EP0297306B1 - Aqueous acid bath for the galvanic deposition of brightening and leveling copper coatings - Google Patents
Aqueous acid bath for the galvanic deposition of brightening and leveling copper coatings Download PDFInfo
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- EP0297306B1 EP0297306B1 EP88108876A EP88108876A EP0297306B1 EP 0297306 B1 EP0297306 B1 EP 0297306B1 EP 88108876 A EP88108876 A EP 88108876A EP 88108876 A EP88108876 A EP 88108876A EP 0297306 B1 EP0297306 B1 EP 0297306B1
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- EP
- European Patent Office
- Prior art keywords
- accordance
- aqueous acid
- acid bath
- bath
- acid
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052802 copper Inorganic materials 0.000 title claims description 20
- 239000010949 copper Substances 0.000 title claims description 20
- 238000000576 coating method Methods 0.000 title claims description 9
- 239000011260 aqueous acid Substances 0.000 title claims 14
- 230000008021 deposition Effects 0.000 title description 6
- 238000005282 brightening Methods 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- -1 benzothiazole compound Chemical class 0.000 claims description 6
- 229920000151 polyglycol Polymers 0.000 claims description 6
- 239000010695 polyglycol Substances 0.000 claims description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000003381 solubilizing effect Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 229920001521 polyalkylene glycol ether Polymers 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims 2
- 150000003557 thiazoles Chemical class 0.000 claims 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 claims 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 239000001768 carboxy methyl cellulose Substances 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- 229940049964 oleate Drugs 0.000 claims 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical class [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 0 CC=CC=C[C@](C(N*)=CC#N)SC Chemical compound CC=CC=C[C@](C(N*)=CC#N)SC 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- AQFXIWDRLHRFIC-UHFFFAOYSA-N 1-[5-phenyl-3-(trifluoromethyl)pyrazol-1-yl]ethanone Chemical compound CC(=O)N1N=C(C(F)(F)F)C=C1C1=CC=CC=C1 AQFXIWDRLHRFIC-UHFFFAOYSA-N 0.000 description 1
- IZGADWSEDZVYHD-UHFFFAOYSA-N 2-(methylamino)benzenethiol Chemical compound CNC1=CC=CC=C1S IZGADWSEDZVYHD-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Definitions
- the invention relates to an acid bath for the electrodeposition of shiny and leveled copper coatings.
- Baths containing polymeric phenazonium compounds made significant progress. They are mainly used in combination with non-ionic wetting agents and organic sulfur compounds.
- the high leveling in the high current density range is disadvantageous in comparison to the low leveling in the low range, which leads to flattening of the edge of the holes in the drill holes when copper-plating printed circuits.
- the different areas in the current density are noticeably noticeable.
- the object of this invention is to avoid these disadvantages and also to improve the leveling and uniform deposition in the region of low current density.
- levelers such as thiourea derivatives or polymeric phenazonium compounds, can improve the leveling in the high range from case to case.
- the amounts in which the benzothiazolium compounds have to be added in order to achieve a significant improvement in the copper deposition are small and are about 0.0005 to 0.3 g / liter, preferably 0.002 to 0.05 g / liter.
- Table 1 contains examples of substances to be used according to the invention and details of the preferred concentrations in the bath.
- the benzothiazolium compounds are known per se or can be prepared, for example, as follows by processes known per se.
- the corresponding benzothiazole derivative is alkylated on nitrogen, this ring is opened with hydrazine hydrate and converted to the desired product with diaalkylaminobenzoyl chloride.
- Table III contains examples of organic nitrogen-free thio compounds with water-soluble groups for additional use as a component and their preferred use concentration:
- the individual components of the copper bath according to the invention can generally advantageously be present in the ready-to-use bath within the following limit concentrations.
- Thiazolium compound preferred 0.0005 - 0.3 g / liter 0.002-0.05 g / liter
- Oxygen-containing, high molecular compounds preferably 0.005 - 20 g / liter 0.01 - 5 g / liter
- Organic thio compounds with water solubilizing groups are preferred 0.0005 - 0.2 g / liter 0.001 - 0.03 g / liter
- the basic composition of the bath according to the invention can vary within wide limits.
- an aqueous solution of the following composition is used: Copper sulfate (CuSO4. 5H20) preferably 20 - 250 g / liter, 60 - 80 g / liter or 180 - 220 g / liter
- CuSO4. 5H20 Copper sulfate
- Sodium chloride preferably 0.02 - 0.25 g / liter, 0.05-0.12 g / liter
- copper sulfate instead of copper sulfate, other copper salts can also be used, at least in part.
- Some or all of the sulfuric acid can be replaced by fluoroboric acid, methanesulfonic acid or other acids.
- the addition of sodium chloride can be omitted in whole or in part if the additives already contain halogen ions.
- the bathroom can also contain customary brighteners, levelers, such as thiourea derivatives or polymeric phenazonium compounds, and / or wetting agents.
- the working conditions of the bath are as follows: PH value: ⁇ 1 Temperature: 15 - 45 ° C, preferably 25 ° C cath. Current density: 0.5 - 12 A / dm2, preferably 2 - 4 A / dm2
- Electrolyte movement takes place by blowing clean air so strongly that the electrolyte surface is in a strong surge.
- Copper with a content of 0.02 to 0.067% phosphorus is used as the anode.
- the Hull cell contains shiny deposits at a current density above 0.8 A / dm2, whereas matt deposits are present at a current density below 0.8 A / dm2.
- an electrolyte temperature of 27 ° C with a current density of 1 A / dm2 and air injection, shiny copper coatings are obtained, the leveling is only 27% with a layer thickness of 3.4 ⁇ m. If 0.01 g / liter of substance 1 (Table I) is added to the bath, the leveling increases to 35% under the same working conditions. So it increases by 30%.
- a printed via circuit is copper-plated for 50 minutes.
- the plate looks greasy and shiny and has very strong defects at the edges of the borehole.
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electroplating Methods And Accessories (AREA)
Description
Die Erfindung betrifft ein saures Bad zur galvanischen Abscheidung glänzender und eingeebneter Kupferüberzüge.The invention relates to an acid bath for the electrodeposition of shiny and leveled copper coatings.
Es ist seit langem bekannt, daß sauren, insbesondere den am meisten verbreiteten, schwefelsauren Kupferelektrolyten bestimmte organische Substanzen in geringen Mengen zugesetzt werden können, um statt einer kristallin-matten Abscheidung glänzende Kupferüberzüge zu erhalten. Für diesen Zweck sind zum Beispiel bekanntgeworden Polyäthylenglycol, Thioharnstoff, Gelatine, Melasse, Kaffee-Extrakt, "basische" Farbstoffe und Thiophosphorsäureester, die jedoch keinerlei praktische Bedeutung mehr besitzen, da die Qualität der mit Ihnen erhaltenen Kupferüberzüge nicht den heutigen Anforderungen entsprechen. So sind die Überzüge entweder zu spröde oder sie besitzen einen zu geringen Glanz beziehungsweise fallen in bestimmten Stromdichtebereichen reliefartig aus.It has long been known that acidic, in particular the most widespread, sulfuric acid copper electrolytes, certain organic substances can be added in small amounts in order to obtain shiny copper coatings instead of a crystalline matt deposition. For this purpose, for example, polyethylene glycol, thiourea, gelatin, molasses, coffee extract, "basic" dyes and thiophosphoric acid esters have become known, but they no longer have any practical significance, since the quality of the copper coatings obtained with them does not meet today's requirements. For example, the coatings are either too brittle or have a low gloss or are relief-like in certain current density ranges.
Gemische verschiedener chemisch unterschiedlicher Inhibitoren mit Thioverbindung verbesserten die Kupferabscheidung:Mixtures of different chemically different inhibitors with thio compound improved the copper deposition:
Vorgeschlagen wurde der Zusatz von Polyaly kliminen in Verbindung mit organischen Thioverbindungen (DE-PS 1246347) und Polyvinylverbindungen in Mischung mit sauerstoffhaltigen hochmolekularen Verbindungen und organischen insbesondere aromatischen Thioverbindungen (DE AS 15 21 062). Derartige Kupferelektrolyte erlauben aber nicht den Einsatz höherer kathodischer Stromdichten, und die abgeschiedenen Kupferüberzüge können außerdem nur nach einer vorausgegangenen Zwischenbehandlung vernickelt werden. In der genannten DE AS 15 21 062 wird außerdem ein saures Kupferbad beschrieben, das neben einer polymeren sauerstoffhaltigen Verbindung mit wasserlöslich machender Gruppe noch mindestens eine substituierte Phenazoniumverbindung gelöst enthält.The addition of polyalcohols in connection with organic thio compounds (DE-PS 1246347) and polyvinyl compounds in a mixture with oxygen-containing high-molecular compounds and organic, in particular aromatic thio compounds (DE AS 15 21 062) was proposed. However, such copper electrolytes do not allow the use of higher cathodic current densities, and the deposited copper coatings can also only be nickel-plated after a previous intermediate treatment. In the aforementioned DE AS 15 21 062 an acidic copper bath is also described which, in addition to a polymeric oxygen-containing compound with a water-solubilizing group, also contains at least one substituted phenazonium compound in solution.
Bei diesen monomeren Phenazoniumverbindungen ist die anwendbare Stromdichte sowie das Alterungsverhalten nicht ausreichend. Weitere Veröffentlichungen verwenden die Kombination von organischen Thioverbindungen und nichtiogenen Netzmitteln mit anderen Farbstoffen wie zum Beispiel Kristall-Violett (Eu-PS 71512), Methylviolett (DE PS 225584), Amiden (US PS 4181582), Phthalocyanin-De1ivaten mit Apo-Safranin (US PS 3420999).With these monomeric phenazonium compounds, the current density that can be used and the aging behavior are not sufficient. Other publications use the combination of organic thio compounds and non-ionic wetting agents with other dyes such as crystal violet (Eu-PS 71512), methyl violet (DE PS 225584), amides (US Pat. No. 4181582), phthalocyanine derivatives with apo-safranin (US PS 3420999).
Anstelle des Farbstoffes wurden auch undefinierte Umsetzungsprodukte von Polyaminen mit Benzylchlorid (US PS 4110176) beziehungsweise Epichlorhydrin (EU PS 68807) oder solche mit Thioverbindungen und Acrylamid (EU PS 107109) vorgeschlagen.Instead of the dye, undefined reaction products of polyamines with benzyl chloride (US PS 4110176) or epichlorohydrin (EU PS 68807) or those with thio compounds and acrylamide (EU PS 107109) have also been proposed.
Sie ergeben alle ungleichmäßige Abscheidungen insbesondere in Kombination mit stickstoffhaltigen Thioverbindungen.They all result in non-uniform deposits, especially in combination with nitrogen-containing thio compounds.
Einen wesentlichen Fortschritt erbrachten Bäder, die polymere Phenazoniumverbindungen (DE PS 2039831) enthielten. Sie finden hauptsächlich in Kombination mit nichtionogenen Netzmitteln und organischen Schwefelverbindungen Anwendung.Baths containing polymeric phenazonium compounds (DE PS 2039831) made significant progress. They are mainly used in combination with non-ionic wetting agents and organic sulfur compounds.
Nachteilig ist die hohe Einebnung im hohen Stromdichtebereich im Vergleich zur geringen Einebnung im niedrigen Bereich, was bei der Verkupferung von gedruckten Schaltungen zu Lochrandabflachungen an den Bohrlöchern führt. In der dekorativen Kupferabscheidung machen sich die unterschiedlichen Bereiche in der Stromdichte unschön bemerkbar.The high leveling in the high current density range is disadvantageous in comparison to the low leveling in the low range, which leads to flattening of the edge of the holes in the drill holes when copper-plating printed circuits. In the decorative copper deposition, the different areas in the current density are noticeably noticeable.
Aufgabe dieser Erfindung ist es, diese Nachteile zu vermeiden und darüber hinaus die Einebnung und gleichmäßige Abscheidung im Bereich niedriger Stromdichte zu verbessern.The object of this invention is to avoid these disadvantages and also to improve the leveling and uniform deposition in the region of low current density.
Diese Aufgabe wird erfindungsgemäß durch ein saures Bad gemäß dem kennzeichnenden Teil des Patentanspruchs gelöst.This object is achieved by an acid bath according to the characterizing part of the patent claim.
Vorteilhafte Weiterentwicklungen sind in den Unteransprüchen aufgeführt.Advantageous further developments are listed in the subclaims.
Zusätzlich können noch Einebner, wie zum Beispiel Thioharnstoffderivate oder polymere Phenazoniumverbindungen von Fall zu Fall die Einebnung im hohen Bereich verbessern.In addition, levelers, such as thiourea derivatives or polymeric phenazonium compounds, can improve the leveling in the high range from case to case.
Die Mengen, in denen die Benzthiazolium-Verbindungen zugegeben werden müssen, um eine deutliche Verbesserung der Kupferabscheidung zu erzielen, sind gering und betragen etwa 0.0005 bis 0.3 g/Liter vorzugsweise 0.002 bis 0.05 g/Liter. Tabelle 1 enthält Beispiele für erfindungsgemäß zu verwendende Substanzen und Angaben über die bevorzugten Konzentrationen im Bad.
Die Benzthiazolium-Verbindungen sind an sich bekannt oder können nach an sich bekannten Verfahren beispielsweise wie folgt hergestellt werden.The benzothiazolium compounds are known per se or can be prepared, for example, as follows by processes known per se.
Zunächst wird das entsprechende Benzthiazolderivat am Stickstoff alkyliert, dieser Ring mit Hydrazin-hydrat geöffnet und mit Diaalkylaminobenzoylchlorid zum gewünschten Produkt umgesetzt.First, the corresponding benzothiazole derivative is alkylated on nitrogen, this ring is opened with hydrazine hydrate and converted to the desired product with diaalkylaminobenzoyl chloride.
In einem 4-l-Drehhalskolben mit KPG-Rührer, Rückflußkühler und Tropftrichter mit Druckausgleich werden 587 g ( 3.20 mol) 4-Dimethylamino-benzoylchlorid in 2,4 l Toluol suspendiert, auf 60° C erwärmt und unter Stickstoff in 30 min mit einer Lösung von 445 g (3,20 mol) N-Methyl-2-mercaptoanilin versetzt. Man rührt 1 h bei Siedetemperatur, läßt abkühlen und saugt das ausgefallene Produkt ab. Nach Waschen mit ca. 2 l Toluol und Trocknen bei 50° C im Vakuum erhält man 940 g (96 % der Theorie) hellgelbes Pulver, das zwischen 180 und 220° C unter Zersetzung schmilzt.587 g (3.20 mol) of 4-dimethylamino-benzoyl chloride are suspended in 2.4 l of toluene in a 4-liter rotary neck flask with KPG stirrer, reflux condenser and dropping funnel with pressure equalization, heated to 60 ° C. and heated under nitrogen in 30 minutes with a Solution of 445 g (3.20 mol) of N-methyl-2-mercaptoaniline was added. The mixture is stirred at boiling temperature for 1 h, allowed to cool and the product which has precipitated is filtered off with suction. After washing with about 2 l of toluene and drying at 50 ° C. in vacuo, 940 g (96% of theory) of light yellow powder are obtained, which melts between 180 and 220 ° C. with decomposition.
Die folgende Tabelle II enthält Beispiele für sauerstoffhaltige, hochmolekulare Verbindungen zur Verwendung als zusätzliche Komponente und deren bevorzugte Anwendungskonzentrationen:
Die folgende Tabelle III enthält Beispiele für organische stickstofffreie Thioverbindungen mit wasserlöslichen Gruppen zur zusätzlichen Verwendung als Komponente und deren bevorzugte Anwendungskonzentration:
Die Einzelkomponenten des erfindungsgemäßen Kupferbades können im allgemeinen vorteilhaft innerhalb folgender Grenzkonzentrationen im anwendungsfertigen Bad enthalten sein.
Die Grundzusammensetzung des erfindungsgemäßen Bades kann in weiten Grenzen schwanken. Im allgemeinen wird eine wässrige Lösung folgender Zusammensetzung benutzt:
Anstelle von Kupfersulfat können zumindest teilweise auch andere Kupfersalze benutzt werden. Auch die Schwefelsäure kann teilweise oder ganz durch Fluoroborsäure, Methansulfonsäure oder andere Säuren ersetzt werden. Die Zugabe von Natriumchlorid kann ganz oder teilweise entfallen, wenn in den Zusätzen bereits Halogenionen enthalten sind.Instead of copper sulfate, other copper salts can also be used, at least in part. Some or all of the sulfuric acid can be replaced by fluoroboric acid, methanesulfonic acid or other acids. The addition of sodium chloride can be omitted in whole or in part if the additives already contain halogen ions.
Außerdem können im Bad auch zusätzlich übliche Glanzbildner, Einebner, wie zum Beispiel Thioharnstoffderivate oder polymere Phenazoniumverbindungen, und/oder Netzmittel enthalten sein.In addition, the bathroom can also contain customary brighteners, levelers, such as thiourea derivatives or polymeric phenazonium compounds, and / or wetting agents.
Zur Herstellung des erfindungsgemäßen Bades werden die Einzelkomponenten der Grundzusammensetzung hinzugefügt.To produce the bath according to the invention, the individual components of the basic composition are added.
Die Arbeitsbedingungen des Bades sind wie folgt:
Elektrolytbewegung erfolgt durch Einblasen von sauberer Luft, so stark, Daß die Elektrolytoberfläche in starker Wallung sich befindet.Electrolyte movement takes place by blowing clean air so strongly that the electrolyte surface is in a strong surge.
Als Anode wird Kupfer mit einem Gehalt von 0.02 bis 0.067 % Phosphor verwendet.Copper with a content of 0.02 to 0.067% phosphorus is used as the anode.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung:The following examples serve to illustrate the invention:
Einem Kupferbad der Zusammensetzung
80 g/Liter Kupfersulfat (CuSo₄.5H₂O)
180 g/Liter Schwefelsäure konz.
0,08 g/Liter Natriumchlorid
werden als Glanzbilder
0,6 g/Liter Polypropylenglycol und
0,02 g/Liter 3-Mercaptopropan-sulfonsäure, Natriumsalz
zugegeben. Bei einer Elektrolyttemperatur von 30° C enthält man in der Hull-Zelle bei einer Stromdichte oberhalb 0,8 A/dm² glänzende Abscheidungen, bei einer Stromdichte unterhalb 0,8 A/dm² dagegen matte Abscheidungen.A copper bath of the composition
80 g / liter copper sulfate (CuSo₄.5H₂O)
180 g / liter sulfuric acid conc.
0.08 g / liter sodium chloride
are used as glossy pictures
0.6 g / liter polypropylene glycol and
0.02 g / liter 3-mercaptopropanesulfonic acid, sodium salt
admitted. At an electrolyte temperature of 30 ° C, the Hull cell contains shiny deposits at a current density above 0.8 A / dm², whereas matt deposits are present at a current density below 0.8 A / dm².
Setzt man dem Bad
0,02 g/Liter Verbindung Nr. 1 oder
0,01 g/Liter Verbindung Nr. 2 oder
0,01 g/Liter Verbindung Nr. 3 oder
0,02 g/Liter Verbindung Nr. 4 oder
0,04 g/Liter Verbindung Nr. 5 oder
0,01 g/Liter Verbindung Nr. 6 oder
0,01 g/Liter Verbindung Nr.7 aus Tabelle I
zu, so ist der gesamte Stromdichtebereich auf dem Hull-Zellen-Prüfblech glänzend.If you put the bathroom
0.02 g / liter of compound No. 1 or
0.01 g / liter of compound No. 2 or
0.01 g / liter of compound No. 3 or
0.02 g / liter of compound No. 4 or
0.04 g / liter of compound No. 5 or
0.01 g / liter of compound No. 6 or
0.01 g / liter of compound No. 7 from Table I
closed, the entire current density range on the Hull cell test plate is shiny.
Einem Kupferbad folgender Zusammensetzung
60 g/Liter Kupfersulfat (CuSO₄.5H₂O)
220 g/Liter Schwefelsäure konz.
0,1 g/Liter Natriumchlorid
werden
1,0 g/Liter βNaphthol -polyglycoläther und
0,01 g/Liter Bis (w-sulfohydroxypropyl)disulfid. Dinatriumsalz zugegeben.A copper bath with the following composition
60 g / liter copper sulfate (CuSO₄.5H₂O)
220 g / liter sulfuric acid conc.
0.1 g / liter sodium chloride
will
1.0 g / liter of β-naphthol polyglycol ether and
0.01 g / liter bis (w-sulfohydroxypropyl) disulfide. Disodium salt added.
Bei einer mittleren Stromdichte von 2 A/dm² wird eine gedruckte, nach der Additivtechnik verkupferte Schaltung 60 Minuten verstärkt. Hierbei zeigen sich um die Bohrlöcher matte abgeflachte Höfe, die nach dem Verzinnen deutliche Risse aufweisen.At an average current density of 2 A / dm², a printed circuit, copper-plated using the additive technology, is amplified for 60 minutes. This shows matte, flattened courtyards around the boreholes, which show marked cracks after tinning.
Setzt man dem Bad außerdem 0,02 g/Liter Verbindung 7 aus Tabelle I zu, so sind die Bohrlöcher auch nach dem Verzinnen einwandfrei.If 0.02 g / liter of compound 7 from Table I is also added to the bath, the boreholes are also perfect after tinning.
Einem Kupferbad der Zusammensetzung
200,0 g/Liter Kupfersulfat (CuSO₄ .5 H₂O)
65,0 g/Liter Schwefelsäure
0,2 g/Liter Natriumchlorid
werden als Glanzbildner 0.2 g/Liter Polyäthylenglycol, 0.01 g/Liter Bis (w-sulfopropyl)-disulfid, Dinatriumsalz, und
0.02 g/Liter polymeres 7-Dimethylamino-5-phenyl-phenazonium-chlorid
zugegeben. Bei einer Elektrolyttemperatur von 27°C erhält man bei einer Stromdichte von 1 A/dm² und Lufteinblasung zwar glänzende Kupferüberzüge, die Einebnung beträgt bei einer Schichtdicke von 3.4 µm nur 27%. Gibt man dem Bad zusätzlich 0.01 g/Liter der Substanz 1 (Tabelle I) zu, so steigt die Einebnung unter gleichen Arbeitsbedingungen auf 35% an. Sie erhöht sich also um 30%.A copper bath of the composition
200.0 g / liter copper sulfate (CuSO₄ .5 H₂O)
65.0 g / liter sulfuric acid
0.2 g / liter sodium chloride
0.2 g / liter of polyethylene glycol, 0.01 g / liter of bis (w-sulfopropyl) disulfide, disodium salt, and
0.02 g / liter polymeric 7-dimethylamino-5-phenylphenazonium chloride
admitted. At an electrolyte temperature of 27 ° C, with a current density of 1 A / dm² and air injection, shiny copper coatings are obtained, the leveling is only 27% with a layer thickness of 3.4 µm. If 0.01 g / liter of substance 1 (Table I) is added to the bath, the leveling increases to 35% under the same working conditions. So it increases by 30%.
Einem Kupferbad folgender Zusammensetzung
80 g/Liter Kupfersulfat (CuSO₄ . 5 H₂O)
200 g/Liter Schwefelsäure, konz.
0,06 g/Liter Natriumchlorid
werden
0,4 g/Liter Oktanolpolyalkylenglykoläther
0,01 g/Liter Di-n-propylthioäther-di-w-sulfonsäure, Dinatriumsalz und
0,01 g/Liter polymeres 7-Dimethylamino-5-phelyl-phenazoniumchlorid zugegeben.A copper bath with the following composition
80 g / liter copper sulfate (CuSO₄. 5 H₂O)
200 g / liter sulfuric acid, conc.
0.06 g / liter sodium chloride
will
0.4 g / liter octanol polyalkylene glycol ether
0.01 g / liter di-n-propylthioether-di-w-sulfonic acid, disodium salt and
0.01 g / liter of polymeric 7-dimethylamino-5-phelyl-phenazonium chloride was added.
Bei einer mittleren Stromdichte von 2,4 A/dm² wird eine gedruckte durchkontaktierte Schaltung 50 Minuten verkupfert. Die Platte sieht speckig glänzend aus und hat sehr starke Fehlstellen an den Bohrlochkanten.With an average current density of 2.4 A / dm², a printed via circuit is copper-plated for 50 minutes. The plate looks greasy and shiny and has very strong defects at the edges of the borehole.
Ersetzt man das polymere Produkt durch 0.01 g/Liter der Verbindung 4 aus Tabelle I, so ist die Schaltung glänzend und hat gute Bohrlochkanten.If you replace the polymer product with 0.01 g / liter of compound 4 from Table I, the circuit is shiny and has good borehole edges.
Claims (14)
- Aqueous acid bath for electrodeposition of brilliant and levelled copper coatings characterized by a content of at least one benzothiazole compound of the general formula
R₁ represents C₁-C₅-alkyl or, as the case may be, a substituted aryl or aralkyl group,R₂ represents hydrogen, a C₁-C₅-alkyl or C₁-C₅-alkoxy group,R₃ and R₄ in each case represent a C₁-C₅-alkyl group, andX represents an acid radical. - Aqueous acid bath in accordance with Claim 1, whereR₁ represents methyl, ethyl, n-propyl, iso-propyl, phenyl or benzyl,R₂ represents hydrogen, methyl, ethyl, n-propyl or isopropyl,R₃ and R₄ in each case represent methyl, ethyl, n-propyl or iso-propyl, andX represents an acid radical.
- Aqueous acid bath in accordance with Claims 1 and 2, where the R₂-group is in the 5 or 6 position.
- Aqueous acid bath in accordance with Claims 1 and 2, where X represents a radical of hydrochloric acid, sulphuric acid, methanesulphonic acid, acetic acid, toluenesulphonic acid or methanesulphuric acid.
- Aqueous acid bath in accordance with Claims 1 to 4, containing said thiazole compounds in concentrations of 0.0005 to 0.3 g/litre, preferably 0.002 to 0.05 g/litre.
- Aqueous acid bath in accordance with Claims 1 to 5, characterized in that it contains at least one additional oxygen-containing high molecular compound.
- Aqueous acid bath in accordance with Claim 6, containing polyvinyl alcohol,
carboxymethyl cellulose,
polyethylene glycol,
polypropylene glycol,
polyglycol stearate,
polyglycol oleate,
stearyl alcohol polyglycol ether,
nonylphenol polyglycol ether,
octanolpolyalkylene glycol ether,
octanediol-bis-(polyalkylene glycol ether),
polyoxypropylene glycol,
polyethylene-propylene glycol, or
β-naphthol polyglycol ether. - Aqueous acid bath in accordance with Claims 6 and 7, containing said oxygen-containing high molecular compounds in concentrations of 0.005 to 20 g/litre, perferably 0.01 to 5 g/litre.
- Aqueous acid bath in accordance with Claims 1 to 5, characterized in that it contains an additional organic nitrogen-free thio compound with water-solubilizing groups.
- Aqueous acid bath in accordance with Claim 9, containing 3-mercaptopropane-1-sulphonic acid, sodium salt,
o-ethyl-bis-(w-sulphopropyl)-thiophosphate, disodium salt,
tris-(w-sulphopropyl)-thiophosphate, trisodium salt,
thioglycolic acid,
ethylene dithiodipropyl sulphonic acid, sodium salt,
di-n-propylthio-ether-di-w-sulphonic acid, disodium salt,
bis(w-sulphopropyl)disulphide, disodium salt,
bis(w-sulphodydroxypropyl)disulphide, disodium salt,
bis(w-sulphobutyl)disulphide, disodium salt,
methyl-(w-sulphopropyl)disulphide, sodium salt, or
methyl-(w-sulphobutyl)trisulphide, sodium salt. - Aqueous acid bath in accordance with Claims 9 and 10, containing said organic nitrogen-free thio compounds with solubilizing groups in concentrations of 0.0005 to 0.2 g/litre, preferably 0.001 to 0.03 g/litre.
- Aqueous acid bath, characterized in that it contains thiazole compounds in accordance with Claims 1 to 5, oxygen-containing high molecular compounds in accordance with Claims 6 to 8 and organic nitrogen-free thio compounds with solubilizing groups in accordance with Claims 9 to 11.
- Aqueous acid bath in accordance with Claim 11, characterized in that said bath has a pH of less than 1.
- Method for the electrodeposition of brilliant and levelled copper coatings, characterized in that the electrolytic copper baths in accordance with Claims 1 to 13 are used at temperatures of 15 to 45 °C and current densities of 0.5 to 12 A/dm².
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873721985 DE3721985A1 (en) | 1987-06-30 | 1987-06-30 | AQUEOUS ACID BATH FOR GALVANIC DEPOSITION OF GLOSSY AND LEVELED COPPER COATINGS |
| DE3721985 | 1987-06-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0297306A1 EP0297306A1 (en) | 1989-01-04 |
| EP0297306B1 true EP0297306B1 (en) | 1993-01-20 |
Family
ID=6330825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88108876A Expired - Lifetime EP0297306B1 (en) | 1987-06-30 | 1988-06-03 | Aqueous acid bath for the galvanic deposition of brightening and leveling copper coatings |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0297306B1 (en) |
| JP (1) | JPH01100292A (en) |
| AT (1) | AT396946B (en) |
| DE (2) | DE3721985A1 (en) |
| ES (1) | ES2045013T3 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5051154A (en) * | 1988-08-23 | 1991-09-24 | Shipley Company Inc. | Additive for acid-copper electroplating baths to increase throwing power |
| JPH04120692A (en) * | 1990-09-11 | 1992-04-21 | Koatsu Gas Kogyo Kk | Sensor testing device |
| DE4032864A1 (en) * | 1990-10-13 | 1992-04-16 | Schering Ag | ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION |
| DE4133299A1 (en) * | 1991-10-08 | 1993-04-15 | Basf Lacke & Farben | CATHODICALLY ADDIBLE ELECTRO DIP VARNISH |
| US5252196A (en) * | 1991-12-05 | 1993-10-12 | Shipley Company Inc. | Copper electroplating solutions and processes |
| DE10000090A1 (en) * | 2000-01-04 | 2001-08-30 | Elfo Ag Sachseln Sachseln | Electrical connecting element production method has embossed substrate provided with selectively etched conductive galvanic coating |
| EP1348320A1 (en) * | 2001-01-04 | 2003-10-01 | Elmicron AG | Method for producing electroconductive structures |
| US6736954B2 (en) * | 2001-10-02 | 2004-05-18 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| US7153408B1 (en) * | 2006-04-13 | 2006-12-26 | Herdman Roderick D | Copper electroplating of printing cylinders |
| EP2568063A1 (en) * | 2011-09-09 | 2013-03-13 | Rohm and Haas Electronic Materials LLC | Low internal stress copper electroplating method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5817272A (en) * | 1981-07-20 | 1983-02-01 | Yamatake Honeywell Co Ltd | Actuator for control valve |
| US4490220A (en) * | 1982-09-30 | 1984-12-25 | Learonal, Inc. | Electrolytic copper plating solutions |
| WO1984001393A1 (en) * | 1982-09-30 | 1984-04-12 | Learonal Inc | Electrolytic copper plating solutions |
-
1987
- 1987-06-30 DE DE19873721985 patent/DE3721985A1/en not_active Withdrawn
-
1988
- 1988-06-03 DE DE8888108876T patent/DE3877633D1/en not_active Expired - Lifetime
- 1988-06-03 ES ES88108876T patent/ES2045013T3/en not_active Expired - Lifetime
- 1988-06-03 EP EP88108876A patent/EP0297306B1/en not_active Expired - Lifetime
- 1988-06-27 AT AT0166488A patent/AT396946B/en not_active IP Right Cessation
- 1988-06-30 JP JP63161089A patent/JPH01100292A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3721985A1 (en) | 1989-01-12 |
| ES2045013T3 (en) | 1994-01-16 |
| ATA166488A (en) | 1993-05-15 |
| AT396946B (en) | 1993-12-27 |
| DE3877633D1 (en) | 1993-03-04 |
| JPH01100292A (en) | 1989-04-18 |
| EP0297306A1 (en) | 1989-01-04 |
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