WO2007045650A2 - Bain aqueux, alcalin et exempt de cyanure pour le dépôt galvanique de revêtements en zinc et en alliages de zinc - Google Patents

Bain aqueux, alcalin et exempt de cyanure pour le dépôt galvanique de revêtements en zinc et en alliages de zinc Download PDF

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WO2007045650A2
WO2007045650A2 PCT/EP2006/067495 EP2006067495W WO2007045650A2 WO 2007045650 A2 WO2007045650 A2 WO 2007045650A2 EP 2006067495 W EP2006067495 W EP 2006067495W WO 2007045650 A2 WO2007045650 A2 WO 2007045650A2
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zinc
aqueous
cyanide
alkaline
free
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PCT/EP2006/067495
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German (de)
English (en)
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WO2007045650A3 (fr
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Thomas Heidenfelder
Jessica Neumann
Helmut Witteler
Lidcay Herrera Taboada
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Basf Se
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    • 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 present invention relates to an aqueous, alkaline, cyanide-free bath containing specific cationic polycondensation products, a process for the electrodeposition of zinc or zinc alloy coatings, and the use of the specific cationic polycondensation product or the aqueous, alkaline, cyanide-free bath for the electrodeposition of zinc or zinc alloy coatings.
  • US Pat. No. 5,405,523 describes aqueous, alkaline, cyanide-free baths which contain polymers prepared from urea and mono (N, N-dialkylaminoalkyl) amines.
  • the polymers described in DE-C 198 40 019, which are likewise used in an aqueous, alkaline, cyanide-free bath, are obtained by reacting N, N'-bis [3- (dialkylamino) alkyl] ureas with dihaloalkane.
  • Cationic polycondensation products which are prepared by condensation of i) noncyclic amines or ii) mixtures of noncyclic amines and cyclic amines with bifunctional compounds such as halomethyloxiranes and bisepoxides are already known from the German application with the application no. 10 2005 013 780.6 known.
  • the cationic polycondensation products described in this application are used as color-fixing and / or dye-transfer-inhibiting additives for detergents and laundry aftertreatment agents.
  • a use of these cationic polycondensation products in aqueous, alkaline, cyanide-free baths is not disclosed.
  • aqueous, alkaline, cyanide-free baths previously used for galvanic deposition of zinc or zinc alloy coatings can not satisfactorily solve the problem of uneven layer thickness distribution, it is an object of the present invention to provide further aqueous, alkaline, cyanide-free baths for electrodeposition.
  • this object is achieved by containing an aqueous, alkaline cyanide-free bath
  • A1a Mono (N, N-dialkylaminoalkyl) amine (A1a) with a bifunctional compound (A1b) selected from the group consisting of urea, thiourea, dialkyl carbonates, aliphatic and aromatic dicarboxylic acids and aliphatic and aromatic diisocyanates, in the molar ratio (A1a) to ( A1b) from 1.2: 1 to 2.1: 1,
  • At least one bifunctional compound (B) selected from the group of halomethyloxiranes and bisepoxides and, if at least one cyclic amine (A3) is condensed, of the alkylene dihalides and dihalogenoalkyl ethers in a molar ratio (B) to (A1) or (B) (A2) from 0.6: 1 to 1.3: 1.
  • aqueous, alkaline, cyanide-free baths according to the invention are particularly advantageous since they bring about both an improved layer thickness distribution and an improved gloss effect compared with the baths known from the prior art, which contain, for example, the commercial product Mirapol WT.
  • the aqueous, alkaline, cyanide-free baths of the present invention comprise as component (I) at least one zinc ion source and as component (II) at least one cationic polycondensation ons.
  • the baths of the invention may contain other components.
  • the baths according to the invention are prepared by methods known to the person skilled in the art, for example by mixing the individual components with water.
  • the alkaline pH of the baths according to the invention is adjusted by adding a hydroxide ion source.
  • hydroxide ion source for adjusting the pH sodium hydroxide (NaOH) or potassium hydroxide (KOH), preferably NaOH, are usually used.
  • the concentration of NaOH is usually 80 to 250 g / l.
  • the pH can also be adjusted by other alkali or alkaline earth metal hydroxides and mixtures thereof or with other substances known to the person skilled in the art.
  • the pH in the baths according to the invention is 9 to 13.
  • substances such as sodium carbonate (Na 2 CO 3 ) may also be added to the baths according to the invention.
  • the baths according to the invention contain the usual zinc ion sources, such as, for example, zinc metal, zinc salts and zinc oxide, but preference is given to zinc oxide, which is present in zinc solution as an alkaline solution.
  • zinc ion sources such as, for example, zinc metal, zinc salts and zinc oxide, but preference is given to zinc oxide, which is present in zinc solution as an alkaline solution.
  • the concentration of zinc in the baths according to the invention is in the range customary for such baths from 0.2 to 20 g / l, preferably 5 to 20 g / l. - A -
  • the baths contain a source of other metal ions.
  • other metal ions are preferably cobalt, nickel, manganese and / or iron ions into consideration.
  • sources of these additional metal ions salts of the corresponding metals, preferably of the above-described metals, if appropriate also in a mixture, are used.
  • Suitable salts are nickel sulfate, iron sulfate, cobalt sulfate and manganese chloride.
  • the concentration of the metal ions in the baths according to the invention can vary within a wide range and is preferably 0.01 to 100 g / l. Since different alloying types are required for different alloy types, for example to improve corrosion protection, this concentration varies from metal ion to metal ion.
  • the baths contain zinc in an amount of 0.2 to 20 g / l, cobalt in an amount of 10 to 120 mg / l, nickel in an amount of 0.3 to 3 g / l, manganese in an amount of 10 to 100 g / l and iron in an amount of 10 to 120 mg / l. These concentrations are based on the amount of metal ions contained in the bath. Corresponding conversions provide the amounts of the respective salts of these metals to be used.
  • baths according to the invention contain the abovementioned additional metal ions, then it is expedient to add to the baths complexing agents which are also matched to these additional metal ions, in order to control the deposition potentials and to enable joint reduction with the zinc ions present.
  • chelating agents are preferred.
  • suitable chelating agents are hydroxycarboxylates such as sodium gluconate, amino alcohols such as triethanolamine, polyamines such as polyethylenediamine, aminocarboxylates such as EDTA, aminophosphonates such as amino-tris (methylenephosphonic acid) and polyhydric alcohols such as sorbitol or sucrose.
  • the chelating agent can be contained individually or in admixture in the baths according to the invention, the amount of which is preferably in the range from 2 to 200 g / l.
  • the aqueous alkaline cyanide-free bath according to the invention contains, as component (II), at least one cationic polycondensation product obtainable by condensation of:
  • bifunctional compound (B) selected from the group of halomethyloxiranes and bisepoxides, wherein the molar ratio of (B) to (A1) of
  • bifunctional compound (B) selected from the group of the alkylene dihalides, dihaloalkyl ethers, halomethyloxiranes and bisepoxides in a molar ratio (B) to (A2) of 0.6: 1 to 1.3: 1.
  • Suitable mono (N, N-dialkylaminoalkyl) amines (A1a) which are used for the preparation of the noncyclic amine (A1) are in principle all known to those skilled mono (N, N-dialkylaminoalkyl) amines, wherein the individual alkyl fragments of these compounds, if appropriate can carry further substituents.
  • R 1 , R 2 are independently C 1 -C 6 -alkyl, preferably C 1 -C 4 -alkyl, which may be substituted by hydroxy; n 2 to 6.
  • dialkylaminoalkylamines of the formula (I) which carry the same alkyl radicals on the nitrogen atom.
  • dimethylaminoalkylamines especially dimethylaminopropylamine, are again particularly preferred.
  • bifunctional compound (A1 b) As the bifunctional compound (A1 b), urea, thiourea, dialkyl carbonates, dicarboxylic acids or diisocyanates are used.
  • Suitable dialkyl carbonates (A1b) have, in particular, C 1 -C 3 -alkyl radicals, dimethyl carbonate and diethyl carbonate being mentioned as preferred examples.
  • the dicarboxylic acids (A1b) may be aliphatic saturated or unsaturated or aromatic dicarboxylic acids and in particular have 2 to 10 carbon atoms.
  • dicarboxylic acids examples include: oxalic, malonic, succinic, tartaric, maleic, itaconic, glutaric, adipic, suberic, sebacic, phthalic and terephthalic acids.
  • the dicarboxylic acids (A1b) can be used in the form of the free acids or as carboxylic acid derivatives, such as anhydrides, esters, in particular di (C 1 -C 2 -alkyl) esters, amides and acid halides, in particular acid chlorides.
  • suitable acid derivatives include: maleic anhydride, succinic anhydride, itaconic anhydride and phthalic anhydride; Dimethyl adipate, diethyl adipate and dimethyl tartrate; Adipic acid diamide, adipic acid monoamide and glutaric acid diamide; Adipic acid.
  • the free acid or its anhydrides are used.
  • Particularly preferred dicarboxylic acids (A1b) are succinic acid, glutaric acid, adipic acid and maleic acid.
  • aliphatic and cyclic aliphatic and aromatic diisocyanates are also suitable as diisocyanates (A1b).
  • the hydrocarbon radicals of the diisocyanates (A1b) have in particular from 4 to 12 carbon atoms.
  • diisocyanates examples include: tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,3,3-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,2 Bis (4-isocyanatocyclohexyl) propane, 1, 4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate (TDI) and their isomer mixtures, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), o- and m-xylylenediisocyanate (XDI), 1,5-naphthylene diisocyanate, tetramethylxylylene diisocyanate (TMX
  • mixtures of different diisocyanates can be used.
  • bifunctional compound (A1b) As the bifunctional compound (A1b), urea, succinic acid, adipic acid, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred. Very particular preference is as a bifunctional compound (A1 b) urea.
  • the molar ratio of dialkylaminoalkylamine (A1a) to bifunctional compound (A1b) is 1, 2: 1 to 2.1: 1, preferably 1, 5: 1 to 2.1: 1.
  • reaction products are formed which, when urea is used as components (A1b), have a free urea end group and have a regulating effect on the molecular weight of the cationic polycondensation products.
  • the molecular weight can be controlled by suitable choice of this molar ratio.
  • noncyclic amines (A1) containing urea or dicarboxylic acids as a bifunctional component (A1b) can be carried out, for example, by reacting the components (A1a) and (A1b) in bulk at 120 to 180 ° C, in which case the dicarboxylic acids to remove the resulting reaction water is.
  • Noncyclic amines (A1) which are based on diisocyanates as component (A1b) can be prepared, for example, by initially introducing the bifunctional component (A1b) in an organic solvent, for example a carboxylic acid ester, such as ethyl acetate, at ⁇ 5 ° C and the amine (A1a) is added dropwise.
  • an organic solvent for example a carboxylic acid ester, such as ethyl acetate
  • mixtures (A2) of at least one noncyclic amine (A1) with at least one cyclic amine (A3) for the preparation of the cationic polycondensation products.
  • the cyclic amines (A3) can be both aromatic and aliphatic. Normally, a cyclic amine (A3) is used, but if desired, mixtures of two or more different cyclic amines (A3) can also be used.
  • the mixture (A2) preferably contains one cyclic and one noncyclic amine.
  • Particularly suitable cyclic amines (A3) are imidazole and its alkyl derivatives, piperazine and its alkyl derivatives, pyrazine and pyrimidine.
  • alkyl derivatives should also be understood as meaning derivatives whose alkyl substituents are functionalized, for example, by amino or hydroxyl groups.
  • piperazine and imino dazolderivate are such as 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole and 1- (3-aminopropyl) imidazole; 2,4-di (Ci-C 2 5-alkyl) imidazoles, especially 2,4-di (Ci-C 6 alkyl) imidazoles, such as 2-ethyl-4-methylimidazole; 1- (2 S- CrC alkyl) piperazines, especially 1- (CrC 6 alkyl) piperazine, such as 1-methylpiperazine; 1,4-di (C 1 -C 5 -alkyl) piperazines, especially 1,4-di (C 1 -C 6 -alkyl) piperazines, such as 1, 4-dimethylpiperaz
  • Preferred cyclic amines (A3) are unsubstituted imidazole and with dC 6 alkyl in the 1-, 2- or 4-position at least monosubstituted imidazole, with unsubstituted imidazole being particularly preferred.
  • the mixtures (A2) have a molar ratio of noncyclic amine (A1) to cyclic amine (A3) of 10: 1 to 1:10, preferably from 7: 1 to 1: 7, particularly preferably from 4: 1 to 1: 4 and most preferably from 4: 1 to 1: 2.
  • the cationic polycondensation products to be used in the aqueous, alkaline, cyanide-free bath according to the invention are obtainable by condensation of the noncyclic amine (A1) or the mixtures (A2) of noncyclic amine (A1) and cyclic amine (A3) with at least one bifunctional compound (B) , Preferably, a bifunctional compound (B) is used.
  • AIs bifunctional compounds (B) Halomethyloxirane or bisepoxides or mixtures of these compounds are used. If the reaction is carried out in the presence of at least one cyclic amine (A3), bifunctional compound (B) can also be alkylene dihalides or dihaloalkyl ethers.
  • alkylenedihalides (B) are the .omega.,. Omega .'-dichlorides, dibromides and diiodides of unbranched alkanes having 2 to 8 carbon atoms, the bromides being preferred and the chlorides being particularly preferred.
  • alkylene dihalides (B) are, for example: 1,2-dichloroethane, 1,2-dibromoethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane and 1,6-dichlorohexane, where 1, 2-dichloroethane, 1, 4-dichlorobutane and 1, 6-dichlorohexane are preferred.
  • dihaloalkyl ethers are di ( ⁇ , ⁇ '-halogeno-C 2 -C 6 -alkyl) ethers and ( ⁇ -halogeno-C 2 -C 6 -alkoxy-C 2 -C 6 -alkyl) ( ⁇ -halogeno-C 2 -C 6 -alkyl) ether, where halogen may in turn denote chlorine, bromine or iodine, bromine being preferred and chlorine being particularly preferred.
  • Examples include di (2-chloroethyl) ether and (2-chloro-ethoxyethyl) (2-chloroethyl) ether.
  • Suitable halomethyloxiranes (B) preferably have 3 to 7 carbon atoms, and here too the chlorine compounds are preferred. Particularly preferred halomethyloxirane (B) is epichlorohydrin.
  • Suitable bisepoxides (B) are, in particular, bisepoxialkanes having 4 to 7 carbon atoms and bisepoxides based on oligomeric and polymeric alkylene glycols, in particular C 2 -C 3 -alkylene glycols, such as oligo- and polyethylene glycol bis-epoxides, oligo- and polypropyleneglycol bisepoxides and bisepoxides of EO / PO copolymers.
  • Preferred bisepoxides (B) are bisepoxibutane and oligo- and polyethylene glycol bis-epoxides.
  • Preferred bifunctional compound (B) are haloethyloxiranes and bisepoxides, especially halomethyloxiranes. Particularly preferred as the bifunctional compound (B) is epichlorohydrin.
  • the molar ratio of bifunctional compound (B) to amine component (A1) or (A2) is 0.6: 1 to 1.3: 1, preferably 0.8: 1 to 1.1: 1.
  • the choice of the molar ratio of (B) to (A1) or (A2) represents a further possibility to specifically control the molecular weight of the cationic polycondensation products.
  • the condensation reaction can also be carried out as usual for such reactions.
  • the polycondensation of (B) with (A1) or (A2) in aqueous solution at 80 to 120 ° C. has proven to be particularly advantageous.
  • cationic polycondensation products prepared by condensing a noncyclic amine (A1) with a bifunctional compound (B) selected from halomethyloxirane and bisepoxide, preferably epichlorohydrin.
  • the cationic polycondensation product contains the fragment of the formula (II)
  • n 1 to 80.
  • cationic polycondensation products which are prepared by condensation from a mixture of a noncyclic amine which is prepared by reacting N, N-dimethylaminopropylamine and urea, and imidazole with epichlorohydrin.
  • the cationic polycondensation products which still contain tertiary amino groups can additionally be reacted with alkylating agents, for example dimethyl sulfate, C 1 -C 22 -alkyl halides or benzyl chloride, by means of which the tertiary amino groups are quaternized.
  • alkylating agents for example dimethyl sulfate, C 1 -C 22 -alkyl halides or benzyl chloride
  • reaction with the alkylating agent can be carried out directly in the reaction mixture obtained in the condensation by generally known methods.
  • the average molecular weight M w of the cationic polycondensation products can be 500 to 1,000,000. Preference is given to average molecular weights M w of from 1000 to 100,000 and more preferably from 1500 to 50,000.
  • the cationic polycondensates are water-soluble or readily dispersible in water.
  • the polymer of the formula (I) is contained in the bath of the invention in an amount of 0.01 to 50 g / l, preferably 0.05 to 10 g / l.
  • the baths according to the invention optionally contain one or more of the other components listed below.
  • the bath contains as further additive a quaternary derivative of a pyridine-3-carboxylic acid of the formula (III) and / or a quaternary derivative of a pyridine-3-carboxylic acid of the formula (IV),
  • R 6 is a saturated or unsaturated, aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 12 carbon atoms.
  • a quaternary derivative of the formula (III) is used, in particular Benzylpyrimidiniumcarboxylat, which is available under the trade name Lugalvan BPC 48.
  • the amount of this additional additive in the bath according to the invention is 0.005 to 0.5 g / l, preferably 0.01 to 0.2 g / l.
  • the quaternary derivatives of a pyridine-3-carboxylic acid of the formula (IM) or (IV) used as further additives in the bath according to the invention are compounds known per se and are described, for example, in B.S. James, M. Phil Thesis, Aston Univ. 1979 and DE 40 38 721 described.
  • the preparation of these derivatives is generally carried out by reaction of nicotinic acid with aliphatic, aromatic or araliphatic hydrogen halides.
  • the novel baths can contain further polymers, for example the polymers mentioned in the abovementioned publications (DE 198 40 019 C, US Pat. No. 5,435,898 and US Pat. No. 5,405,523).
  • the cyano-free zinc baths according to the invention correspond to the customary aqueous alkaline cyanide-free baths, as used to deposit zinc or zinc alloy coatings on various substrates. Standard baths of this type are described for example in DE 25 25 264 and US 3,884,774.
  • the baths according to the invention may contain known planarizers such as 3-mercapto-1, 2,4-triazole and / or thiourea, with thiourea being preferred.
  • concentration of the leveler is the usual concentration of zinc baths and is for example 0.01 to 0.50 g / l.
  • Further additives for the baths according to the invention are aromatic aldehydes or bisulfite adducts thereof.
  • Preferred aromatic aldehydes are selected from the group consisting of 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), 3,4-dimethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 2-hydroxybenzaldehyde and 4-hydroxybenzaldehyde or mixtures thereof.
  • These additives whose concentration is in the range from 0.005 to 1.0 g / l, preferably from 0.01 to 0.50 g / l, act as brighteners in a manner known per se.
  • a particularly preferred example of such a brightener is vanillin.
  • bath according to the invention as brightener, other substances, such as substances selected from the group of sulfur compounds, aldehydes, ketones, amines, polyvinyl alcohol, polyvinylpyrrolidone, proteins or reaction products of halohydrins with aliphatic or aromatic amines, polyamines or heterocyclic nitrogen compounds and mixtures thereof, contain.
  • the baths according to the invention may also contain water-softening agents, since the addition of such additives reduces the sensitivity of the bath according to the invention to foreign metal ions, in particular calcium and magnesium, from tap water.
  • water-softening agents are EDTA, sodium silicates and tartaric acid.
  • the baths according to the invention it is possible to provide (conventional) objects, for example conductive metal substrates, with a coating of zinc or a zinc alloy by the method known to the person skilled in the art (galvanic deposition of zinc coatings or zinc alloy coatings). Accordingly, the present invention further relates to the use of the above-described aqueous, alkaline, cyanide-free baths and the component (II) as such for the deposition of zinc or zinc alloy coatings and to a process for the electrodeposition of zinc or zinc alloy coatings.
  • the method according to the invention for the electrodeposition of zinc coatings or of zinc alloy coatings comprises the positioning of an object to which the zinc or zinc alloy coating is to be deposited in one of the abovementioned baths according to the invention, wherein a current is applied in the bath according to the invention.
  • the electrodeposition processes and the articles to be coated are known to those skilled in the art.
  • the deposition of the coatings at a current density in the range of 0.01 to 10 A / dm 2 and / or at a temperature in the range of 15 to 45 ° C.
  • the inventive method can be carried out when used for bulk parts, for example as Trommelgalvanisiermaschine and for deposition on larger workpieces as Gestellgalvanisiermaschine.
  • Anodes are used which can be soluble, such as zinc anodes, which also serve as the zinc ion source, to recover the zinc deposited on the cathode by dissolving zinc at the anode.
  • insoluble anodes such as, for example, iron anodes, with those being the electrolyte withdrawn zinc ions must be added again in other ways, for example using a zinc dissolving container.
  • the method according to the invention can also be operated with air injection with goods movement or without movement, without resulting in any disadvantages for the coatings obtained.
  • a mixture of 916.6 g (9.0 mol) of N, N-dimethylaminopropylamine (compound (AIa)) and 300.5 g (5.0 mol) of urea (compound (AIb)) is first introduced in a nitrogen inlet under 35 ° C heated to 122 ° C and then in 4 h to 155 ° C and then stirred for a further 12 h at this temperature.
  • the amine (A1) (precursor 1) is obtained in the form of a yellowish, clear liquid.
  • the layer thickness measurement is carried out with the X-ray fluorescence spectrometer.
  • 3 cm from the lower edge and 2.5 cm from the right and left lateral edges at 2 points are measured at high (3.0 A / dm 2 ) and low current density (0.6 A / dm 2 ).
  • the layer thickness distribution results from the ratio of the measured values for the layer thickness at high (HJ) and low current density (LJ).
  • the visual assessment of the sheets is done visually.
  • Electrolyte B
  • Table 2 Layer thickness distribution and visual assessment
  • the use of the baths according to the invention results in an improved coating thickness distribution of the coating on the metal sheet.
  • the layer thickness distribution is more uniform (better) the closer the value approaches HJ: LJ 1.
  • a polycondensation product called Mirapol WT is used instead of the inventive baths as component II.
  • Mirapol WT is a commercially available polymer which is widely used in aqueous, alkaline, cyanide-free baths, prepared by reacting the reaction product of N, N-dimethylaminopropylamine and urea with dichloroethyl ether. Such polymers are disclosed, for example, in US Pat. No. 5,435,898.
  • the use of the galvanic baths according to the invention also allows an improved gloss effect than the use of corresponding baths according to the prior art.

Abstract

Bains aqueux, alcalins et exempts de cyanure qui contiennent (I) une source d'ions de zinc et éventuellement une source d'autres ions métalliques, et (II) au moins un produit de polycondensation cationique pouvant être obtenu par condensation (i) d'une amine non cyclique (A1) produite par mise en réaction de mono(N,N-dialkylaminoalkyl)amine (A1a) avec un composé bifonctionnel (A1b) choisi dans le groupe constitué par urée, thiourée, carbonates de dialkyle, acides dicarboxyliques aliphatiques et aromatiques et diisocyanates aliphatiques et aromatiques, dans un rapport molaire (A1a) à (A1b) de 1,2 / 1 à 2,1 / 1, ou (ii) d'un mélange (A2) d'au moins une amine non cyclique (A1) et d'au moins une amine cyclique (A3) dans un rapport molaire (A1) à (A3) de 10 / 1 à 1 / 10 avec au moins un composé bifonctionnel (B) choisi parmi les halométhyloxiranes et les bisépoxydes, et dans la mesure où au moins une amine cyclique (A3) est condensée, parmi les dihalogénures d'alkylène et les dihalogènalkyléthers, dans un rapport molaire (B) à (A1) ou (B) à (A2) de 0,6 / 1 à 1,3 / 1.
PCT/EP2006/067495 2005-10-18 2006-10-17 Bain aqueux, alcalin et exempt de cyanure pour le dépôt galvanique de revêtements en zinc et en alliages de zinc WO2007045650A2 (fr)

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DE200510049789 DE102005049789A1 (de) 2005-10-18 2005-10-18 Wässriges, alkylisches, cyanidfreies Bad zur galvanischen Abscheidung von Zink- und Zinklegierungsüberzügen
DE102005049789.6 2005-10-18

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EP2175048A1 (fr) * 2008-10-13 2010-04-14 Atotech Deutschland Gmbh Composition de placage métallique pour le dépôt d'alliages d'étain et de zinc sur un substrat
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JP7002548B2 (ja) * 2016-12-22 2022-01-20 カール・フロイデンベルク・カー・ゲー 金属ピース品の表面に亜鉛含有皮膜を析出させるための水性アルカリ電解液
KR102641595B1 (ko) * 2017-09-04 2024-02-27 바스프 에스이 평탄화 제제를 포함하는 금속 전기 도금용 조성물
EP3581684B1 (fr) * 2018-06-11 2020-11-18 ATOTECH Deutschland GmbH Bain d'électrodéposition de zinc acidique ou d'alliage de nickel-zinc pour déposer une couche d'alliage de zinc ou de nickel-zinc

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