EP0416342B1 - Galvanisches Goldlegierungsbad - Google Patents
Galvanisches Goldlegierungsbad Download PDFInfo
- Publication number
- EP0416342B1 EP0416342B1 EP90115670A EP90115670A EP0416342B1 EP 0416342 B1 EP0416342 B1 EP 0416342B1 EP 90115670 A EP90115670 A EP 90115670A EP 90115670 A EP90115670 A EP 90115670A EP 0416342 B1 EP0416342 B1 EP 0416342B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cyanide
- potassium
- gold
- copper
- silver
- 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
- 239000003353 gold alloy Substances 0.000 title claims abstract description 12
- 229910001020 Au alloy Inorganic materials 0.000 title claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052709 silver Inorganic materials 0.000 claims abstract description 15
- 239000004332 silver Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 6
- VDMJCVUEUHKGOY-JXMROGBWSA-N (1e)-4-fluoro-n-hydroxybenzenecarboximidoyl chloride Chemical compound O\N=C(\Cl)C1=CC=C(F)C=C1 VDMJCVUEUHKGOY-JXMROGBWSA-N 0.000 claims abstract description 5
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 claims abstract description 5
- IVDPWEKOUUEEBD-UHFFFAOYSA-N potassium;copper(1+);dicyanide Chemical compound [K+].[Cu+].N#[C-].N#[C-] IVDPWEKOUUEEBD-UHFFFAOYSA-N 0.000 claims abstract description 5
- OBITVHZFHDIQGH-UHFFFAOYSA-N [Au].[K]C#N Chemical compound [Au].[K]C#N OBITVHZFHDIQGH-UHFFFAOYSA-N 0.000 claims abstract description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 8
- 229940065287 selenium compound Drugs 0.000 claims description 6
- 150000003343 selenium compounds Chemical class 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 239000011669 selenium Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 16
- 229910000960 colored gold Inorganic materials 0.000 abstract description 2
- 150000002825 nitriles Chemical class 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- -1 alkali metal cyanide Chemical class 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 230000008021 deposition Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QOGLYAWBNATGQE-UHFFFAOYSA-N copper;gold;silver Chemical compound [Cu].[Au][Ag] QOGLYAWBNATGQE-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 229910002065 alloy metal Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- KYEKHFSRAXRJBR-UHFFFAOYSA-M potassium;selenocyanate Chemical compound [K+].[Se-]C#N KYEKHFSRAXRJBR-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GSMCZRMXOTVCGF-UHFFFAOYSA-N 2-bromo-1-(5-methyl-1,2-oxazol-3-yl)ethanone Chemical compound CC1=CC(C(=O)CBr)=NO1 GSMCZRMXOTVCGF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- OVKMDTVKFLNYRN-UHFFFAOYSA-N [Cd].[Cu].[Au] Chemical compound [Cd].[Cu].[Au] OVKMDTVKFLNYRN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
Definitions
- the invention relates to a galvanic gold alloy bath containing 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l silver as potassium silver ( I) cyanide, free alkali cyanide, dipotassium hydrogen phosphate, as well as a selenium compound and a pH of 8.5 to 11.
- the galvanic deposition of gold alloys has become particularly important for decorative and technical purposes.
- the soft, cell yellow, matt pure gold layers can be characterized by the deposition of other metals in their properties, e.g. change in gloss, hardness, wear resistance or color in many ways.
- a substantial proportion of the deposited gold alloy coatings have 14 - 18 carat, yellow or rose-colored coatings, which, in addition to copper as an alloy metal to lighten the resulting red color, contain a white-coloring metal such as cadmium, silver or zinc.
- Such coatings are used, for example, in the jewelry and glasses industry, where double layers have been largely replaced by galvanic coatings. Such coatings are also used in electrical engineering when low contact resistance is not required, such as with slip ring and rotary contacts.
- the galvanic deposition of gold / copper / silver alloy coatings causes considerable difficulties due to the potential position of the metals in the electrolyte and has so far only been solved unsatisfactorily.
- the basis for the joint deposition are aqueous solutions of the cyano complexes of the three metals. In the alkaline range, in which these baths are only stable, the potential of silver is much nobler than that of gold and copper, so that silver is preferentially deposited and therefore only coatings, depending on the silver content, are obtained with a whitish-yellow or greenish-yellow color .
- DE-PS 801 312 therefore attempts to shift the potential of the silver to less noble values by using the lowest possible pH.
- DD-PS 59022 also works in neutral and attempts to achieve glossy layers by applying current changes with a low concentration of free alkali metal cyanide, which in practice often leads to coatings with a non-uniform color.
- the gloss formation of the coatings can also be achieved with chemical compounds.
- DE-PS 750 185 the deposition of silver or copper coatings from an alkaline cyanide bath has a shine or tellurium effect.
- JP-A-59 76891 (Chem. Abstr. Vol. 101, No. 12, page 587, 100245f) describes a galvanic gold-silver-copper bath which contains gold, silver and copper as alkali metal cyanides, free cyanide in quantities 10 g / l and hydrogen carbonate, but contains no selenium compounds. Shiny layers can only be obtained if two gold alloy layers of different compositions are deposited one above the other with different current densities and then thermal diffusion of the two layers into one another is carried out at 600 ° C.
- FR-A-22 02 954 discloses a galvanic gold-copper-cadmium bath which calculates the alloy metals as alkali metal cyanides, free alkali metal cyanide and a selenium compound in amounts of 0.1 mg / l up to 5 g / l as selenium Contains brightener. References to galvanic gold-silver-copper baths are not contained in this document.
- the US-A-4,121,982 describes a galvanic gold-silver bath, which acts as a brightener, a combination of 0.1 to 0.5 mg / l selenium compound and 4 to 75 mg / l of a polyethyleneimine per gram of silver or gold content of the bath contains. Again, there is no evidence of galvanic gold-silver-copper baths.
- It was therefore an object of the present invention to develop a galvanic gold alloy bath which contains 1 to 15 g / l gold as potassium gold (I) cyanide, 5 to 50 g / l copper as potassium copper (I) cyanide, 0.05 to 5 g / l of silver as potassium silver (I) cyanide, free alkali metal cyanide dipotassium hydrogen phosphate, and also contains a selenium compound and has a pH value of 8.5 to 11, which is stable and shiny without expensive aids, and depending on the copper content and current density, yellow to supplies rose gold-copper-silver alloy plating.
- This object is achieved in that the content of free alkali cyanide is at most 10 g / l and that it contains 0.1 to 1 mg / l selenium as potassium selenocyanate.
- the bath preferably additionally contains 0.1 to 5 ml / l of a surfactant from the group of nonionic wetting agents of the ethylene oxide adduct type and their phosphate esters.
- a surfactant from the group of nonionic wetting agents of the ethylene oxide adduct type and their phosphate esters.
- alkyl polyglycol ether butyl or nonylphenol polyglycol ether and their phosphate esters can be used.
- the galvanic gold alloy baths according to the invention are preferably composed as follows: 1 - 15 g / l gold as KAu (CN) 2 5 - 50 g / l copper as K2Cu (CN) 3 0.05 - 5 g / l silver as KAg (CN) 2 0.1-10 g / l free alkali cyanide 1 - 10 g / l di-potassium hydrogen phosphate 0.1 - 5 m / l surfactant 0.1 - 1 mg / l selenium as KSeCN
- a phosphate ester such as, for example, nonylphenol polyglycol ether phosphate ester, is suitable as the surfactant which supports the formation of gloss.
- the bath has a pH between 8.5 and 11 and is preferably operated at a bath temperature of 60 - 75 ° C and current densities of 0.2 - 2.5 A / dm2.
- the following bath composition is preferably used for the 14-18 carat yellow or rose-colored gold alloy coatings that are deposited most frequently in practice: 3 - 5 g / l gold as KAu (CN) 2 20 - 25 g / l copper as K2Cu (CN) 3 0.2 - 0.5 g / l silver as KAg (CN) 2 2-4 g / l free alkali cyanide 2-4 g / l di-potassium hydrogen phosphate 0.1-1 ml / l surfactant 0.1 - 0.5 mg / l selenium as KSeCN.
- the bath is preferably operated at a pH of 9-10 and a bath temperature of 60-70 ° C.
- Shiny coatings are obtained in the current density range between 0.3 and 1.5 A / dm2, the carat content of the layers decreasing with increasing current density.
- the deposited layers are very ductile and even low-carat coatings have good corrosion resistance in the copper chloride test.
- the pH is adjusted to 9 with potassium hydroxide.
- the bath is now heated to 65 ° C and a prepared, shiny nickel-plated copper sheet with a surface area of 0.25 dm2 is gold-plated with 2.5 amine at a current density of 0.5 A / dm2.
- the result is a shiny coating with a weak rose color, which has a carat content of 17.2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Cosmetics (AREA)
- Dental Preparations (AREA)
- Laminated Bodies (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Materials For Medical Uses (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3929569A DE3929569C1 (zh) | 1989-09-06 | 1989-09-06 | |
DE3929569 | 1989-09-06 | ||
SG79294A SG79294G (en) | 1989-09-06 | 1994-06-16 | Galvante gold alloy bath. |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0416342A1 EP0416342A1 (de) | 1991-03-13 |
EP0416342B1 true EP0416342B1 (de) | 1994-03-16 |
Family
ID=25884802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90115670A Expired - Lifetime EP0416342B1 (de) | 1989-09-06 | 1990-08-16 | Galvanisches Goldlegierungsbad |
Country Status (13)
Country | Link |
---|---|
US (1) | US5006208A (zh) |
EP (1) | EP0416342B1 (zh) |
JP (1) | JPH03100194A (zh) |
AT (1) | ATE103018T1 (zh) |
BR (1) | BR9004378A (zh) |
DD (1) | DD297668A5 (zh) |
DE (2) | DE3929569C1 (zh) |
DK (1) | DK0416342T3 (zh) |
ES (1) | ES2050317T3 (zh) |
FI (1) | FI93661C (zh) |
HK (1) | HK67794A (zh) |
NO (1) | NO903868L (zh) |
SG (1) | SG79294G (zh) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5256275A (en) * | 1992-04-15 | 1993-10-26 | Learonal, Inc. | Electroplated gold-copper-silver alloys |
DE4317210C2 (de) * | 1993-05-21 | 1998-10-15 | Norbert Muerrle | Halbzeug zur Herstellung von Schmuck und Verfahren zu dessen Bearbeitung |
DE10107675B4 (de) | 2001-02-19 | 2004-11-25 | Implantcast Gmbh | Endoprothese und Verfahren zu ihrer Herstellung |
DE10354760A1 (de) * | 2003-11-21 | 2005-06-23 | Enthone Inc., West Haven | Verfahren zur Abscheidung von Nickel und Chrom(VI)freien metallischen Mattschichten |
US20090104463A1 (en) | 2006-06-02 | 2009-04-23 | Rohm And Haas Electronic Materials Llc | Gold alloy electrolytes |
SG127854A1 (en) * | 2005-06-02 | 2006-12-29 | Rohm & Haas Elect Mat | Improved gold electrolytes |
JP4711227B2 (ja) * | 2005-11-09 | 2011-06-29 | 央 澤栗 | 浴用ガス溶解製造装置 |
CH714243B1 (fr) * | 2006-10-03 | 2019-04-15 | Swatch Group Res & Dev Ltd | Procédé d'électroformage et pièce ou couche obtenue par ce procédé. |
EP3170924A1 (en) | 2007-04-19 | 2017-05-24 | Enthone, Inc. | Electrolyte and method for electrolytic deposition of gold-copper alloys |
CH710184B1 (fr) | 2007-09-21 | 2016-03-31 | Aliprandini Laboratoires G | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux ou métalloïdes toxiques. |
EP2312021B1 (fr) * | 2009-10-15 | 2020-03-18 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
EP2505691B1 (fr) * | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
DE102013109400A1 (de) * | 2013-08-29 | 2015-03-05 | Harting Kgaa | Kontaktelement mit Goldbeschichtung |
CN112663095A (zh) * | 2020-11-10 | 2021-04-16 | 杭州科尔贵金属有限公司 | 一种改进型3d硬金电铸药水配方及制备工艺 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE750185C (de) * | 1939-07-08 | 1944-12-27 | Baeder zur elektrolytischen Abscheidung von glaenzenden Metallniederschlaegen | |
DE801312C (de) * | 1949-05-05 | 1950-11-23 | Pforzheimer Elektrizitäts - Gesellschaft m. b. H., Pforzheim | Verfahren zur elektrolvtischen Abscheidung von Gold und Goldlegierungen |
NL219700A (zh) * | 1956-09-08 | |||
CH418085A (fr) * | 1964-08-19 | 1966-07-31 | Pilot Pen Co Ltd | Electrolyte pour le dépôt galvanique d'alliages d'or |
US3532610A (en) * | 1967-10-27 | 1970-10-06 | Kewanee Oil Co | Selenium compounds as brighteners in copper plating baths |
CH522740A (de) * | 1968-06-28 | 1972-06-30 | Degussa | Verfahren zur galvanischen Abscheidung von Gold-Kupfer-Cadmium-Legierungsüberzügen |
DE2251285C3 (de) * | 1972-10-14 | 1981-01-22 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Alkalisches Bad für die galvanische Abscheidung von Goldlegierungen |
US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
JPS585273B2 (ja) * | 1979-07-24 | 1983-01-29 | 日本電鍍工業株式会社 | 硬質金合金被膜の製造方法 |
CH662583A5 (fr) * | 1985-03-01 | 1987-10-15 | Heinz Emmenegger | Bain galvanique pour le depot electrolytique d'alliages d'or-cuivre-cadmium-zinc. |
-
1989
- 1989-09-06 DE DE3929569A patent/DE3929569C1/de not_active Expired - Lifetime
-
1990
- 1990-08-16 AT AT90115670T patent/ATE103018T1/de not_active IP Right Cessation
- 1990-08-16 EP EP90115670A patent/EP0416342B1/de not_active Expired - Lifetime
- 1990-08-16 DE DE90115670T patent/DE59004996D1/de not_active Expired - Fee Related
- 1990-08-16 ES ES90115670T patent/ES2050317T3/es not_active Expired - Lifetime
- 1990-08-16 DK DK90115670.3T patent/DK0416342T3/da active
- 1990-08-29 US US07/574,359 patent/US5006208A/en not_active Expired - Fee Related
- 1990-09-04 BR BR909004378A patent/BR9004378A/pt not_active Application Discontinuation
- 1990-09-05 DD DD90343836A patent/DD297668A5/de not_active IP Right Cessation
- 1990-09-05 NO NO90903868A patent/NO903868L/no unknown
- 1990-09-05 FI FI904377A patent/FI93661C/fi not_active IP Right Cessation
- 1990-09-06 JP JP2234655A patent/JPH03100194A/ja active Pending
-
1994
- 1994-06-16 SG SG79294A patent/SG79294G/en unknown
- 1994-07-14 HK HK67794A patent/HK67794A/xx unknown
Also Published As
Publication number | Publication date |
---|---|
EP0416342A1 (de) | 1991-03-13 |
US5006208A (en) | 1991-04-09 |
ES2050317T3 (es) | 1994-05-16 |
NO903868L (no) | 1991-03-07 |
JPH03100194A (ja) | 1991-04-25 |
HK67794A (en) | 1994-07-22 |
FI93661B (fi) | 1995-01-31 |
DE59004996D1 (de) | 1994-04-21 |
DK0416342T3 (da) | 1994-04-05 |
FI93661C (fi) | 1995-05-10 |
ATE103018T1 (de) | 1994-04-15 |
FI904377A0 (fi) | 1990-09-05 |
BR9004378A (pt) | 1991-09-03 |
DD297668A5 (de) | 1992-01-16 |
NO903868D0 (no) | 1990-09-05 |
SG79294G (en) | 1994-10-14 |
DE3929569C1 (zh) | 1991-04-18 |
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