EP0343559B1 - Use of 2-substituted ethane sulfone compounds as galvanic auxiliary agents - Google Patents
Use of 2-substituted ethane sulfone compounds as galvanic auxiliary agents Download PDFInfo
- Publication number
- EP0343559B1 EP0343559B1 EP89109164A EP89109164A EP0343559B1 EP 0343559 B1 EP0343559 B1 EP 0343559B1 EP 89109164 A EP89109164 A EP 89109164A EP 89109164 A EP89109164 A EP 89109164A EP 0343559 B1 EP0343559 B1 EP 0343559B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compounds
- galvanic
- residue
- auxiliary agents
- substituted ethane
- 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
- -1 2-substituted ethane sulfone compounds Chemical class 0.000 title description 3
- 239000012752 auxiliary agent Substances 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- BMPBPPRKJPBLKR-UHFFFAOYSA-N CC(C[N+]1=CC=CC=C1)S([O-])(=O)=O Chemical compound CC(C[N+]1=CC=CC=C1)S([O-])(=O)=O BMPBPPRKJPBLKR-UHFFFAOYSA-N 0.000 description 1
- HIIAZTSDAJUCDC-UHFFFAOYSA-N CCCC(C[N+]1=CC=CC=C1)S([O-])(=O)=O Chemical compound CCCC(C[N+]1=CC=CC=C1)S([O-])(=O)=O HIIAZTSDAJUCDC-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- PVYOEOXGRHEUNY-UHFFFAOYSA-M sodium;2-sulfanylpropane-1-sulfonate Chemical compound [Na+].CC(S)CS([O-])(=O)=O PVYOEOXGRHEUNY-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- GINSRDSEEGBTJO-UHFFFAOYSA-N thietane 1-oxide Chemical class O=S1CCC1 GINSRDSEEGBTJO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
- 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
Definitions
- propane sulfone compounds with a pyridinium substituent or a quinoline substituent in the 3-position are known as electroplating agents and brighteners in acidic nickel baths (cf. DE-PS 1 004 011).
- the 2-substituted ethanesulfone compounds used according to the invention with an alkyl chain branching at the C2 show good gloss formation and leveling, in particular of nickel and copper coatings, although the steric hindrance leads to poor results. In this way, numerous substance variants allow adaptation and optimization to different galvanic requirements.
- the pyridine and quinoline derivatives of the 2-substituted ethanesulfone betaines in particular are particularly good brighteners and levelers in acidic nickel baths, while the mercapto derivatives are suitable as brighteners in acidic copper baths.
- a galvanic nickel bath was set up as follows: distilled water to 1 liter, pH 4.0 adjusted with sulfuric acid.
- the sheets After the nickel plating, the sheets showed a uniform surface, good gloss and leveling.
- the storage stability of the prepared additional solution at 60 ° C was good.
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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
Description
Die Erfindung betrifft die Verwendung von 2-substituierten Ethansulfonverbindungen der allgemeinen Formel I
- 1.) ein Pyridinium-Rest
- 2.) ein Mercaptorest -S-R4 ist, in dem R4 Wasserstoff oder die Gruppe
als galvanotechnische Hilfsstoffe.The invention relates to the use of 2-substituted ethanesulfone compounds of the general formula I.
- 1.) a pyridinium residue
- 2.) is a mercapto residue -SR 4 , in which R 4 is hydrogen or the group
as galvanotechnical auxiliaries.
Einige dieser Verbindungen, nämlich solche der Formel I mit A-Pyridinium und R3 = CH3 (Can. J. Chem. 1984, 62 (19), Seiten 1977-95) und R3 = n - C4 Hg) (J. Am. Chem. Soc. 76, (1954) Seite 3945) sind zwar bekannt, aber nicht für galvanotechnische Zwecke.Some of these compounds, namely those of the formula I with A-pyridinium and R 3 = CH 3 (Can. J. Chem. 1984, 62 (19), pages 1977-95) and R 3 = n - C 4 Hg) (J Chem. Soc. 76, (1954) page 3945) are known, but not for electroplating purposes.
Andererseits sind Propansulfonverbindungen mit einem Pyridiniumsubstituenten bzw. einem Chinolinsubstituenten in 3-Stellung für galvanotechnische Zwecke als Glanzbildner und Einebner in sauren Nickelbädern bekannt (vgl. DE-PS 1 004 011). Überraschenderweise zeigen erfindungsgemäß verwendete 2- substituierte Ethansulfonverbindungen mit einer Alkylkettenverzweigung am C2 gute Glanzbildung und Einebnung insbesondere von Nickel- und Kupferüberzügen, obwohl die sterische Hinderung schlechte Ergebnisse erwarten läßt. Auf diese Weise ist durch zahlreiche Substanzvarianten Anpassung und Optimierung an verschiedene galvanische Forderungen möglich.On the other hand, propane sulfone compounds with a pyridinium substituent or a quinoline substituent in the 3-position are known as electroplating agents and brighteners in acidic nickel baths (cf. DE-PS 1 004 011). Surprisingly, the 2-substituted ethanesulfone compounds used according to the invention with an alkyl chain branching at the C2 show good gloss formation and leveling, in particular of nickel and copper coatings, although the steric hindrance leads to poor results. In this way, numerous substance variants allow adaptation and optimization to different galvanic requirements.
Die Herstellung solcher erfindungsgemäß verwendeter Verbindungen erfolgt durch gleichzeitiges Umsetzen von Verbindungen AH oder A mit einem Olefin R3-CH = CH2 mit Schwefeltrioxid in einem inerten Lösungsmittel bzw. Lösungsmittelgemisch oder durch Sulfonieren des Olefins im Gemisch mit Dioxan in einem Fallfilmreaktor und Umsetzen des erhaltenen 1,2-Sulfons mit der Verbindung AH oder A.Such compounds used according to the invention are prepared by simultaneously reacting compounds AH or A with an olefin R 3 -CH = CH 2 with sulfur trioxide in an inert solvent or solvent mixture or by sulfonating the olefin in a mixture with dioxane in a falling film reactor and reacting the resultant 1,2-sulfones with the compound AH or A.
Beide Verfahrensweisen sind Gegenstand älterer nicht vorveröffentlichter Schutzrechte.Both procedures are the subject of older, unpublished property rights.
Wie gefunden wurde, sind insbesondere die Pyridin- und Chinolinderivate der 2-substituierten Ethansulfonbetaine besonders gute Glanzbildner und Einebner in sauren Nickelbädern, während die Mercaptoderivate als Glanzbildner in sauren Kupferbädern geeignet sind.As was found, the pyridine and quinoline derivatives of the 2-substituted ethanesulfone betaines in particular are particularly good brighteners and levelers in acidic nickel baths, while the mercapto derivatives are suitable as brighteners in acidic copper baths.
Die Erfindung wird durch folgende Beispiele erläutert:The invention is illustrated by the following examples:
Es wurde ein galvanisches Nickelbad wie folgt angesetzt:
Es wurde jeweils 10 min. bei 2 A/dm2 und 60°C ein Messingblech in einer Hull-Zelle vernickelt. Das Blech war vorher in alkalischer Lösung und nach dem Waschen mit Wasser bei 2,5 A 2 min. kathodisch entfettet worden. Anschließend wurden die Bleche mit Wasser gespült und 30 sec. in einen Beizentfetter getaucht und danach mit Zellstoff abgerieben und nochmals mit Wasser gespült. Die Bewegung des Bades geschah durch Lufteinperlen.It was 10 min each. at 2 A / dm 2 and 60 ° C nickel-plated brass sheet in a Hull cell. The sheet was previously in alkaline solution and after washing with water at 2.5 A for 2 min. have been degreased cathodically. The sheets were then rinsed with water and immersed in a pickling degreaser for 30 seconds and then rubbed with cellulose and rinsed again with water. The movement of the bath was done by bubbling in air.
Es wurden als Versuchsverbindungen zum Beispiel
- a.) 1-(2-Sulfopropyl)-pyridiniumbetain und
- b.) 1-(2-Sulfopentyl)-pyridiniumbetain
eingesetzt.There were test compounds for example
- a.) 1- (2-Sulfopropyl) pyridinium betaine and
- b.) 1- (2-Sulfopentyl) pyridinium betaine
used.
Die Bleche zeigten nach der Vernickelung eine einheitliche Fläche, guten Glanz und Einebnung. Die Lagerstabilität der angesetzten Zusatzlösung bei 60 ° C war gut.After the nickel plating, the sheets showed a uniform surface, good gloss and leveling. The storage stability of the prepared additional solution at 60 ° C was good.
Es wurde ein Bad aus
verwendet.It became a bath
used.
Hierzu wurden steigende Konzentrationen von Natrium-2-mercapto-propan-1-sulfonat eingesetzt. Es wurde eine Prüf-Zelle von 1,5 I Badinhalt verwendet. Die Versuchskupferbleche waren matt und gewinkelt. Sie wurden mit 0,8 m/min senkrecht zur Anode bewegt (3 cm Hub). Es wurde mit einer kathodischen Stromdichte von 3 A/dm2 30 min bei 25 ° C galvanisch verkupfert. Die Kathode bestand aus gewinkeltem Kupferblech.Rising concentrations of sodium 2-mercapto-propane-1-sulfonate were used for this. A test cell with a bath content of 1.5 l was used. The test copper sheets were matt and angled. They were moved perpendicular to the anode at 0.8 m / min (3 cm stroke). It was galvanically copper-plated with a cathodic current density of 3 A / dm 2 for 30 min at 25 ° C. The cathode was made of angled copper sheet.
Bei einer Konzentration von 0,2 bis 0,4 mg/I ergab die Verbindung einen sehr guten Glanz.At a concentration of 0.2 to 0.4 mg / l, the compound gave a very good gloss.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3817722A DE3817722A1 (en) | 1988-05-25 | 1988-05-25 | USE OF 2-SUBSTITUTED ETHANESULPHONE COMPOUNDS AS GALVANOTECHNICAL AUXILIARIES |
| DE3817722 | 1988-05-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0343559A1 EP0343559A1 (en) | 1989-11-29 |
| EP0343559B1 true EP0343559B1 (en) | 1993-03-31 |
| EP0343559B2 EP0343559B2 (en) | 1996-07-10 |
Family
ID=6355072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89109164A Expired - Lifetime EP0343559B2 (en) | 1988-05-25 | 1989-05-22 | Use of 2-substituted ethane sulfone compounds as galvanic auxiliary agents |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5024736A (en) |
| EP (1) | EP0343559B2 (en) |
| JP (1) | JP2505281B2 (en) |
| DE (2) | DE3817722A1 (en) |
| ES (1) | ES2053865T5 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2242200B (en) * | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| DE4013349A1 (en) * | 1990-04-23 | 1991-10-24 | Schering Ag | 1- (2-SULFOAETHYL) PYRIDINIUMBETAIN, METHOD FOR THE PRODUCTION THEREOF AND ACID NICKEL BATH CONTAINING THIS COMPOUND |
| US5523861A (en) | 1991-05-15 | 1996-06-04 | Canon Kabushiki Kaisha | Image reader capable of setting density and illumination |
| US6605204B1 (en) * | 1999-10-14 | 2003-08-12 | Atofina Chemicals, Inc. | Electroplating of copper from alkanesulfonate electrolytes |
| US6776893B1 (en) * | 2000-11-20 | 2004-08-17 | Enthone Inc. | Electroplating chemistry for the CU filling of submicron features of VLSI/ULSI interconnect |
| EP2801640A1 (en) * | 2013-05-08 | 2014-11-12 | ATOTECH Deutschland GmbH | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or nickel alloy |
| DE102014207778B3 (en) * | 2014-04-25 | 2015-05-21 | Kiesow Dr. Brinkmann GmbH & Co. KG | Use of a mixture for use in a plating bath or plating bath to produce a bright nickel plating, and to a method of making an article having a bright nickel plating |
| KR20210094558A (en) | 2018-11-07 | 2021-07-29 | 코벤트야 인크. | Satin Copper Bath and Satin Copper Layer Deposition Method |
| DE102020212830B4 (en) | 2020-10-12 | 2022-08-18 | Sms Group Gmbh | Adjustment system for adjusting the guide play of a slide for moving parts of a press and method for adjusting the position of at least one sliding block of a slide on a press |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1075398B (en) * | 1954-03-22 | 1960-02-11 | DEHYDAG Deutsche Hydrierwerke G.m.b.H., Düsseldorf | Bath for the galvanic production of metal coatings |
| BE545564A (en) * | 1955-03-16 | |||
| DE1092744B (en) * | 1958-12-17 | 1960-11-10 | Dehydag Gmbh | Acid galvanic nickel bath |
| DE1238032B (en) * | 1962-07-21 | 1967-04-06 | Dehydag Gmbh | Process for the preparation of sulfobetaines containing oxy groups |
| DE1205973B (en) * | 1963-02-02 | 1965-12-02 | Dehydag Gmbh | Process for the preparation of thiosulfobetaines containing oxy groups |
| DE1191652B (en) * | 1963-05-15 | 1965-04-22 | Dehydag Gmbh | Acid galvanic nickel bath |
| US3328273A (en) * | 1966-08-15 | 1967-06-27 | Udylite Corp | Electro-deposition of copper from acidic baths |
| DE2803493A1 (en) * | 1978-01-27 | 1979-08-02 | Agfa Gevaert Ag | PROCESS FOR THE MANUFACTURING OF SULFOALKYL QUARTER SALTS |
| FI70304C (en) * | 1980-02-27 | 1986-09-15 | Kee Klamps Ltd | ROERANSLUTNING |
| US4526968A (en) * | 1981-08-24 | 1985-07-02 | M&T Chemicals Inc. | Quaternary aminehydroxypropane sulfobetaines |
| US4555315A (en) * | 1984-05-29 | 1985-11-26 | Omi International Corporation | High speed copper electroplating process and bath therefor |
| DE3541098A1 (en) * | 1985-11-21 | 1987-05-27 | Agfa Gevaert Ag | SULFOALKYLATION PROCESS |
-
1988
- 1988-05-25 DE DE3817722A patent/DE3817722A1/en not_active Withdrawn
-
1989
- 1989-05-22 EP EP89109164A patent/EP0343559B2/en not_active Expired - Lifetime
- 1989-05-22 DE DE8989109164T patent/DE58903912D1/en not_active Expired - Fee Related
- 1989-05-22 ES ES89109164T patent/ES2053865T5/en not_active Expired - Lifetime
- 1989-05-24 US US07/357,044 patent/US5024736A/en not_active Expired - Lifetime
- 1989-05-24 JP JP1129048A patent/JP2505281B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2505281B2 (en) | 1996-06-05 |
| ES2053865T5 (en) | 1996-11-16 |
| US5024736A (en) | 1991-06-18 |
| JPH0273990A (en) | 1990-03-13 |
| DE3817722A1 (en) | 1989-12-14 |
| EP0343559B2 (en) | 1996-07-10 |
| DE58903912D1 (en) | 1993-05-06 |
| EP0343559A1 (en) | 1989-11-29 |
| ES2053865T3 (en) | 1994-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2255584C2 (en) | Acid copper plating bath | |
| DE2152785C2 (en) | Aqueous acid electroplating bath for the deposition of tin, lead and alloys thereof | |
| DE2541897C2 (en) | Aqueous acid bath for the galvanic deposition of ductile and shiny copper coatings | |
| DE1207177B (en) | Process for the production of shiny galvanic metal coatings | |
| DE2706521A1 (en) | PROCESS FOR THE PRODUCTION OF FLAT COPPER COATINGS AND SUITABLE ACID PLATING BATH | |
| EP2103717B1 (en) | Pyrophosphate-based bath for depositing tin alloy layers | |
| DE1521062B2 (en) | AQUATIC ACID GALVANIC COPPER BATH FOR DEPOSITING DUCTILE GLAZING COPPER | |
| DE1007592B (en) | Bath for the production of galvanic metal coatings | |
| EP0343559B1 (en) | Use of 2-substituted ethane sulfone compounds as galvanic auxiliary agents | |
| DE1001078B (en) | Galvanic baths for the production of metal coatings | |
| DE1184172B (en) | Process for the galvanic deposition of firmly adhering and high-gloss copper coatings | |
| DE2319197C3 (en) | Aqueous bath and process for the galvanic deposition of a ductile, firmly adhering zinc coating | |
| DE2630980C2 (en) | ||
| DE2459428C2 (en) | Process for the production of a brightener for acidic galvanic tin baths and its use | |
| DE3722778A1 (en) | POLYALKYLENE GLYCOL NAPHTHYL-3-SULPHOPROPYL DIETHERS AND THEIR SALTS, PROCESS FOR PREPARING THESE COMPOUNDS AND THEIR USE AS A NETWORK IN GALVANO TECHNOLOGY | |
| DE1952218A1 (en) | Process and means for electroplating | |
| DE1208593B (en) | Acid galvanic nickel bath for the deposition of semi-glossy coatings | |
| DE2815786A1 (en) | AQUATIC BATH FOR EDECTROCHEMICAL DEPOSITION OF GLOSSY IRON-NICKEL COATING | |
| DE1956144A1 (en) | Process and bath for galvanic tinning | |
| DE3139641A1 (en) | "GALVANIC BATH AND METHOD FOR SEPARATING SEMI-GLOSSY DUCTILERS AND TENSION-FREE NICKEL COATINGS" | |
| DE2948999C2 (en) | Aqueous, acidic bath for the electrodeposition of gold and method for the electrodeposition of hard gold with its use | |
| DE1233690B (en) | Galvanic nickel bath | |
| DE1228886C2 (en) | Acid galvanic bath | |
| DE1496817B1 (en) | Galvanic nickel bath | |
| DE1039809B (en) | Bath and process for the galvanic deposition of shiny antimony coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE |
|
| 17P | Request for examination filed |
Effective date: 19900518 |
|
| 17Q | First examination report despatched |
Effective date: 19920518 |
|
| RBV | Designated contracting states (corrected) |
Designated state(s): BE CH DE ES FR GB IT LI NL SE |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IT LI NL SE |
|
| ITF | It: translation for a ep patent filed | ||
| REF | Corresponds to: |
Ref document number: 58903912 Country of ref document: DE Date of ref document: 19930506 |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19930429 |
|
| ET | Fr: translation filed | ||
| PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
| 26 | Opposition filed |
Opponent name: BASF AKTIENGESELLSCHAFT, PATENTE, MARKEN UND LIZEN Effective date: 19931227 |
|
| NLR1 | Nl: opposition has been filed with the epo |
Opponent name: BASF AKTIENGESELLSCHAFT, PATENTE, MARKEN UND LIZEN |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2053865 Country of ref document: ES Kind code of ref document: T5 |
|
| EAL | Se: european patent in force in sweden |
Ref document number: 89109164.7 |
|
| PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
| PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
| 27A | Patent maintained in amended form |
Effective date: 19960710 |
|
| AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): BE CH DE ES FR GB IT LI NL SE |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN Free format text: AUFRECHTERHALTUNG DES PATENTES IN GEAENDERTER FORM |
|
| GBTA | Gb: translation of amended ep patent filed (gb section 77(6)(b)/1977) |
Effective date: 19960731 |
|
| NLR2 | Nl: decision of opposition | ||
| ITF | It: translation for a ep patent filed | ||
| NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Kind code of ref document: T5 Effective date: 19961008 |
|
| ET3 | Fr: translation filed ** decision concerning opposition |
Free format text: CORRECTIONS |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20040510 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20040518 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20040519 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20040524 Year of fee payment: 16 Ref country code: ES Payment date: 20040524 Year of fee payment: 16 Ref country code: CH Payment date: 20040524 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20040525 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20040527 Year of fee payment: 16 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050522 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050522 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050523 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050523 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050531 |
|
| BERE | Be: lapsed |
Owner name: *RASCHIG A.G. Effective date: 20050531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051201 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051201 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| EUG | Se: european patent has lapsed | ||
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20050522 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060131 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20051201 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20060131 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20050523 |
|
| BERE | Be: lapsed |
Owner name: *RASCHIG A.G. Effective date: 20050531 |
|
| PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |