DE1099300B - Acid galvanic copper baths - Google Patents
Acid galvanic copper bathsInfo
- Publication number
- DE1099300B DE1099300B DED30623A DED0030623A DE1099300B DE 1099300 B DE1099300 B DE 1099300B DE D30623 A DED30623 A DE D30623A DE D0030623 A DED0030623 A DE D0030623A DE 1099300 B DE1099300 B DE 1099300B
- Authority
- DE
- Germany
- Prior art keywords
- content
- baths
- thiourea
- acid
- sulfonic acid
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 20
- 239000010949 copper Substances 0.000 title claims description 20
- 229910052802 copper Inorganic materials 0.000 title claims description 20
- 239000002253 acid Substances 0.000 title claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- -1 sulfuric acid ester Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 1
- 230000008707 rearrangement Effects 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 150000003585 thioureas Chemical class 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 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 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 4
- UWTLARNSDZXILM-UHFFFAOYSA-N 2-(phenylcarbamothioylamino)acetic acid Chemical compound OC(=O)CNC(=S)NC1=CC=CC=C1 UWTLARNSDZXILM-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- ONCNGNKRKZAPSO-UHFFFAOYSA-N 6-(phenylcarbamothioylamino)hexanoic acid Chemical compound OC(=O)CCCCCNC(=S)NC1=CC=CC=C1 ONCNGNKRKZAPSO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- UDOVOKOBUPRTPG-UHFFFAOYSA-N 2-(butylcarbamothioylamino)acetic acid Chemical compound CCCCNC(=S)NCC(O)=O UDOVOKOBUPRTPG-UHFFFAOYSA-N 0.000 description 1
- PICNOIKUSBPBFN-UHFFFAOYSA-N 2-(naphthalen-1-ylcarbamothioylamino)acetic acid Chemical compound OC(=O)CNC(=S)NC1=CC=CC2=CC=CC=C12 PICNOIKUSBPBFN-UHFFFAOYSA-N 0.000 description 1
- YZKFAIKNFGGKER-UHFFFAOYSA-N 4-(phenylcarbamothioylamino)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1NC(=S)NC1=CC=CC=C1 YZKFAIKNFGGKER-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
Die vorliegende Erfindung befaßt sich mit der Erzeugung einebnender Hochglanzkupferniederschläge aus sauren Hochleistungskupferbädern und ist im besonderen auf die Erzielung einer guten Einebnungswirkung über einen sehr weiten Stromdichtebereich gerichtet.The present invention is concerned with the production of leveling, mirror-finish copper deposits from acidic high-performance copper baths and is particularly focused on achieving a good leveling effect directed a very wide current density range.
Es ist bekannt, Thioharnstoffabkömmlinge, die einen oder mehrere Alkyl- oder Arylreste im Molekül enthalten, als Einebnungsmittel in sauren Hochglanzkupferbädern zu verwenden. Als besonders wirksam wurden dabei Alkyl- oder Arylderivate festgestellt, die im Alkyl- und/ oder Arylrest Hydroxyl- und/oder Äthergruppen enthalten. Allerdings zeigt sich die Wirkung der genannten Verbindungen nicht über den ganzen technisch interessanten Stromdichtebereich.It is known that thiourea derivatives that contain one or more alkyl or aryl radicals in the molecule, to be used as a leveling agent in acidic high-gloss copper baths. They were found to be particularly effective Found alkyl or aryl derivatives which contain hydroxyl and / or ether groups in the alkyl and / or aryl radical. However, the effect of the compounds mentioned is not evident over the whole of the technically interesting ones Current density range.
Es wurde nun gefunden, daß man eine beträchtliche ig Verbesserung saurer Hochglanzkupferbäder erzielen kann, wenn man neben üblichen Glanzchemikalien an Stelle der oben bezeichneten Thioharnstoffabkömrnlinge solche Alkyl- und Arylderivate des Thioharnstoff s verwendet, die im Molekül wenigstens eine alkyl- oder arylgebundene ao Carboxylgruppe enthalten. Dabei hat sich gezeigt, daß die carboxylgruppentragenden Alkyl- und Arylreste über ein Stickstoffatom gebunden sein müssen, weil die Verbindungen mit einer Bindung dieser Reste über das Schwefelatom keine Einebnungswirkung ergeben.It has now been found that a considerable ig Improvement of acidic high-gloss copper baths can be achieved if one takes the place of the usual bright chemicals of the thiourea derivatives mentioned above are those Alkyl and aryl derivatives of thiourea s used that contain at least one alkyl or aryl bonded ao in the molecule Contain carboxyl group. It has been shown that the alkyl and aryl radicals bearing carboxyl groups have a nitrogen atom must be bound because the compounds with a bond of these residues via the Sulfur atom do not give a leveling effect.
Die Überlegenheit der carboxylgruppentragenden Thioharnstoffderivate gegenüber anderen Einebnungsmitteln äußert sich besonders in der großen Stromdichtetoleranz der damit eingestellten Bäder, die vor allem auch in den niedrigen Stromdichtebereichen voll wirksam sind. Man erzielt durch gemeinsamen Einsatz dieser Mittel mit bekannten Hochglanzmitteln besonders hochwertige Kupferüberzüge, welche völlig eben sind und über den gesamten Stromdichtebereich Spiegelglanz ergeben.The superiority of the carboxyl group-bearing thiourea derivatives Compared to other leveling agents, this is particularly evident in the large current density tolerance the baths set with it, which are fully effective, especially in the low current density ranges. Man achieves particularly high-quality copper coatings by using these agents together with known high-gloss agents, which are completely flat and give a mirror finish over the entire current density range.
Als Beispiele für geeignete Thioharnstoffabkömmlinge sind die Salze, insbesondere Alkalisalze, nachstehender Carbonsäure zu nennen:Examples of suitable thiourea derivatives are the salts, particularly alkali salts, below To name carboxylic acid:
N-Phenyl-N'-carboxymethyl-thioharnstoff,N-phenyl-N'-carboxymethyl-thiourea,
N-Phenyl-N'-carboxypentyl-thioharnstoff,N-phenyl-N'-carboxypentyl-thiourea,
N-Phenyl-N'-^carboxyphenyl-tMoharnstoff,N-phenyl-N '- ^ carboxyphenyl-t-urea,
N-Phenyl-N'-S-carboxyphenyl-thioharnstoff,N-phenyl-N'-S-carboxyphenyl-thiourea,
N-Phenyl-N'-S^-dicarboxyphenyl-thioharnstoff,N-phenyl-N'-S ^ -dicarboxyphenyl-thiourea,
N-Butyl-N'-'i-carboxyphenyl-thioharnstoff,N-butyl-N '-' i-carboxyphenyl thiourea,
N-Octyl-N'-3,4-dicarboxyphenyl-tMoharnstoff,N-Octyl-N'-3,4-dicarboxyphenyl-t-urea,
N-Butyl-N'-carboxymethyl-thioharnstoff,N-butyl-N'-carboxymethyl-thiourea,
N-a-Naphthyl-N'-carboxymethyl-thioharnstoff.N-α-naphthyl-N'-carboxymethyl thiourea.
4040
4545
Die erfindungsgemäßen Thioharnstoffderivate zeigen vor allem mit solchen Hochglanzmitteln gute Einebnungswirkung, die im Molekül ein oder mehrere Kohlenstoffatome enthalten, welche nur an Heteroatome gebunden sind und über ein Schwefelatom gebunden einen kurzen aliphatischen Rest besitzen, der eine Sulfosäuregruppe oder eine andere wasserlöslichmachende Gruppe trägt, Saure galvanische KupferbäderThe thiourea derivatives according to the invention show a good leveling effect, especially with such high-gloss agents, which contain one or more carbon atoms in the molecule which are only bound to heteroatoms and have a short aliphatic radical bonded via a sulfur atom, which is a sulfonic acid group or another water-solubilizing group carries, acidic galvanic copper baths
Anmelder:Applicant:
DEHYDAGDEHYDAG
Deutsche Hydrierwerke G.m.b.H.,
Düsseldorf, Henkelstr. 67Deutsche Hydrierwerke GmbH,
Düsseldorf, Henkelstr. 67
Dr. Wennemar Strauss, Düsseldorf-Holthausen,Dr. Wennemar Strauss, Düsseldorf-Holthausen,
und Dr. Hans Wedeil, Düsseldorf-Holthausen,and Dr. Hans Wedeil, Düsseldorf-Holthausen,
sind als Erfinder genannt wordenhave been named as inventors
wie z. B. N.N-pentamethylen-dithiocarbaminsäure-n-propylester-cD-sulfosaures Natrium, N, N-dimethyl-dithiocarbaminsäure - η - propylester - ω - sulfosaures Natrium, N^-Diäthylamino-dithiocarbaminsäure-S^S-dihydroxypropylester, N-butyl-dithiocarbaminsäure-N, S-bis-propan- ω -sulfosaures Kalium, dithiocarbaminsäure-S-methylester-N-äthyl-N-butyl-co-sulfosaures Kalium, 1,3,5-triazin-2,4,6-tri-mercapto-2'-hydroxypropansaures Natrium, l^.S-triazm^^o-tri-mercapto-athansulfonsaures Ammonium und andere Hochglanzmittel ähnlicher Konstitution.such as BNN-pentamethylene-dithiocarbamic acid-n-propyl ester-cD-sulfonic acid sodium, N, N-dimethyl-dithiocarbamic acid - η - propyl ester - ω - sulfonic acid sodium, N ^ -diethylamino-dithiocarbamic acid-S ^ S-dihydroxypropyl-acid ester, N-butyl-dithiocarbylic acid -N, S-bis-propane- ω -sulfonic acid potassium, dithiocarbamic acid-S-methyl ester-N-ethyl-N-butyl-co-sulfonic acid potassium, 1,3,5-triazine-2,4,6-tri-mercapto -2'-hydroxypropanoic acid sodium, l ^ .S-triazm ^^ o-tri-mercapto-athansulphonic acid ammonium and other high-gloss agents of similar constitution.
Die gemeinsame Verwendung der erfindungsgemäßen Thioharnstoffderivate mit den oben beschriebenen Hochglanzmitteln kann insbesondere auch bei dem Verfahren zur galvanischen Direktverkupferung erfolgen, bei dem man ohne cyanidische Vorverkupferung auf unedle Metalle, wie z. B. Eisen, festhaftende Kupferüberzüge aufbringt, indem man die zu verkupfernden Metallgegenstände in einem sauren Beizbad unter Zusatz von Sparbeizmitteln hoher Inhibitorwirkung vorbehandelt und anschließend unmittelbar ohne Zwischenspülung in einem sauren Kupferbad galvanisiert.The joint use of the thiourea derivatives according to the invention with the high-gloss agents described above can in particular also take place in the process for galvanic direct copper plating, in which one without cyanidic pre-copper plating on base metals, such as z. B. iron, applies firmly adhering copper coatings, by placing the metal objects to be copper-plated in an acidic pickling bath with the addition of economical pickling agents pretreated with a high inhibitory effect and then immediately without intermediate rinsing in one acidic copper bath galvanized.
Es hat sich ferner als vorteilhaft erwiesen, den Bädern, welche die obigen Mittel enthalten, zur Erhöhung der Duktilität der entstehenden Kupferüberzüge bestimmte organische carboxylgruppenfreie Aminoverbindungen zuzusetzen, wie z. B. 1,3-Propylendiamin, l,3-Bis-(diäthylamino)-propanol-2, N,N,N',N'-Tetrabutyl-l,3-diaminopropanol-2, N,N,N',N'-Tetraäthyl-l,3-diamino-propanol-2 oder auch deren Sulfonsäure- bzw. Schwefelsäureesterabkömmlinge, die eine oder mehrere Sulfonsäuregruppen oder Schwefelsäureestergruppen enthalten. Weiterhin kommen als Mittel zur Erhöhung der Duktilität carboxylgruppenfreie halogenhaltige tertiäre Aminoverbindungen, wie 2-Diäthylamino-3-chlorpropanol-2 oder die aus diesenIt has also proven to be advantageous to use the baths which contain the above agents to increase the Ductility of the resulting copper coatings to add certain organic carboxyl-free amino compounds, such as B. 1,3-propylenediamine, l, 3-bis (diethylamino) -propanol-2, N, N, N ', N'-Tetrabutyl-1,3-diaminopropanol-2, N, N, N', N'-tetraethyl-1,3-diamino-propanol-2 or their sulfonic acid or sulfuric acid ester derivatives, which contain one or more sulfonic acid groups or contain sulfuric acid ester groups. Furthermore, as a means of increasing the ductility there are carboxyl group-free halogen-containing tertiary amino compounds, such as 2-diethylamino-3-chloropropanol-2 or those made from these
109509/510109509/510
gebildeten quatemärenUrnlagerimgsprodukte, welche das Halogen in ionogener Bindung enthalten, in Betracht. Die erfindungsgemäßen Thioharnstoffalkyl- bzw. -arylcarbonsäuren oder deren Salze werden in Mengen von 0,0001 bis 2,5 g/l Badflüssigkeit angewendet. Im übrigen werden die Bäder unter üblichen Konzentrations-, Temperatur- und Stromdichtebedingungen betrieben.formed quaternary stockpiling products, which the Contain halogen in an ionic bond, into consideration. The thiourea alkyl or aryl carboxylic acids according to the invention or their salts are used in amounts of 0.0001 to 2.5 g / l bath liquid. Furthermore the baths are operated under the usual concentration, temperature and current density conditions.
IOIO
1. Versetzt man ein saures Kupferbad, welches 2,0 g/l CuSO4-5 H2O, 60 g/l konzentrierte H2SO4 und als Glanzmittel 0,05 g/lN.N-diäthyl-dithiocarbarninsäureäthylester-ra-sulfosauresNatriumsowieO,25g/lN,N,N',N'-Tetrabutyl-l,3-diaminopropanol-2 und 2,5 g/l des Reaktionsproduktes aus Dodecylalkohol und 8 Mol Äthylenoxyd enthält, mit 0,004 g/l des Natriumsalzes des N-phenyl-N'-carboxymethylthioharnstoffs, so erhält man im Stromdichtebereich von 0,25 bis 8 Amp./dm2 auf unpoliertem Messingblech hochglänzende Kupferüberzüge. Durch diese Galvanisierung werden Unebenheiten von etwa 7 μ Tiefe mit Kupferauflagen von 15 bis 20 μ eingeebnet. Ohne den Zusatz des ITüohaxnstoffabkömmlings fallen die Kupferüberzüge zwar auch hochglänzend aus, besitzen jedoch keine Einebnung.1. An acidic copper bath is added, which contains 2.0 g / l CuSO 4 -5 H 2 O, 60 g / l concentrated H 2 SO 4 and 0.05 g / lN.N-diethyl-dithiocarbarnic acid ethyl ester-ra- sulfonic acid sodium and O, 25g / lN, N, N ', N'-tetrabutyl-l, 3-diaminopropanol-2 and 2.5 g / l of the reaction product of dodecyl alcohol and 8 mol of ethylene oxide, with 0.004 g / l of the sodium salt of the N- phenyl-N'-carboxymethylthiourea, high-gloss copper coatings are obtained on unpolished sheet brass in the current density range from 0.25 to 8 amps / dm 2. This electroplating smoothes any unevenness of about 7 μ in depth with copper layers of 15 to 20 μ. Without the addition of the ceramic substance derivative, the copper coatings are also high-gloss, but do not have any leveling.
2. Saures Kupferbad wie im Beispiel 1, welches an Stelle des dort angewandten Na-Salzes des N-Phenyl-N'-carboxymethyl-thioharnstoffs als Einebnungsmittel 0,007 g/l des Na-Salzes des N-Phenyl-N'-4-carboxyphenyl-thioharnstoffs enthält und einen ähnlichen Glanzeffekt liefert.2. Acidic copper bath as in Example 1, which replaces the Na salt of N-phenyl-N'-carboxymethyl-thiourea used there as leveling agent 0.007 g / l of the Na salt of N-phenyl-N'-4-carboxyphenyl-thiourea contains and provides a similar gloss effect.
3. Saures Kupferbad wie im Beispiel 1, welches 0,003 g/l des Na-Salzes des N-Phenyl-N'-S-carboxyphenylthioharnstoffs als Einebnungsmittel enthält und einen ähnlichen Glanzeffekt liefert.3. Acidic copper bath as in Example 1, which contains 0.003 g / l of the Na salt of N-phenyl-N'-S-carboxyphenylthiourea as a leveling agent and provides a similar gloss effect.
4. Saures Kupferbad wie im Beispiel 1, welches 0,016 g/l des Nä-Salzes des N-Phenyl-N'-carboxypentylthioharnstoffs enthält und einen ähnlichen Glanzeffekt liefert.4. Acidic copper bath as in Example 1, which contains 0.016 g / l of the Na salt of N-phenyl-N'-carboxypentylthiourea contains and provides a similar gloss effect.
Claims (4)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED30623A DE1099300B (en) | 1959-05-06 | 1959-05-06 | Acid galvanic copper baths |
| FR825452A FR1254882A (en) | 1959-05-06 | 1960-04-27 | Electrolytic copper bath |
| FR888291A FR81182E (en) | 1959-05-06 | 1962-02-16 | Electrolytic copper bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED30623A DE1099300B (en) | 1959-05-06 | 1959-05-06 | Acid galvanic copper baths |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1099300B true DE1099300B (en) | 1961-02-09 |
Family
ID=32236315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED30623A Pending DE1099300B (en) | 1959-05-06 | 1959-05-06 | Acid galvanic copper baths |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1099300B (en) |
| FR (1) | FR1254882A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1218247B (en) * | 1960-06-09 | 1966-06-02 | Riedel & Co | Acid galvanic copper bath |
-
1959
- 1959-05-06 DE DED30623A patent/DE1099300B/en active Pending
-
1960
- 1960-04-27 FR FR825452A patent/FR1254882A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1218247B (en) * | 1960-06-09 | 1966-06-02 | Riedel & Co | Acid galvanic copper bath |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1254882A (en) | 1961-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE969005C (en) | Process for the production of high-gloss copper coatings on base metals | |
| DE2845439C2 (en) | Bath for the galvanic deposition of coatings made of tin or tin alloys | |
| DE1207177B (en) | Process for the production of shiny galvanic metal coatings | |
| DE1053274B (en) | Bath for the production of galvanic metal coatings | |
| DE1214069B (en) | Galvanic copper baths | |
| DE1011242B (en) | Galvanic baths for the production of metal coatings | |
| DE1098781B (en) | Bath for the production of high-gloss galvanic metal coatings | |
| DE1007592B (en) | Bath for the production of galvanic metal coatings | |
| DE2517779A1 (en) | METHOD AND BATH FOR ELECTRIC PLATING OF ALUMINUM ALLOYS | |
| DE934508C (en) | Process for the production of galvanic metal coatings | |
| DE3447813C2 (en) | ||
| DE1184172B (en) | Process for the galvanic deposition of firmly adhering and high-gloss copper coatings | |
| DE1004011B (en) | Acid galvanic nickel bath | |
| DE1213697B (en) | Acid cyanide bath, mixture for the production of the bath and process for the galvanic deposition of shiny gold or gold alloy coatings | |
| EP0343559B1 (en) | Use of 2-substituted ethane sulfone compounds as galvanic auxiliary agents | |
| DE1446259B2 (en) | Aqueous, alkaline gold plating bath | |
| DE1099300B (en) | Acid galvanic copper baths | |
| DE1204044B (en) | Shiny galvanic metal baths | |
| DE1142741B (en) | Acid galvanic copper baths | |
| DE1168208B (en) | Galvanic metal baths | |
| DE888191C (en) | Bath and process for galvanic nickel plating | |
| DE3226364C2 (en) | ||
| DE1146322B (en) | Acid galvanic metal baths | |
| DE1016527B (en) | Bath and process for the galvanic production of leveling iron, iron-nickel or iron-nickel-zinc coatings | |
| DE1084098B (en) | Acid baths for the production of galvanic copper coatings |