EP0244685B1 - Bain acide aqueux galvanique - Google Patents

Bain acide aqueux galvanique Download PDF

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Publication number
EP0244685B1
EP0244685B1 EP87105754A EP87105754A EP0244685B1 EP 0244685 B1 EP0244685 B1 EP 0244685B1 EP 87105754 A EP87105754 A EP 87105754A EP 87105754 A EP87105754 A EP 87105754A EP 0244685 B1 EP0244685 B1 EP 0244685B1
Authority
EP
European Patent Office
Prior art keywords
zinc
formula
bath
baths
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP87105754A
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German (de)
English (en)
Other versions
EP0244685A1 (fr
Inventor
Norbert Dr. Greif
Chung-Ji Dr. Tschang
Klaus Glaser
Ekhard Dr. Winkler
Knut Dr. Oppenlaender
Christos Dr. Vamvakaris
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
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Publication of EP0244685A1 publication Critical patent/EP0244685A1/fr
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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

  • auxiliaries are, for example, conductive salts, which are used to improve the conductivity of the baths, and so-called brighteners, which give the zinc coatings on the metals an increased sheen.
  • the brighteners also make it possible to work at low current densities.
  • the brighteners which can be assigned to a wide variety of chemical substance classes, are often poorly or not at all soluble in water and especially in salt solutions, so that another group of auxiliaries, namely surfactants, is required to fine-tune the brighteners in the electroplating bath Bring distribution.
  • the surfactants act as emulsifiers for the brighteners and produce clear, transparent microemulsions from which a uniform deposition of the zinc on the substrates is made possible.
  • nonionic surfactants have hitherto been used as surfactants in galvanic zinc baths, cf. GB-PS 1 149 106. From US Pat. No. 3,787,296 it is also known to use sulfated alkylphenol alkoxylates as surfactants in galvanic zinc baths. The gloss and ductility of the deposited zinc layers are not always optimal when using these compounds.
  • EP-A-115 020 discloses the use of sulfated alkylphenol ethoxylates, the phenolic core of which still carries a sulfonic acid group, as a surfactant in aqueous acidic galvanic zinc baths. These surfactants are able to solubilize the other water-poorly soluble auxiliaries, such as brighteners, and produce high-gloss, uniform and ductile coatings. However, these surfactants are not optimally effective in ammonium salt-free baths, which are sought among other things for reasons of environmental compatibility.
  • the present invention is based on the object of providing surfactants for aqueous acidic galvanic baths for the electrolytic deposition of zinc, in particular ammonium salt-free zinc baths, from which zinc coatings with improved properties, in particular gloss and ductility, can be deposited on metals compared to the known acidic zinc baths .
  • the compounds of formula 1 are preferably used as a surfactant in aqueous, acidic, ammonium salt-free galvanic baths for the electrolytic deposition of zinc in the presence of brighteners.
  • the compounds of the formula I are known and differ from the surfactants which, according to EP-A-115 020, are used in aqueous acidic electroplating baths for the electrolytic deposition of zinc in the presence of brighteners by the partial or complete replacement of ethylene oxide units by propylene oxide and / or butylene oxide units. At least one ethylene oxide unit of the surfactants according to the EP regulation mentioned is replaced by a propylene oxide or butylene oxide unit.
  • the substituent R 1 is a C 4 - to C 2 o -alkyl group.
  • Suitable Me are hydrogen, alkali metal or equivalents of an alkaline earth metal or zinc atom, preferably sodium and potassium.
  • the substituent R in formula I preferably has the meaning CH 3 -.
  • the alkoxylation of the phenol derivatives can also be carried out using a mixed gas of ethylene oxide and propylene oxide and, if appropriate, butylene oxide.
  • the compounds of formula I are obtained from the alkoxylated phenol derivatives by esterifying the alkoxylated products with sulfuric acid and optionally neutralizing them.
  • the compounds of the formula I must be water-soluble.
  • the surfactants of the formula I to be used according to the invention are present in the baths in an amount of 1 to 30, preferably 2 to 15 g / l.
  • the compounds of the formula I can optionally be used in a mixture with known surfactants which are usually used in electroplating baths, for example compounds such as pC 4 H 9 to C 12 H 25 alkylphenol ethoxylates with 10 to 30 ethylene oxide units or ⁇ - naphthol ethoxylates with 5 to 20 ethylene oxide units.
  • the additional surfactants that are considered, if they are used, are used in an amount of 1 to 15 g / l of the bath.
  • 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. These include representatives of the most diverse classes of substances, in particular certain aromatic or heteroaromatic ketones, as are described, for example, in GB-PS 1 149 106 or 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 Cs-alkyl, or crude products containing these compounds.
  • This class of compounds includes representatives such as:
  • benzal acetone is preferred.
  • o-chlorobenzaldehyde can be used as a brightener alone or as a mixture with a compound of the formula II.
  • the zinc baths advantageously contain brighteners in a total amount of 1 to 10 g / l and the top brighteners in an amount of 0.1 to 2.0 g / l, preferably 0.1 to 1 g / l.
  • the baths have the usual compositions. They contain, for example, 50 to 150 g / l zinc chloride or the equivalent amount of zinc sulfate, 100 to 250 g / l potassium chloride (conductive salt), 15 to 25 g / l boric acid, 1 to 8 g / l sodium benzoate and optionally 1 to 4 g / l an agent to increase scatter, e.g. Naphthalenesulfonic acid-formaldehyde condensation products. 10 to 150 g / l ammonium chloride or sodium chloride can also be used as conductive salts.
  • the pH of the baths is usually 3 to 6. The pH is adjusted by adding acids to the bath, e.g. Sulfuric acid or hydrochloric acid.
  • metals mainly iron and steel, are galvanized in order to protect them against corrosion and at the same time to give them a high gloss.
  • Bath 1 is an ammonium salt-free bath according to the preferred embodiment of the invention, while bath 2 is an ammonium salt-containing bath.
  • bath 1 The pH of bath 1 is 4.8, bath 2 has a pH of 4.5.
  • the pH is adjusted with dilute hydrochloric acid.
  • the galvanizing of steel sheets for testing purposes takes place over 10 minutes by galvanizing in a Hull cell with 1 ampere at approx. 23 ° C.
  • the quality of the zinc coatings obtained and the composition of the surfactants contained in the baths are given in the following table.

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)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (5)

1. Bain galvanique aqueux pour le dépôt électrolytique de zinc, ce bain contenant comme adjuvants essentiels des sels conducteurs, des lustrants et des agents tensio-actifs, caractérisé en ce que le bain contient des agents tensio-actifs d'un composé de formule
Figure imgb0013
dans laquelle
R = CH3-, CH3-CH2-,
x,z = 0 à 49,
y=1 à25,
x+y+z = 3 à 50,
R1 = alkyle en C4 à C20,
R2 = H, alkyle en C4 à C20 et
Me = H, atome de métal alcalin ou un équivalent d'un atome de métal alcalino-terreux ou d'un atome de zinc.
2. Bain suivant la revendication 1, caractérisé en ce que l'on utilise des agents tensio-actifs de la formule I, dans laquelle R2 = H.
3. Bain suivant la revendication 1 ou 2, caractérisé en ce que l'on utilise des agents tensio-actifs de la formule I, dans laquelle R = CH3, x, y et z = 3 à 15, soit x soit z étant égal à zéro.
4. Bain suivant l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on utilise comme lustrant un composé de formule
Figure imgb0014
dans laquelle R3 représente un radical aromatique ou hétéroaromatique et R4 un groupe alkyle en C1 à Cs, et/ou l'o-chlorobenzaldéhyde.
5. Utilisation de composés de la formule
Figure imgb0015
dans laquelle
R = CHa-, CH3―CH2―,
x,z = 0 à 49,
Y = 1 à 25,
x+y+z = 3 à 50,
R1 = alkyle en C4 à C20,
R2 - H, alkyle en 04 à C20 et
Me = H, atome de métal alcalin ou un équivalent d'un atome de métal alcalino-terreux ou d'un atome de zinc, comme agents tensio-actifs dans des bains galvaniques acides aqueux exempts de sels d'ammonium, pour le dépôt électrolytique de zinc en présence de lustrants.
EP87105754A 1986-04-24 1987-04-18 Bain acide aqueux galvanique Expired EP0244685B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3613874 1986-04-24
DE19863613874 DE3613874A1 (de) 1986-04-24 1986-04-24 Waessriges saures galvanisches bad

Publications (2)

Publication Number Publication Date
EP0244685A1 EP0244685A1 (fr) 1987-11-11
EP0244685B1 true EP0244685B1 (fr) 1989-07-26

Family

ID=6299436

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87105754A Expired EP0244685B1 (fr) 1986-04-24 1987-04-18 Bain acide aqueux galvanique

Country Status (2)

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EP (1) EP0244685B1 (fr)
DE (2) DE3613874A1 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4270990A (en) * 1979-06-07 1981-06-02 Minnesota Mining And Manufacturing Company Acidic electroplating baths with novel surfactants
DE3248503A1 (de) * 1982-12-29 1984-07-05 Basf Ag, 6700 Ludwigshafen Saures galvanisches zinkbad

Also Published As

Publication number Publication date
DE3760367D1 (en) 1989-08-31
EP0244685A1 (fr) 1987-11-11
DE3613874A1 (de) 1987-10-29

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