EP0343559B2 - 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
- EP0343559B2 EP0343559B2 EP89109164A EP89109164A EP0343559B2 EP 0343559 B2 EP0343559 B2 EP 0343559B2 EP 89109164 A EP89109164 A EP 89109164A EP 89109164 A EP89109164 A EP 89109164A EP 0343559 B2 EP0343559 B2 EP 0343559B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- compounds
- galvanic
- auxiliary agents
- substituted ethane
- pyridinium
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000009713 electroplating Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000001447 alkali salts Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 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
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 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
- 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
- 239000000080 wetting agent Substances 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
- propanesulfone compounds with a pyridinium substituent or a quinoline substituent in the 3-position are known for electroplating purposes as brighteners and levelers in acidic nickel baths (cf. DE-PS 1 004 011).
- 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: 50 g / l Boric acid 70 g / l Nickel chloride .6 H 2 O 330 g / l Nickel sulfate .7 H 2 O 2 g / l Saccharin 0.2 g / l Trial connection 0.02 g / l Leveler (epichlorohydrin-propargyl alcohol adduct) 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.) eine SH-Gruppe
ist,
- 1.) a pyridinium residue
- 2.) an SH group
is
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 - C4Hg) (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 H g ) ( J. Am. Chem. Soc. 76, (1954) page 3945) are known, but not for electroplating purposes.
Andererseits sind Propansulfonverbindungen mit einem Pyridiniumsubstituenten bzw. einem Chinolin-substituenten 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, propanesulfone compounds with a pyridinium substituent or a quinoline substituent in the 3-position are known for electroplating purposes as brighteners and levelers in acidic nickel baths (cf. DE-PS 1 004 011). Surprisingly, 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. 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
- a.) 1- (2-Sulfopropyl) pyridinium betaine and
- b.) 1- (2-Sulfopentyl) pyridinium betaine
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
Hierzu wurden steigende Konzentrationen von Natrium-2-mercapto-propan-1-sulfonat eingesetzt. Es wurde eine Prüf-Zelle von 1,5 l 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 volume 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 electroplated 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/l 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)
- Use of 2-substituted ethane sulphone compounds of the general formula I
[A-CHR3-CH2-SO3 ]- (I)
and the alkali or ammonium salts thereof wherein R3 is a C1 - C4 lower alkyl residue and A is(1) a pyridinium residue
(2) a SH-groupas galvanotechnical adjuvants. - Use of the compounds of formula I wherein A = (1) as brighteners and levelling agents in acid nickel electroplating baths.
- Use of the compounds of formula I with A = (2) as brighteners in acid copper electroplating baths.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3817722 | 1988-05-25 | ||
| DE3817722A DE3817722A1 (en) | 1988-05-25 | 1988-05-25 | USE OF 2-SUBSTITUTED ETHANESULPHONE COMPOUNDS AS GALVANOTECHNICAL AUXILIARIES |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0343559A1 EP0343559A1 (en) | 1989-11-29 |
| EP0343559B1 EP0343559B1 (en) | 1993-03-31 |
| EP0343559B2 true 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 (10)
| 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 |
| WO2020096906A1 (en) | 2018-11-07 | 2020-05-14 | Coventya, Inc. | Satin copper bath and method of depositing a satin copper layer |
| US11408085B2 (en) * | 2019-04-15 | 2022-08-09 | Atotech Deutschland Gmbh | Galvanic nickel or nickel alloy electroplating bath for depositing a semi-bright nickel or semi-bright nickel alloy coating |
| 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 |
|---|---|---|---|---|
| BE534701A (en) * | 1954-03-22 | |||
| 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 ES ES89109164T patent/ES2053865T5/en not_active Expired - Lifetime
- 1989-05-22 DE DE8989109164T patent/DE58903912D1/en not_active Expired - Fee Related
- 1989-05-22 EP EP89109164A patent/EP0343559B2/en not_active Expired - Lifetime
- 1989-05-24 JP JP1129048A patent/JP2505281B2/en not_active Expired - Fee Related
- 1989-05-24 US US07/357,044 patent/US5024736A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0273990A (en) | 1990-03-13 |
| EP0343559B1 (en) | 1993-03-31 |
| DE3817722A1 (en) | 1989-12-14 |
| ES2053865T3 (en) | 1994-08-01 |
| EP0343559A1 (en) | 1989-11-29 |
| JP2505281B2 (en) | 1996-06-05 |
| DE58903912D1 (en) | 1993-05-06 |
| ES2053865T5 (en) | 1996-11-16 |
| US5024736A (en) | 1991-06-18 |
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