US3075899A - Baths for the production of metal electroplates - Google Patents
Baths for the production of metal electroplates Download PDFInfo
- Publication number
- US3075899A US3075899A US807290A US80729059A US3075899A US 3075899 A US3075899 A US 3075899A US 807290 A US807290 A US 807290A US 80729059 A US80729059 A US 80729059A US 3075899 A US3075899 A US 3075899A
- Authority
- US
- United States
- Prior art keywords
- acid
- propane
- sulfonic acid
- brightening
- baths
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 title description 14
- 239000002184 metal Substances 0.000 title description 14
- 238000005282 brightening Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 23
- -1 SULFONIC ACID COMPOUND Chemical class 0.000 claims description 21
- 238000009713 electroplating Methods 0.000 claims description 20
- 239000002659 electrodeposit Substances 0.000 claims description 15
- 239000010953 base metal Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 description 38
- 239000003795 chemical substances by application Substances 0.000 description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 150000003556 thioamides Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 241000272534 Struthio camelus Species 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- LVQFQZZGTZFUNF-UHFFFAOYSA-N 2-hydroxy-3-[4-(2-hydroxy-3-sulfonatopropyl)piperazine-1,4-diium-1-yl]propane-1-sulfonate Chemical compound OS(=O)(=O)CC(O)CN1CCN(CC(O)CS(O)(=O)=O)CC1 LVQFQZZGTZFUNF-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 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
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- MBVGZSSYNIBAKI-UHFFFAOYSA-N pyridine-2-carbothioic s-acid Chemical compound OC(=S)C1=CC=CC=N1 MBVGZSSYNIBAKI-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 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
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
Definitions
- This invention relates to a method and bath for obtaining bright metal electrodeposits. It more particularly relates to the use of sulfonic acid derivatives of thioamides or isothioamides for obtaining bright metal electrodeposits.
- Another object of this invention is to provide electroplating bath brightener compounds which have high stability and long life.
- the compounds. used as brighteningragents in accordance with the invention have the general. structural for .wherein R, R and R", represent hydrocarbon radicals,
- R and/or R may also be hydrogen atoms.
- R and R may further form a polymethylene chain, so that the -thioamide group is a member ofa heterocyclic ring.
- Thehydrocarbon radicals are R and R"
- Brightening agents of this type are, for example,
- am-ide-N'-(propane w-sulfonic acid) betain am-ide-N'-(propane w-sulfonic acid) betain.
- the production of these compounds takes place, for example by reaction of the thioamides or isothioamide-S- esters with' organic amino sulfo-nic acids'or their salts.
- the isothioami'de S s'ters may also be reacted with haloalkanesulfonic acids or sultones.
- Suitable sulfonic .acids are. primarily those of the. aliphatic or aromatic series which react with the "thioamides or isothioamides in aqueous or non-aqueous, for example in' alcoholic solution or suspension.
- the reaction with the sultones may also take place in the -molten state. The reactions proceed readily and smoothly and as a rule produce high yields,
- thioamides or isothioamides which generally contain no sulfonic acid groups may be simultaneously used. In this manner'the working temperature may be increased up to .55" C. and
- wetting agents and ductility improving agents such as amino compounds free from carboxyl groups.
- ductility improving agents such as amino compounds free from carboxyl groups.
- the addition of the last-mentioned agents has the effect that inorganic impurities, such as those which are present in the hardness components of water and in technical grade metal salts, will not have a detrimental eifect upon the brightening effect.
- Amino compounds free from carboxyl groups of this type are, for example, N,N,N',N-tetraethyl-l,3-diamino propanol-2; N,N,N',N'-tetrahydroxyethyl-ethylene diamine-Z diethylamino-ethylchloride l; N,N dimethyl 4- bromoanilin-3-diethylamino-l-chloropropanol-Z; as well as halogen salts of quartenary ammonium compounds which have been formed from the last-mentioned substituents by internal rearrangement, as well as sulfuric acid derivatives which are derived from the first-mentioned amino compounds, such as N,N,N',N'-tetra-n-butyl-l,3- diaminopropanol-Z-monosulfuric acid ester and piperazine-N,N'-bis-(2-hydroxypropane-sulfonic
- the brightening agents according to the invention may also be advantageously used in an acid direct copper plating process, that is a process in which the, metal ob jects are treated prior to electroplating in an acid pickling bath containing inhibitors with a high inhibiting effect, and subsequently directly electroplated in said copper baths containing the agents accordinging to the invention, without intermediate rinsing.
- the brightening agents according to the invention may he used in acid, cyanide and alkaline electroplating baths for the production of copper, zinc, cadmium, tin, brass, bronze, silver and gold electroplates.
- the brightening agents are added to the baths in quantities from 0.001 gm./liter to 5 gm./liter, preferably from 0.05 to 0.03 gin/liter, and the electroplating process is carried out at bath temperatures from room temperature to 60? C., in alkaline baths up to 90 C., and'in current density ranges from 0.5 a'mp/dm. to 16 amp/dink, in'alkaline baths up to 40 am'pJdmP.
- Example I A customary acid copper electroplating 'bath which contained 210 gin/liter CuSO .5H O, 60 gm./ liter H 80, and as' brightening agent 2 gmJliter of a condensation product of dodecylalcohol and mols ethylene oxid Which had been 25% transformed into. the sulfuric acid ester, was modified with 0.3 gun/liter of the sodium saltof"caprothiolactam-N-(propane-w-sulfonic acid) having the structural formula Ii QHs-CHa-C mom nt usom A; brightening agent for the acid copper hath illustrated in Example I:
- Example IV Uniform brass electroplates. on iron and steel objects were. obtained when these materials were electroplated in a bath which contained 30 gm./liter copper cyanide, 9.4 gm./liter zinc cyanide, 56 gm./liter sodium cyanide,
- Example VII A tin electroplating bath which contained 420 gm./ liter potassium stannate and 22.5 gm./liter potassium hydroxide was modified with 3.5 gm./liter of potassium salt of caprothiolactam Ns(propane-w-sultonic acid). At current densitiesfofZ to 40 amp/din. and attemperatures
- Example VIII Thioacetamide N (propane w sulfonic acid) sodium salt having the following structural formula:
- CHa-(f-NH-CHI CHICHZ-S O N8 may be prepared by the following method. 16.1 gm./ liter (0.1 mol) w-aminopropanesodium sulfonate and 7.5 gm. (0.1 mol) thioacetamide were dissolved in 50 cc. water and the solution was heated for some time to 80 C., whereby ammonia escaped. After the evolution of ammonia had ceased the solution was evaporated in a vacuum. 20.7 gm. of a greenish-yellow product remained as a residue, which was purified by dissolving it in a small amount of water and reprecipitating it by adding an ether-acetone mixture. The use of this compound as a brightening agent is illustrated in Example II.
- CHr-(fi-SCHr- N-CHzCHgCHz-SOsNB may be prepared by the following method. 20.1 gm. of
- a method for producing bright metal electrodeposits on a base metal which comprises adding as a brightening compound to the electroplating bath solution containing a compound of the metal to be electrodeposited, a sulfonic acid compound having a structural formula, selected from the group consisting of:
- R and R are selected from the group consisting of hydrogen, hydrocarbon radicals, and taken together a polymethylene chain of a heterocyclic ring, and R" is a hydrocarbon radical, said brightening agent being added in sufiicient amount to obtain said bright electrodeposits.
- R and R are selected from the group consisting of hydrogen, hydrocarbon radicals, and taken together a polymethylene chain of heterocyclic ring, and R" is a hydrocarbon radical, and
- a method for producing bright copper electrodeposits on a base metal which comprises adding as a brightening compound to an acid copper electroplating bath solution a sulfonic acid "compound having a structural formula, selected from the'group consisting of:
- R and R' are selected from the group consisting of hydrogen, hydrocarbon radicals, and taken together a polymethylene chain of a heterocyclic ring, and R is a hydrocarbon radical, said brightening agent being added in sufficient amount to obtain said bright electrodeposits.
- An electroplating bath for producing bright metal electrodeposits on base metals which comprises an aqueous solution of a compound of the metal to be deposited and a brightening compound which is a sulfonic ama s acid compound having a structural formula, selected from the group consisting of: i i r R R"SO;H
- R and R are selected from the group consisting of hydrogen, hydrocarbon radicals, and taken together a polymethylene chain of a heterocyclic ring, and R" is a hydrocarbon radical, said brightening agent being added in sufficient amount to obtain said bright electrodeposits.
- An electroplating bath as defined in claim 7 selected from the group consisting of acid, cyanide and alkaline baths.
- An electroplating bath for producing bright metal elec'trodepositson base metals which comprises an aqueous solution of a compound of the metal to be deposited, a brightening compound which is a 'sulfonic acid compound having a structural formula, selected from the group consisting of:
- R and R are selected from the group consisting of hydrogen, hydrocarbon radicals, and taken together a'polyrnethylene chain of a heterocyclic ring, and R is a hydrocarbon radical, and in addition compounds having a structural formula selected from the group consisting of ,S RI wherein R, R and R" represent groups as above defined, said brightening agent being added in sufficient amount to obtain said bright electrodeposits.
- An acid copper electroplating bath for directly producing bright copper electrodeposits on base metals which comprises an aqueous acid solution of a copper salt and a brightening compound which is a sulfonic acid compound having a structural formula, selected from the group consisting of:
- N.-- R"-s0,rr R-G SR and their alkali metal salts wherein R and R are s e lected from the group consisting of hydrogen, hydrocarbon radicals, and taken together a polymethylene chain of a heterocyclic ring, and R is a hydrocarbon radical, said brightening agent being added in sufficient amount to obtain said bright electrodeposits.
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- 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)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED27981A DE1204044B (de) | 1958-04-26 | 1958-04-26 | Glanzgebende galvanische Metallbaeder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3075899A true US3075899A (en) | 1963-01-29 |
Family
ID=7039483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US807290A Expired - Lifetime US3075899A (en) | 1958-04-26 | 1959-04-20 | Baths for the production of metal electroplates |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3075899A (en:Method) |
| BE (1) | BE576264A (en:Method) |
| CH (1) | CH405863A (en:Method) |
| DE (1) | DE1204044B (en:Method) |
| FR (1) | FR1235348A (en:Method) |
| GB (1) | GB875846A (en:Method) |
| NL (1) | NL238490A (en:Method) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3277144A (en) * | 1963-11-18 | 1966-10-04 | Merck & Co Inc | 3-(n-acyl-n-methyl)-amino-1-hydrocarbonsulfonoxy propane compounds and method of preparation |
| US3642590A (en) * | 1969-07-16 | 1972-02-15 | Philips Corp | Acid electroplating bath for depositing tin |
| US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
| US4022676A (en) * | 1975-04-09 | 1977-05-10 | Francine Popescu | Alkaline bright zinc electroplating bath |
| US4244791A (en) * | 1979-04-19 | 1981-01-13 | Swiss Aluminium Ltd. | Acidic electrolyte containing SnII ions |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| DE102012004348A1 (de) | 2012-03-07 | 2013-09-12 | Umicore Galvanotechnik Gmbh | Zusatz zur Verbesserung der Schichtdickenverteilung in galvanischen Trommelelektrolyten |
| CN110777402A (zh) * | 2019-11-21 | 2020-02-11 | 武汉奥邦表面技术有限公司 | 一种酸性镀锌载体及其制备方法 |
| CN116041236A (zh) * | 2022-12-30 | 2023-05-02 | 光华科学技术研究院(广东)有限公司 | 二硫代酯类有机物及其制备方法与应用、镀铜液 |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489538A (en) * | 1941-05-24 | 1949-11-29 | Gen Motors Corp | Electrodeposition of copper |
| US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
| US2742413A (en) * | 1952-07-05 | 1956-04-17 | Metallic Industry Nv | Bright copper plating bath |
| US2772309A (en) * | 1954-08-12 | 1956-11-27 | Dow Chemical Co | Dithiooxamides |
| US2806879A (en) * | 1954-07-13 | 1957-09-17 | American Cyanamid Co | Preparation of dithiooxamide |
| US2830014A (en) * | 1954-03-22 | 1958-04-08 | Dehydag Gmbh | Electroplating process |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849352A (en) * | 1956-06-15 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2903403A (en) * | 1954-02-10 | 1959-09-08 | Dehydag Gmbh | Method of copper-plating metal surfaces |
| US2905602A (en) * | 1954-11-05 | 1959-09-22 | Dehydag Gmbh | Production of metal electrodeposits |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| US2950235A (en) * | 1957-12-17 | 1960-08-23 | Dehydag Gmbh | Acid copper electroplating baths |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR955898A (en:Method) * | 1945-07-07 | 1950-01-20 |
-
0
- NL NL238490D patent/NL238490A/xx unknown
-
1958
- 1958-04-26 DE DED27981A patent/DE1204044B/de active Pending
-
1959
- 1959-03-02 BE BE576264A patent/BE576264A/fr unknown
- 1959-03-16 CH CH7083259A patent/CH405863A/de unknown
- 1959-04-14 GB GB12562/59A patent/GB875846A/en not_active Expired
- 1959-04-20 US US807290A patent/US3075899A/en not_active Expired - Lifetime
- 1959-04-24 FR FR793038A patent/FR1235348A/fr not_active Expired
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489538A (en) * | 1941-05-24 | 1949-11-29 | Gen Motors Corp | Electrodeposition of copper |
| US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
| US2742413A (en) * | 1952-07-05 | 1956-04-17 | Metallic Industry Nv | Bright copper plating bath |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2903403A (en) * | 1954-02-10 | 1959-09-08 | Dehydag Gmbh | Method of copper-plating metal surfaces |
| US2830014A (en) * | 1954-03-22 | 1958-04-08 | Dehydag Gmbh | Electroplating process |
| US2806879A (en) * | 1954-07-13 | 1957-09-17 | American Cyanamid Co | Preparation of dithiooxamide |
| US2772309A (en) * | 1954-08-12 | 1956-11-27 | Dow Chemical Co | Dithiooxamides |
| US2905602A (en) * | 1954-11-05 | 1959-09-22 | Dehydag Gmbh | Production of metal electrodeposits |
| US2849352A (en) * | 1956-06-15 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2950235A (en) * | 1957-12-17 | 1960-08-23 | Dehydag Gmbh | Acid copper electroplating baths |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3277144A (en) * | 1963-11-18 | 1966-10-04 | Merck & Co Inc | 3-(n-acyl-n-methyl)-amino-1-hydrocarbonsulfonoxy propane compounds and method of preparation |
| US3642590A (en) * | 1969-07-16 | 1972-02-15 | Philips Corp | Acid electroplating bath for depositing tin |
| US3787297A (en) * | 1971-10-26 | 1974-01-22 | Conversion Chem Corp | Zinc plating bath and method |
| US4022676A (en) * | 1975-04-09 | 1977-05-10 | Francine Popescu | Alkaline bright zinc electroplating bath |
| US4244791A (en) * | 1979-04-19 | 1981-01-13 | Swiss Aluminium Ltd. | Acidic electrolyte containing SnII ions |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| DE102012004348A1 (de) | 2012-03-07 | 2013-09-12 | Umicore Galvanotechnik Gmbh | Zusatz zur Verbesserung der Schichtdickenverteilung in galvanischen Trommelelektrolyten |
| WO2013131784A1 (de) | 2012-03-07 | 2013-09-12 | Umicore Galvanotechnik Gmbh | Zusatz zur verbesserung der schichtdickenverteilung in galvanischen trommelelektrolyten |
| CN110777402A (zh) * | 2019-11-21 | 2020-02-11 | 武汉奥邦表面技术有限公司 | 一种酸性镀锌载体及其制备方法 |
| CN116041236A (zh) * | 2022-12-30 | 2023-05-02 | 光华科学技术研究院(广东)有限公司 | 二硫代酯类有机物及其制备方法与应用、镀铜液 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1235348A (fr) | 1960-07-08 |
| BE576264A (fr) | 1959-07-01 |
| GB875846A (en) | 1961-08-23 |
| NL238490A (en:Method) | |
| DE1204044B (de) | 1965-10-28 |
| CH405863A (de) | 1966-01-15 |
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