EP1373336A2 - Utilisation de polyolefines ayant des substituants basiques aromatiques comme auxiliaires dans la precipitation electrolytique de couches metalliques - Google Patents

Utilisation de polyolefines ayant des substituants basiques aromatiques comme auxiliaires dans la precipitation electrolytique de couches metalliques

Info

Publication number
EP1373336A2
EP1373336A2 EP01985881A EP01985881A EP1373336A2 EP 1373336 A2 EP1373336 A2 EP 1373336A2 EP 01985881 A EP01985881 A EP 01985881A EP 01985881 A EP01985881 A EP 01985881A EP 1373336 A2 EP1373336 A2 EP 1373336A2
Authority
EP
European Patent Office
Prior art keywords
polyolefins
bath
use according
basic
alkaline
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Withdrawn
Application number
EP01985881A
Other languages
German (de)
English (en)
Inventor
Ferdinand Leifeld
Rainer Urich
Isolde Ortmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raschig GmbH
Original Assignee
Raschig GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Raschig GmbH filed Critical Raschig GmbH
Publication of EP1373336A2 publication Critical patent/EP1373336A2/fr
Withdrawn legal-status Critical Current

Links

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
    • 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 present invention relates to the use of polyolefins with basic, aromatic substituents as auxiliaries for the electrolytic deposition of metallic layers.
  • the product can be used in acidic, galvanic copper baths as well as in alkaline zinc baths or in alkaline zinc alloy baths.
  • the copper baths can be used for decorative deposition, for example for automotive parts and for reinforcing conductor tracks in printed circuits.
  • the alkaline zinc baths serve mainly as protection against corrosion.
  • US Pat. No. 3,328,273 (1967) describes the deposition of copper from an acidic, galvanic bath in the presence of SPS, polypropylene glycol and the Janus green dye.
  • DE-OS 2541 897 describes a combination of SPS, ethoxylated or propoxylated polyethyleneimines, which were then reacted with the benzyl chloride.
  • US-P 4,036,711 proposes the use of quaternized alkyl and aryl amines together with sulphoalkyl sulfides and polyethylene glycols.
  • DE-PS 20 39 831 the use of polymeric phenazonium compounds is presented.
  • DE 19643 091 A1 describes the use of water-soluble polyamides crosslinked with epichlorohydrin. Galvanizing from alkaline, cyanidic zinc baths has been known for many years. Due to disposal problems and toxicity of cyanides, this type of bath is increasingly being replaced by alkaline, non-cyanide baths.
  • US Pat. No. 4,135,992 (1979) describes an alkaline, cyanide-free zinc bath in which alkylated polyimines in combination with aldehydes, benzyl-3-sodium-carboxy-pyridinium chloride (BN-betaine) or imidazole derivatives lead to a shiny zinc layer.
  • galvanic baths described often lead to unsatisfactory results in terms of gloss, leveling and metal distribution as well as problems with the layer properties, such as corrosion protection and ductility.
  • Acidic copper baths can deposit layers with good gloss and scattering, but they have problems with leveling.
  • a particular disadvantage is the lack of leveling in low current densities.
  • nylon fibers or polyester fibers can be improved by incorporating polyvinylpyridines (SU-P 3,361,843 (1963)).
  • polyvinylpyridines are used especially for the production of electrically conductive coatings.
  • electrically conductive coatings from e.g. Polyvinylpyrrolidone or poly (2-vinylpyridine) are described, which make it possible to make non-conductive plastics conductive by coating and thus to make them metallizable.
  • Ar represents a basic aryl radical such as 2- or 4-pyridyl, 2-quinolyl or 2-pyrazolyl or a phenyl, an alkyl having 1 to 8 C atoms or hydrogen, at least 50% of the groups representing a basic aryl radical and n represents an integer from 2 to 3000.
  • Linear polyvinyl pyridine polymers can e.g. according to US Pat. No. 5,824,756 can be produced in different ways from 2-vinylpyridine or 4-vinylpyridine or copolymerization of 2-vinylpyridine and 4-vinylpyridine.
  • the reaction can be initiated via radical initiators, by irradiation or Ziegler-Natter catalysts.
  • the polymerizations can be carried out in bulk, emulsion or solution.
  • the H atoms shown in the general formula at the beginning and end of the chain can be wholly or partly e.g. be replaced by the radical starter.
  • the polymers used in this invention were primarily produced by radical initiators in solution or as an emulsion.
  • Alcohols such as methanol and ethanol or else water and also mixtures thereof can be used as solvents.
  • Sodium peroxodisulfate, for example, Dibenzoyl peroxide or azobisisobutyronitrile can be used.
  • 2-vinylpyridine or 4-vinylpyridine or a mixture of 2-vinylpyridine and 4-vinylpyridine is introduced into the solvent, the radical initiator is added and the mixture is stirred at 30 ° C. to 100 ° C. for 2 to 20 hours.
  • the average molar mass of the reaction products can be in the range from 210 to 300,000 g / mol, preferably in the range from 1,000 to 100,000 g / mol.
  • the polymers according to the invention are obtained from the preparation as a solution or emulsion and are normally used directly without further purification.
  • the concentrations of the solutions achieved are typically between 5 and 30% by weight.
  • the products obtained (based on the solid) are added to the acidic copper bath in amounts of 0.001 to 5 g / l bath. In the case of an alkaline zinc bath or zinc alloy bath, the addition amounts are in the range of 0.005 to 10 grams per liter of bath.
  • the acidic copper bath can also contain further organic additives known per se.
  • the combination with at least one sulfur compound rendered water-soluble by sulfopropylation is advantageous.
  • Table shows some examples with the preferred amounts:
  • wetting agents such as Ralufon NO 14 with 2.5 moles of propylene oxide and 14 moles of ethylene oxide in amounts of 0.001 to 1 g / l can be used as wetting agents, and as crosslinked polyamide EXP 2887 (epoxyimidazole polymer) in amounts of 0.001 to 0.5 g / l.
  • Beta-naphthol alkoxylates such as Ralufon NO 14 with 2.5 moles of propylene oxide and 14 moles of ethylene oxide in amounts of 0.001 to 1 g / l can be used as wetting agents, and as crosslinked polyamide EXP 2887 (epoxyimidazole polymer) in amounts of 0.001 to 0.5 g / l.
  • the inorganic constituents of the acid copper bath are preferably copper sulfate, sulfuric acid and chlorides, but other copper salts and other acids, such as fluoroboric acid or methanesulfonic acid, can also be used instead of sulfuric acid.
  • the bath preferably contains between 50 and 250 g / l copper sulfate (CuSO 4 * 5H 2 O), between 25 and 250 g sulfuric acid and between 0.01 and 0.5 g / l chloride ions.
  • alkaline zinc baths or zinc alloy baths can also contain 0.1-50 g / l of reaction products of epichlorohydrin with amines, benzyl-3-sodium-carboxy-pyridinium chloride, polyimides and their reaction products, and also aldehydes such as anisaldehyde or vaniline the known amounts for such baths contain 0.1 - 10 g / l.
  • the bath usually contains zinc ions as inorganic constituents in amounts of 2-20 g / l, preferably 5-20 g / l, 30-250 g / l NaOH and Na 2 CO 3 .
  • Complexing agents such as gluconates or tartrates (1-50 g / l) can also be added to the baths.
  • the alkaline zinc alloy baths can also contain nickel, iron or cobalt ions.
  • the movement in the galvanic bath is carried out by blowing in air or by moving the cathode. A combination of both types of movement is also possible.
  • composition of the basic bath 210 g / l copper sulfate * 5H 2 0
  • Organic bath additives 0.100 g / l polyethylene glycol (Mg.Approx. 9000 g / mol)
  • a brass sheet coated at 25 ° C, with air movement and at 2 A in a Hull cell showed a shiny, ductile copper layer with good scattering but only slight leveling.
  • the inorganic base bath is unchanged from example 1, the electrolyte temperature was 20 ° C. and it was galvanized at 1.5 A in the Hull cell.
  • the copper deposit is highly shiny and ductile with a very low leveling.
  • 0.03 grams per liter of an approximately 20% ethanolic solution of a poly-4-vinylpyridine with an average molecular weight of approximately 5000 g / l was added.
  • the subsequent coated Hull cell sheet is highly glossy and leveled at a current density of over 0.3 A / dm 2 .
  • composition of the basic bath 12.5 g / l zinc oxide
  • Morpholine and imidazole (MOME according to DE 35 38 147) 2.0 g / l reaction product from epichlorohydrin and imidazole (IME according to DE 35 38 147) 3.0 g / l reaction product from polyimine with propanesulfone
  • the bath was tested at 20 ° C in a Hull cell using a steel sheet as the anode. Air was blown in to move the bath. A steel sheet coated at 1 A for 10 minutes showed a zinc layer with satisfactory Shine. At three different current densities, the following were made
  • a subsequently coated steel sheet showed high gloss over the entire current density range and the following metal distribution: 5 ⁇ m at 4 A / dm 2 , 5 ⁇ m at 2 A / dm 2 and 5 ⁇ m at 0.5 A / dm 2 .

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)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des polyoléfines ayant des substituants basiques aromatiques de la formule générale (I) où Ar représente un reste aryle basique, un phényle, un alkyle ayant 1 à 8 atomes de carbone ou un hydrogène, au moins 50 % des groupes représentant un reste aryle basique et n valant un nombre entier compris entre 2 et 3000. Ces polyoléfines sont utilisés comme additif dans des bains galvaniques. L'invention concerne également des bains de galvanisation contenant ces polyoléfines et un procédé de précipitation élektrolytique de couches métalliques.
EP01985881A 2001-01-11 2001-12-13 Utilisation de polyolefines ayant des substituants basiques aromatiques comme auxiliaires dans la precipitation electrolytique de couches metalliques Withdrawn EP1373336A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10100954 2001-01-11
DE2001100954 DE10100954A1 (de) 2001-01-11 2001-01-11 Verwendung von Polyolefinen mit basischen, aromatischen Substituenten als Hilfsmittel zur elektrolytischen Abscheidung von metallischen Schichten
PCT/EP2001/014675 WO2002055568A2 (fr) 2001-01-11 2001-12-13 Utilisation de polyolefines ayant des substituants basiques aromatiques comme auxiliaires dans la precipitation electrolytique de couches metalliques

Publications (1)

Publication Number Publication Date
EP1373336A2 true EP1373336A2 (fr) 2004-01-02

Family

ID=7670220

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01985881A Withdrawn EP1373336A2 (fr) 2001-01-11 2001-12-13 Utilisation de polyolefines ayant des substituants basiques aromatiques comme auxiliaires dans la precipitation electrolytique de couches metalliques

Country Status (3)

Country Link
EP (1) EP1373336A2 (fr)
DE (1) DE10100954A1 (fr)
WO (1) WO2002055568A2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7316772B2 (en) * 2002-03-05 2008-01-08 Enthone Inc. Defect reduction in electrodeposited copper for semiconductor applications
US8002962B2 (en) * 2002-03-05 2011-08-23 Enthone Inc. Copper electrodeposition in microelectronics
CN105177647B (zh) * 2015-08-28 2018-05-22 上海八菱环保科技有限公司 一种酸性镀铜光亮稳定剂及其制备方法
CN105887144B (zh) * 2016-06-21 2018-09-21 广东光华科技股份有限公司 电镀铜镀液及其电镀铜工艺

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE795359A (fr) * 1972-02-15 1973-05-29 Du Pont Depot electrolytique acide de zinc ou de nickel
DE2360892A1 (de) * 1972-12-14 1974-06-20 M & T Chemicals Inc Waessriges saures galvanisches kupferbad
JPH05271979A (ja) * 1992-03-25 1993-10-19 Electroplating Eng Of Japan Co 金めっき浴及びそれを用いた金めっき品の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02055568A3 *

Also Published As

Publication number Publication date
WO2002055568A2 (fr) 2002-07-18
WO2002055568A3 (fr) 2003-10-23
DE10100954A1 (de) 2002-07-18

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