EP0311971A1 - Bain aqueux, acide, galvanique - Google Patents
Bain aqueux, acide, galvanique Download PDFInfo
- Publication number
- EP0311971A1 EP0311971A1 EP88116840A EP88116840A EP0311971A1 EP 0311971 A1 EP0311971 A1 EP 0311971A1 EP 88116840 A EP88116840 A EP 88116840A EP 88116840 A EP88116840 A EP 88116840A EP 0311971 A1 EP0311971 A1 EP 0311971A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- bath
- naphthaldehyde
- baths
- aqueous
- 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.)
- Withdrawn
Links
- 239000011260 aqueous acid Substances 0.000 title abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 230000002378 acidificating effect Effects 0.000 claims description 13
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 6
- 239000004299 sodium benzoate Substances 0.000 claims description 6
- 235000010234 sodium benzoate Nutrition 0.000 claims description 6
- 238000000151 deposition Methods 0.000 abstract description 9
- 238000009713 electroplating Methods 0.000 abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 5
- 229930008407 benzylideneacetone Natural products 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- -1 heteroaromatic ketones Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- YIQGLTKAOHRZOL-UHFFFAOYSA-N 2-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=CC2=C(C=O)C(OC)=CC=C21 YIQGLTKAOHRZOL-UHFFFAOYSA-N 0.000 description 2
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- MVXMNHYVCLMLDD-UHFFFAOYSA-N 4-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(OC)=CC=C(C=O)C2=C1 MVXMNHYVCLMLDD-UHFFFAOYSA-N 0.000 description 1
- XNBPIZTUCVHIFW-UHFFFAOYSA-N CC(=O)C=CC1=CC=CC=C1.CC(=O)C=CC1=CC=CC=C1 Chemical compound CC(=O)C=CC1=CC=CC=C1.CC(=O)C=CC1=CC=CC=C1 XNBPIZTUCVHIFW-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 208000003251 Pruritus Diseases 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 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
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004532 chromating Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007803 itching Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000002815 nickel Chemical class 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
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- 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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Definitions
- the galvanic baths contain certain auxiliaries, because otherwise the zinc coatings resulting from the acidic solution are usually dull and often also irregular.
- auxiliaries for acidic galvanic baths are, for example, conductive salts which are used to improve the conductivity of the baths, e.g. Potassium chloride, ammonium chloride and sodium chloride.
- gloss agents are divided into basic gloss agents and top gloss agents.
- the basic brightener includes, for example, polyethyleneimine and derivatives thereof, and nonionic and anionic surfactants.
- top gloss formers must also be used in acidic electroplating baths. Since these products are often not sufficiently soluble in the bathroom, they must be solubilized using the tensides.
- Aqueous, acidic, galvanic baths are known for the electrolytic deposition of zinc on metals, which contain conductive salts, brighteners and surfactants, cf. GB-PS 1 149 106, US-PS 3 787 296 and EP-PS 0 115 020.
- Top gloss formers are, for example, benzaldehyde derivatives, such as 2-chlorobenzaldehyde or 4-methoxybenzaldehyde, or aromatic or heteroaromatic ketones.
- the main representative of this group of aids is benzylidene acetone (benzal acetone).
- benzylidene acetone benzal acetone
- a serious disadvantage of benzylidene acetone and its homologues is the fact that these compounds cause allergic reactions such as reddening of the skin and itching in many people who handle it.
- the present invention is based on the object of replacing high-gloss gloss agents based on benzylidene acetone or its derivatives in aqueous, acidic, galvanic baths for the deposition of zinc or zinc alloys by other substances which achieve the effectiveness of the known high-gloss gloss agents but not too bad Impairment of people who handle these substances.
- the aqueous, acidic, galvanic baths have the usual compositions. They contain, for example, 50 to 150 g / l zinc chloride or the equivalent amount of zinc sulfate. If alloys of zinc with cobalt and / or nickel are to be deposited on metallic substrates, the baths additionally contain 1 to 30 g / l of cobalt and / or nickel sulfate or another water-soluble cobalt or nickel salt. Another essential component of the baths are conductive salts.
- a suitable conductive salt is potassium chloride, which is contained in the aqueous, acidic, galvanic bath in amounts of 100 to 250 g / l.
- Other conductive salts are, for example, ammonium chloride or sodium chloride, which are usually used in amounts of 10 to 150 g / l.
- nonionic and anionic surfactants Another essential component of the aqueous, acidic, galvanic baths are nonionic and anionic surfactants, polyethyleneimine and derivatives of polyethyleneimine as well as sodium benzoate.
- Suitable nonionic surfactants are known for example from GB-PS 1 149 106. These are addition products of ethylene oxide with fatty alcohols, for example C8-C18 alcohols or addition products of ethylene oxide with phenol or alkylphenols, especially nonylphenyl. 5 to 100 moles of ethylene oxide are added per mole of alcohol or phenol.
- Suitable anionic surfactants are known, for example, from the above-mentioned US Pat. No. 3,787,296. These are mainly sulfated polyethers, which are obtainable, for example, by adding ethylene oxide to fatty alcohols, fatty amines, amides of C6-C10 carboxylic acids and longer-chain fatty acids and subsequent sulfonation. Sulfonates of polyalkylene oxides or block copolymers of ethylene oxide and propylene oxide are also used as anionic surfactants. Another group of anionic surfactants is known from EP-PS 0 115 020.
- those sulfonated and sulfated products whose polyether chain contains 1 to 25 propylene oxide or butylene oxide units are also suitable as anionic surfactants.
- the advantage of the sulfonated and sulfated alkylphenol alkoxylates is that they have an extremely high cloud point, so that the electrolytic deposition of the zinc not only in the otherwise usual temperature range of 20 to 30 ° C but also at temperatures above 50 ° C, e.g. can be done at 70 ° C.
- the non-ionic and anionic surfactants act as a basic luster and are at the same time a solubilizing agent for compounds that are sparingly soluble in water.
- the surfactants in question and phenol-formaldehyde condensation products or naphthalenesulfonic acid / formaldehyde condensation products are used in amounts of 5 to 20, preferably 8 to 15 g / l in the aqueous, galvanic bath.
- Sodium benzoate can also be used as auxiliary brightener in amounts of 1 to 8, preferably 2 to 5 g / l.
- the pH of the aqueous, acidic, galvanic baths is usually between 4 and 5. It is added to the bath by adding acids, e.g. Sulfuric acid or hydrochloric acid.
- the substituents R1 and R2 in formula I can have either the same or different meanings.
- Compounds of the formula I are, for example, 1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2-naphthaldehyde, 2-methoxy-1-naphthaldehyde and 4-methoxy-1-naphthaldehyde.
- the use of 2-hydroxy-1-naphthaldehyde in amounts of 0.2 to 0.7 g / l is particularly preferred.
- metals mainly iron and steel
- the baths according to the invention provide high-gloss and ductile zinc coatings over the entire range of current density that is technically possible, which correspond in quality to the coatings that are obtainable using benzylidene acetone according to the prior art. It is, of course, possible to use mixtures of compounds of the formula I as lace gloss formers and to use the lace gloss formulas according to formula I together with other known base and lace gloss formulations which do not cause any health problems in the persons who handle these substances.
- composition of bath 1 Zinc chloride 100 g / l Potassium chloride 200 g / l Boric acid 20 g / l commercial naphthalenesulfonic acid / formaldehyde condensation product 2 g / l Sodium benzoate 2 g / l
- Top gloss agent according to the table
- Composition of bath 2 Zinc chloride 100 g / l Ammonium chloride 140 g / l Sodium benzoate 6 g / l commercial nonylphenol polyethylene glycol ether (20 ethylene glycol units) 5 g
- the pH of bath 1 is 4.8, that of bath 2 4.5.
- the pH is adjusted with dilute hydrochloric acid.
- the galvanizing of steel sheets takes 10 minutes each. It is carried out in a 250 ml Hull cell with 1 ampere at approx. 23 ° C. After the galvanizing, blue chromating is carried out.
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)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873735055 DE3735055A1 (de) | 1987-10-16 | 1987-10-16 | Waessriges, saures, galvanisches bad |
| DE3735055 | 1987-10-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0311971A1 true EP0311971A1 (fr) | 1989-04-19 |
Family
ID=6338456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88116840A Withdrawn EP0311971A1 (fr) | 1987-10-16 | 1988-10-11 | Bain aqueux, acide, galvanique |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0311971A1 (fr) |
| JP (1) | JPH01136986A (fr) |
| DE (1) | DE3735055A1 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0492790A3 (en) * | 1990-12-20 | 1992-09-30 | Macdermid Incorporated | Electroplating composition and process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4137133A (en) * | 1977-12-15 | 1979-01-30 | M&T Chemicals Inc. | Acid zinc electroplating process and composition |
| FR2417556A1 (fr) * | 1978-02-17 | 1979-09-14 | Popescu Francine | Nouveaux brillanteurs pour zingage electrolytique acide |
| US4251331A (en) * | 1980-01-17 | 1981-02-17 | Columbia Chemical Corporation | Baths and additives for the electroplating of bright zinc |
-
1987
- 1987-10-16 DE DE19873735055 patent/DE3735055A1/de not_active Withdrawn
-
1988
- 1988-10-11 EP EP88116840A patent/EP0311971A1/fr not_active Withdrawn
- 1988-10-14 JP JP63257423A patent/JPH01136986A/ja active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4137133A (en) * | 1977-12-15 | 1979-01-30 | M&T Chemicals Inc. | Acid zinc electroplating process and composition |
| FR2417556A1 (fr) * | 1978-02-17 | 1979-09-14 | Popescu Francine | Nouveaux brillanteurs pour zingage electrolytique acide |
| US4251331A (en) * | 1980-01-17 | 1981-02-17 | Columbia Chemical Corporation | Baths and additives for the electroplating of bright zinc |
| US4251331B1 (fr) * | 1980-01-17 | 1993-02-09 | Columbia Chem Corp |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0492790A3 (en) * | 1990-12-20 | 1992-09-30 | Macdermid Incorporated | Electroplating composition and process |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3735055A1 (de) | 1989-04-27 |
| JPH01136986A (ja) | 1989-05-30 |
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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): BE CH DE ES FR GB IT LI NL SE |
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| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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| 18W | Application withdrawn |
Withdrawal date: 19890505 |