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WO1993006259A1 - Procede et composition de revetement - Google Patents

Procede et composition de revetement Download PDF

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Publication number
WO1993006259A1
WO1993006259A1 PCT/EP1992/002187 EP9202187W WO9306259A1 WO 1993006259 A1 WO1993006259 A1 WO 1993006259A1 EP 9202187 W EP9202187 W EP 9202187W WO 9306259 A1 WO9306259 A1 WO 9306259A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
carbon atoms
aluminium
carboxylic acid
zirconium
Prior art date
Application number
PCT/EP1992/002187
Other languages
English (en)
Inventor
Neil Clarke
Stephen George Grundy
Original Assignee
Laporte Industries Limited
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 Laporte Industries Limited filed Critical Laporte Industries Limited
Priority to EP92920230A priority Critical patent/EP0605555A1/fr
Publication of WO1993006259A1 publication Critical patent/WO1993006259A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8

Definitions

  • This invention concerns a composition for coating metal surfaces and to a process for the manufacture of such a composition.
  • a zinc-coated steel surface for example, has a tendency, if untreated, to develop a white coloured powdery deposit in storage, so-called "white rust", which detracts from the appearance of the surface and possibly adversely affects the key of paint and the like onto the surface.
  • European Patent Specification No. 356855 relates to the problem outlined above. That specification refers to the established usage of chromium compounds to achieve the inhibition of corrosion of aluminium and zinc, and cites the considerable problems of effluent monitoring and disposal and the need to take precautions to ensure the protection of plant operatives which arises from the extremely toxic nature of the chromium compounds. The specification teaches that certain aluminium-zirconium complexes may be used in place of the chromium compounds.
  • European Patent Specification No. 356855 teaches the coating of the complex- treated surface, after rinsing and drying, with an aqueous solution, emulsion or dispersion of a film-forming agent, such as polyacrylic acid.
  • the aluminium-zirconium complex is used at concentrations of 0.1% or 1.0% by volume of the commercial form, which contains 20-24% wt of the complex, and the organic film- forming composition in 0.5 to 1 g/1.
  • It an object of the present invention to provide a non- chromate composition which is suitable for coating or treating metal surfaces, particularly galvanised metal surfaces, to prevent or retard corrosion. It is a further object of the present invention to provide a composition for coating zinc- galvanised metal surfaces which does not strip zinc from the metal during coating or treating in a dip bath. It is yet a further object of the present invention to provide a coating composition which does not suffer the shrinkage problems associated with prior art compositions.
  • the preferred pH of the composition is from 3 to 7, more preferrably from 4 to 6, though it will be understood that the maximum pH is determined by the pH at which the aluminozirconate precipitates out from the solution, usually at about pH 7 to 8.
  • Galvanised steel panels coated with the compositions of the present invention demonstrate a long term resistance to surface deterioration commensurate with known chromium-based coatings. Further, the compositions of the present invention tend not to suffer the "shrinkage" problems associated with known aluminozirconate coatings.
  • compositions of the present invention are less acidic than any of the known coatings, there is less of a tendency for zinc galvanised to steel to be stripped off the steel in the dip tank containing the composition, thereby reducing the rate at which the dip tank fluid becomes contaminated with zinc ions and so substantially extending the working life time of the dip tank fluid (In comparison with the working life time of known dip tank fluids, either chromium-based compositions or luminozirconate-based compositions, such as the composition disclosed in UK Patent Application No 9024474.0, the working life time of a dip tank fluid based on the composition of the present invention is expected to be at least three times longer).
  • Aluminium-zirconium complexes which may be utilised according to the invention are, for example, the reaction product of a chelated aluminium moiety, a zirconium oxyhalide and an organofuctional ligand.
  • the organofunctional ligand is complexed with and chemically bound to the chelated aluminium moiety and the zirconium moiety.
  • the chelate-stabilised aluminium moiety has the general formula:
  • a and B are halo-, preferably chloro-, or hydroxy-,
  • a is a numerical value of from 0.05 to 2, preferably from 0.1 to 1,
  • -OR ⁇ O- is either an alpha-beta or alpha-gamma glycol group in which R* is an alkyl, alkenyl, or alkynyl group having from 1 to 6 carbon atoms, preferably an alkyl group and preferably having 2 or 3 carbon atoms; or an lpha-hydroxy carboxylic acid residue of the formula -OCH(R3)-COOH, where R ⁇ is H- or an alkyl- group having from 1 to 4 carbon atoms, preferably from 2 to 3 carbon atoms.
  • the zirconium oxyhalide preferably an oxychloride, has the general formula:
  • a and B are as defined for (I) above, preferably one of A and B is chloro- and the other of A and B is hydroxy-, and
  • the organofunctional ligand is derived from one or more of the following: 1) an alkyl-, alkenyl-, alkynyl-, aryl- or aralkyl-carboxylic acid having from 2 to 36 carbon atoms, preferably from 2 to 18 carbon atoms, more preferably from 4 to 18 carbon atoms and even more preferably from 2 to 6 carbon atoms;
  • an aminofunctional carboxylic acid having from 2 to 36 carbon atoms, preferably from 2 to 18 carbon atoms, more preferably from 4 to 18 carbon atoms and more preferably from 2 to 6 carbon atoms;
  • an epoxy functional carboxylic acid having from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms.
  • the aluminium-zirconium complex may be empirically represented by the general formula:
  • one of the A or B groups may be replaced by a (C ⁇ -C5)alkoxy- group, x, y and z are independantly at least
  • the molar ratio of x to z may vary from 1.5 to 10 with the preferred ratio being from 3 to 6 and the ratio of (y/(2x + z)) may vary from 0.05 to 3, preferably from 0.05 to 2.0, and more preferably from 0.1 to 0.5.
  • the aluminium-zirconium complexes utilised according to this invention may be those available under the Trade Name Manchem as about 20% to 25% vol solutions in polar solvents such as the lower alcohols, glycols, or glycol ethers of which suitable products are, for example,those designated APG-X, in which the carboxylic acid component is NI_2-(CH2)2- c 0 OH / °r CPG or CPM, in which the carboxylic acid components are HOOC-(CH2)4 ⁇ COOH.
  • polar solvents such as the lower alcohols, glycols, or glycol ethers of which suitable products are, for example,those designated APG-X, in which the carboxylic acid component is NI_2-(CH2)2- c 0 OH / °r CPG or CPM, in which the carboxylic acid components are HOOC-(CH2)4 ⁇ COOH.
  • the organic film-forming polymer may be any polymer which is available as and curable in an aqueous solution dispersion or emulsion.
  • the film- forming polymer is selected from suitable vinyl polymers or copolymers, for example vinyl-acrylic copolymers, polyacrylic and polymethacrylic acids, and polyacrylates and polymethacrylates.
  • suitable vinyl polymers or copolymers for example vinyl-acrylic copolymers, polyacrylic and polymethacrylic acids, and polyacrylates and polymethacrylates.
  • the most preferred film-forming polymers are emulsions of acrylic coplymers such as those emulsions available under the Trade Name Neocryl (from ICI). Suitably such polymers may themselves contain corrosion inhibitors.
  • a suitable solids content for the organic film-forming polymer is from about 30% to 50%, or even up to 75%, by weight.
  • the aluminium-zirconium complex may be present in the composition of the present invention in an amount of from 0.2% to 20% by weight based on the weight of the total aqueous composition although particularly successful results have been achieved using at least 5% by weight, for example 5 to 20% by weight, on the same basis.
  • the film-forming polymer may be present in greater than 2%, for example from 2% to 20%, by weight of polymer solids on the same basis.
  • a solution of the aluminium-zirconium compound in an organic polar water-miscible solvent may be mixed with the aqueous solution, dispersion, or emulsion of the film- forming polymer, preferably to give the above stated solids concentrations and the resulting product may therefore have a substantial content of said organic, polar solvent .
  • the composition additionally comprises a non-ionic surfactant.
  • the non-ionic surfactant is preferably present in an amount normally considered excessive for the film-forming polymer alone.
  • the level of addition of a non-ionic surfactant is typically no more than 2 % by weight on the weight of latex solids, whereas in the compositions of the present invention the surfactant is preferably present in an amount of from more than 2% up to 8.5 wt%, more preferably from 3 to 8 wt %, and yet more preferrably from 3.5 to 5 wt%, based on the weight of polymer solids of the film forming polymer.
  • the weight of the composition as a whole is equivalent to about 0.02 to 1.275 wt%, and more preferrably 0.035 to 0.75 wt%.
  • any suitable non-ionic surfactant may be employed in the compositions of the present invention, the non-ionic surfactants Synperonic PE/F87 (ICI) , a block copolymer based on ethylene oxide/propylene oxide, or Synperonic NP30 (ICI), a nonyl phenol 30 mole ethylene oxide condensate, are preferred.
  • a small quantity of a defoamer is also preferably included.
  • a typical quantity of about 0.01% to 0.5% by weight of the total composition may be used.
  • a typical defoamer is Tego Foamex 1488 (an emulsion of organo-modified polysiloxanes available from Th. Goldschmidt Ltd. ) .
  • each litre of a preferred composition of the present invention will typically comprise from 20 to 200g, preferably 30 to 150g, of aluminium- zirconium complex, from 1 to lOOg (polymer solids), preferably from 30 to 95g, of film-forming polymer and from 0.25 to lOg, preferably from 0.75 to 5g, nonionic surfactant.
  • the present invention provides a method of preparation of a composition
  • a composition comprising an aqueous solution, emulsion or dispersion of an organic film-forming polymer and an aluminium-zirconium complex , which composition has a pH of from 3 to 8, preferably of from 4 to 7 , characterised in that the method comprises:
  • the final composition comprises a non-ionic surfactant which is added in appropriate amounts to any one of the first and/or second or third vessels.
  • the non-ionic surfactant is added in appropriate amounts to both the first and second vessels.
  • the composition according to the present invention may be applied to the metal surfaces to be treated for example to a metal coil after hot dip or electrogalvanising or aluminium coating and after the temperature of the metal has fallen to below about 85°C preferably to below 80°C.
  • the method of application may be by spray or by immersion with surplus liquid being removed, suitably by passing the metal between rollers or by the use of an air-knife.
  • the metal may then be air or oven dried, for example at from 65°C to 85°C.
  • the thickness of the coating is preferably up to about 50 microns, for example 1 to 10 microns which may be controlled by adjusting the solids concentration of the treating composition appropriately.
  • compositions of the present invention adhere strongly to the metal surface to which they are applied, help to retain the metal surface in bright, uncorroded form, and give a good key to subsequent surface coatings. Accordingly, the compositions of the present invention may suitably be used in or as coatings, such as primers or finishes. These properties may be tested by the following tests.
  • FIG 1 is a photograph of a galvanised steel panel treated in accordance with the process of EP-A-0356855 and illustrates the problems of "shrinkage" where the metal surface has dark and light regions indicating where the metal surface is coated with zircoaluminate composition or uncoated respectively;
  • FIG 2 is a photograph of a galvanised steel panel treated in accordance with the process of the present invention and illustrating a dark, even coating of zircoaluminate composition over the metal surface .
  • composition in accordance with the present invention was prepared as follows:
  • aqueous solution comprising 2.5g Synperonic NP30 commercial surfactant (available from ICI) was prepared by dissolving the surfactant in 846.5g of demineralised (DM) water at 50°C in a scrupulously clean vessel.
  • DM demineralised
  • To the solution was added lg of Tego Foa ex commercial defoamer.
  • the solution was divided equally into two scrupulously clean vessels.
  • To one vessel was added, under stirring, 50g Manchem APG-X commercial a ino zircoaluminate solution (available from Rhone-Poulenc) and to the other vessel, also under stirring, lOOg Neocryl XK-69 commercial film-forming polymer (available from ICI).
  • the compositions in the two vessels were then discharged into another vessel, where the two compositions were blended together, with care being taken never to allow unequal amounts of the two compositions to be present in the blending vessel at the same time, to form a composition of the present invention.
  • composition of the present ivention was prepared by following the process described in Example I, but this time 796.5g of DM water and lOOg Manchem APG-X were used.
  • Galvanised steel panels were treated with the compositions formed in Examples I and II.
  • the compositions were applied at 5% v/v concentration at 20°c by roller application to give a film thickness of 5+/-2 microns after drying.
  • the panels were (a) left unpainted or were coated with (b) a polyester or (c) an alkyd paint.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Composition aqueuse, comprenant un complexe de zirconate d'alumine et un polymère filmogène. Cette composition aqueuse a un pH qui est au moins égal à 3, et elle est utile pour réduire la détérioration à long terme des surfaces métalliques, plus particulièrement des surfaces exposées de panneaux ou de feuilles d'acier galvanisé au zinc.
PCT/EP1992/002187 1991-09-25 1992-09-21 Procede et composition de revetement WO1993006259A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP92920230A EP0605555A1 (fr) 1991-09-25 1992-09-21 Procede et composition de revetement

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB919120442A GB9120442D0 (en) 1991-09-25 1991-09-25 Coating composition and process
GB9120442.0 1991-09-25

Publications (1)

Publication Number Publication Date
WO1993006259A1 true WO1993006259A1 (fr) 1993-04-01

Family

ID=10701976

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002187 WO1993006259A1 (fr) 1991-09-25 1992-09-21 Procede et composition de revetement

Country Status (6)

Country Link
EP (1) EP0605555A1 (fr)
AU (1) AU2641992A (fr)
CA (1) CA2119892A1 (fr)
GB (1) GB9120442D0 (fr)
WO (1) WO1993006259A1 (fr)
ZA (1) ZA927309B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757082B2 (ja) * 1985-09-18 1995-06-14 株式会社日立製作所 永久磁石界磁型電動機

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes
EP0356855A2 (fr) * 1988-08-27 1990-03-07 Gerhard Collardin Gmbh Prétraitement de surfaces en aluminium ou alliages d'aluminium à revêtir avec des matériaux organiques sans utilisation de chrome
WO1992008822A1 (fr) * 1990-11-10 1992-05-29 Oakite Limited Composition et procede de recouvrement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4650526A (en) * 1986-03-18 1987-03-17 Man-Gill Chemical Company Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes
EP0356855A2 (fr) * 1988-08-27 1990-03-07 Gerhard Collardin Gmbh Prétraitement de surfaces en aluminium ou alliages d'aluminium à revêtir avec des matériaux organiques sans utilisation de chrome
WO1992008822A1 (fr) * 1990-11-10 1992-05-29 Oakite Limited Composition et procede de recouvrement

Also Published As

Publication number Publication date
EP0605555A1 (fr) 1994-07-13
AU2641992A (en) 1993-04-27
ZA927309B (en) 1994-02-21
CA2119892A1 (fr) 1993-03-26
GB9120442D0 (en) 1991-11-06

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