02-16 |
TWI468554B (zh) | 2015-01-11 |
KR101593475B1 (ko) | 2016-02-12 |
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