EP0115020A2 - Bain galvanique acide de zinguage - Google Patents
Bain galvanique acide de zinguage Download PDFInfo
- Publication number
- EP0115020A2 EP0115020A2 EP83112804A EP83112804A EP0115020A2 EP 0115020 A2 EP0115020 A2 EP 0115020A2 EP 83112804 A EP83112804 A EP 83112804A EP 83112804 A EP83112804 A EP 83112804A EP 0115020 A2 EP0115020 A2 EP 0115020A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- zinc
- formula
- hydrogen
- radical
- surfactant
- 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.)
- Granted
Links
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 24
- 239000011701 zinc Substances 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 title description 2
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 5
- 238000004070 electrodeposition Methods 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 heteroaromatic ketones Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 0 *c1cc(*)c(*)c(*)c1 Chemical compound *c1cc(*)c(*)c(*)c1 0.000 description 1
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 238000005282 brightening Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 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 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
Definitions
- the invention relates to an aqueous acidic galvanic zinc bath which, in addition to the usual additives, such as conductive salts and brighteners, contains certain surfactants.
- the electrolytic deposition of zinc on metallic substrates from acidic solution depends on several important criteria. Since the resulting zinc coatings are mostly dull and often irregular from acidic solution, so-called brighteners must be present in the baths in addition to the usual conductive salts (to improve the conductivity of the baths), which give the coatings an increased sheen, and which also allow it to work at lower current densities. These brighteners, which can be assigned to a wide variety of chemical substance classes, are often difficult or impossible to dissolve in water and especially salt solutions, so that certain surfactants have to be added to the baths which serve as emulsifiers, which lead to clear, transparent microemulsions. These measures achieve a uniform deposition of the zinc on the substrates.
- nonionic surfactants have hitherto been used for these purposes, as is known, for example, from GB-PS 1 149 106. Furthermore, from JP-OS 74 89 637 the use of alkyldiphenyloxysulfonic acids is known, the latter of which enable the deposition of relatively uniform zinc layers, but the ductility leaves something to be desired and non-covering coatings result in the low current density range.
- the aim of the invention was to find a class of surfactants which solubilize the brighteners used well and which, from acidic, galvanic zinc baths which contain the usual additives and also water-insoluble brighteners, can be used to obtain uniform and ductile zinc coatings on metallic substrates, even at low current densities.
- the subject of the invention is an aqueous, acidic galvanic bath for the electrolytic deposition of zinc, which contains conductive salts, brightening agents and surfactants, which is characterized by a content of a surfactant of the formula I.
- R 1 is a C 4 - to C 20 -alkyl radical
- R 2 is the radical R 1 or hydrogen
- X and Y is a radical of the formula -S0 3 H
- the hydrogen atom being replaced by an alkali metal, alkaline earth metal atom or an equivalent of zinc can and one of the radicals X and Y can be hydrogen
- n is an integer from 5 to 50
- the compounds of the formula I as a surfactant in aqueous, acidic galvanic baths for the electrolytic deposition of zinc in the presence of brighteners.
- R 1 preferably denotes a C 4 to C 15 alkyl radical. Of particular interest from an industrial point of view are C 4 to C 9 alkyl radicals, of which the butyl, tert-butyl, octyl and nonyl radicals should be mentioned specifically.
- R 2 can have the same meaning as R 1 , preferably R 2 is hydrogen.
- X and Y are preferably the radical -S0 3 H, the hydrogen atom being replaced by sodium or potassium.
- n stands for an integer from 5 to 50, preferably 7 to 30.
- the zinc can be electrolytically used in the bath.
- an alkali metal ion especially the sodium or potassium ion, is preferably chosen as the metal ion.
- the surfactants to be used according to the invention are therefore sulfonated and / or sulfated alkylphenol ethoxylates. They can be used individually or in mixtures with known surfactants. Non-ionic surfactants such as pC 4H9 to C 12 H 25 alkylphenol ethoxylates with 10 to 30 ethylene oxide units or ⁇ -naphthol ethoxylates with 5 to 20 ethylene oxide units are particularly suitable as known surfactants. These are expediently used in an amount of 1 to 15 g / l.
- the zinc baths usually contain brighteners.
- the brighteners used can be divided into so-called basic brighteners and top brighteners.
- Polyethyleneimines or their derivatives, for example, are expedient as basic gloss agents.
- the top brighteners are usually poorly or not at all soluble in the aqueous zinc bath. This includes representatives from a wide variety of substance classes, in particular be voted aromatic or heteroaromatic ketones, as described for example in GB-PS 1 149 106, JP-OS 74 89 637.
- R 3 is an aromatic or heteroaromatic radical, preferably an optionally alkyl, halogen or nitro-substituted phenyl or thienyl radical and R 4 is C 1 - to C 6 -alkyl, or crude products containing these compounds, and / or o- Chlorobenzaldehyde.
- the representative class includes:
- benzal acetone is preferred.
- o-chlorobenzaldehyde can be used alone or as a mixture with a compound of the formula II as a brightener.
- the zinc baths appropriately contain brighteners in a total amount of 1 to 10 g / l. They contain lace gloss agents in an amount of 0.1 to 2.0 g / l, preferably 0.1 to 1 g / l.
- the surfactants to be used according to the invention are present in the baths in an amount of 4 to 30, preferably 5 to 15 g / l.
- the baths have the usual compositions. They contain e.g. 50 to 150 g / 1 zinc chloride or the equivalent amount of zinc sulfate, 100 to 250 g / 1 potassium chloride (conductive salt), 15 to 25 g / l boric acid, 1 to 8 g / 1 sodium benzoate and ggi. 1 to 4 g / 1 agent to increase the scatter, such as naphthalenesulfonic acid / formaldehyde condensation products.
- Other baths can also contain 10 to 160 g / l ammonium chloride or sodium chloride. The pH of the baths is usually between 3 and 6.
- the baths according to the invention provide high-gloss and ductile zinc coatings over the entire current density range.
- the sheets used are run for 10 minutes in a Hull cell with 1 ampere at room temperature (approx. 23 ° C).
- an alkylated diphenyl ether disulfonate (commercially available product) was used as the surfactant.
- the cloud point of the bath at 5 g / 1 and 10 g / l surfactant was above 100 ° C.
- test plate was run in the Hull cell with 1 A at room temperature (approx. 23 ° C.) for 10 minutes.
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)
- Cosmetics (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3248503 | 1982-12-29 | ||
| DE19823248503 DE3248503A1 (de) | 1982-12-29 | 1982-12-29 | Saures galvanisches zinkbad |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0115020A2 true EP0115020A2 (fr) | 1984-08-08 |
| EP0115020A3 EP0115020A3 (en) | 1984-10-03 |
| EP0115020B1 EP0115020B1 (fr) | 1987-04-08 |
Family
ID=6182076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83112804A Expired EP0115020B1 (fr) | 1982-12-29 | 1983-12-20 | Bain galvanique acide de zinguage |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4496439A (fr) |
| EP (1) | EP0115020B1 (fr) |
| DE (2) | DE3248503A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2564487A1 (fr) * | 1984-05-21 | 1985-11-22 | Omi Int Corp | Electrolyte de zinc acide aqueux et procede de depot electrolytique de zinc |
| EP0244685A1 (fr) * | 1986-04-24 | 1987-11-11 | BASF Aktiengesellschaft | Bain acide aqueux galvanique |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3432956A1 (de) * | 1984-09-06 | 1986-03-13 | Schering AG, 1000 Berlin und 4709 Bergkamen | Sulfate und sulfoderivate der ss - naphtholpolyglykolaether und saure zinkbaeder enthaltend diese verbindungen |
| US5616232A (en) * | 1994-09-28 | 1997-04-01 | Nippon Steel Corporation | Process for producing zinc-chromium alloy-electroplated steel plate |
| US6143160A (en) * | 1998-09-18 | 2000-11-07 | Pavco, Inc. | Method for improving the macro throwing power for chloride zinc electroplating baths |
| CN106471161B (zh) | 2014-07-04 | 2020-05-12 | 巴斯夫欧洲公司 | 用于碱性镀锌的添加剂 |
| CN107709627B (zh) | 2015-06-25 | 2020-07-28 | 巴斯夫欧洲公司 | 用于碱性镀锌的添加剂 |
| CN111118555A (zh) * | 2020-01-17 | 2020-05-08 | 浙江金欣新材料科技股份有限公司 | 一种水溶性电镀光亮剂及其制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1521029A1 (de) * | 1966-05-28 | 1969-07-24 | Max Schloetter Fabrik Fuer Gal | Saures galvanisches Glanzzinkbad |
| FR2086320A1 (fr) * | 1970-04-24 | 1971-12-31 | Uemura Kogyo Kk |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1327303A (en) * | 1971-03-23 | 1973-08-22 | Cruickshanks Ltd M T | Acidic zinc electroplating bath |
-
1982
- 1982-12-29 DE DE19823248503 patent/DE3248503A1/de not_active Withdrawn
-
1983
- 1983-12-20 EP EP83112804A patent/EP0115020B1/fr not_active Expired
- 1983-12-20 DE DE8383112804T patent/DE3370835D1/de not_active Expired
- 1983-12-23 US US06/565,217 patent/US4496439A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1521029A1 (de) * | 1966-05-28 | 1969-07-24 | Max Schloetter Fabrik Fuer Gal | Saures galvanisches Glanzzinkbad |
| FR2086320A1 (fr) * | 1970-04-24 | 1971-12-31 | Uemura Kogyo Kk |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2564487A1 (fr) * | 1984-05-21 | 1985-11-22 | Omi Int Corp | Electrolyte de zinc acide aqueux et procede de depot electrolytique de zinc |
| GB2159179A (en) * | 1984-05-21 | 1985-11-27 | Omi Int Corp | Carrier brighteners for acid zinc electrolytes |
| GB2159179B (en) * | 1984-05-21 | 1989-03-30 | Omi Int Corp | Carrier brighteners for acid zinc electrolytes |
| EP0244685A1 (fr) * | 1986-04-24 | 1987-11-11 | BASF Aktiengesellschaft | Bain acide aqueux galvanique |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3370835D1 (en) | 1987-05-14 |
| DE3248503A1 (de) | 1984-07-05 |
| US4496439A (en) | 1985-01-29 |
| EP0115020B1 (fr) | 1987-04-08 |
| EP0115020A3 (en) | 1984-10-03 |
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