AU8871391A - Coating composition and process - Google Patents
Coating composition and processInfo
- Publication number
- AU8871391A AU8871391A AU88713/91A AU8871391A AU8871391A AU 8871391 A AU8871391 A AU 8871391A AU 88713/91 A AU88713/91 A AU 88713/91A AU 8871391 A AU8871391 A AU 8871391A AU 8871391 A AU8871391 A AU 8871391A
- Authority
- AU
- Australia
- Prior art keywords
- carbon atoms
- composition
- aluminium
- carboxylic acid
- zirconium
- 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- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims description 9
- 239000008199 coating composition Substances 0.000 title description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 18
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- -1 chloro- Chemical class 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 2
- 229920006163 vinyl copolymer Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 4
- 239000012530 fluid Substances 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Description
- \- Coating composition and process
This invention concerns a composition for coating metal surfaces and to a process for coating metal surfaces.
In the manufacture of zinc-, zinc alloy-, aluminium- or other metal-coated metal articles or sheet, or articles or sheet of aluminium, aluminium alloys, copper, copper alloys, steel or of other metals or alloys, it is desirable to apply one or more protective coatings to the surface with a view to alleviating the problems of deterioration of the surface in storage and/or of the provision of an effective base for later painting, varnishing, priming, enamelling or like operations. It is to these problems that the invention particularly relates.
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.
The approach disclosed in European Patent Specification No. 356855 derived from the earlier teachings in United States Patent No. 4650526 which utilised similar aluminium- zirconium complexes to treat metal surfaces which had
- - already been subjected to a phosphating treatment to improve corrosion resistance, a purpose of the aluminium-zirconium treatment being to improve the adhesion of later siccative organic coatings to the phosphate-treated surface. The United States patent teaches the use of aqueous solutions containing 0.005 to 5% by volume of the commercial aluminium-zirconium complex product. In many instances the performance of the phosphated, aluminium-zirconium complex- treated metal surfaces were found to be inferior to that of chromated metal surfaces in respect of corrosion prevention and adhesion of alkyd paint films.
In order to improve the performance of aluminium- zirconium complex-treated metal surfaces 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 has been found, however, that the process described in the European patent specification may not provide adequate, long-term resistance to surface deterioration since the zircoaluminate coating tends to shrink on drying, before the film-forming agent is applied, leaving regions of the metal surface effectively untreated with complex.
According to the present invention it has been found that excellent corrosion prevention and adhesion properties may be obtained on the aforesaid metals, for example on phosphated or non-phosphated surfaces of zinc-, zinc alloy- or aluminium-coated metals, using a one-coat non-rinse process, by the use of a treating composition characterised in that the composition comprises an aqueous solution, emulsion or dispersion of an organic film-forming polymer and one or more aluminium-zirconium complexes. Galvanised steel panels coated with the compositions of the present invention demonstrate a long
ter 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.
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: Al2(OR10)aAbBc (I) wherein .
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,
"b" is a numerical value of from 0.05 to 5.5, preferably from 1 to 5,
"c" is a numerical value of from 0.05 to 5.5, preferably from 1 to 5, provided that 2a + b + c = 6, and
-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 alpha-hydroxy carboxylic acid residue of the formula -0CH(R3)-C00H, 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:
ZrAdBe (II) wherein
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
"d" and "e" independantly have numerical values of from 0.05 to
4, provided that d + e = 4.
The organofunctional ligand (LIG) 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;
2) 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;
3) a dibasic carboxylic acid having from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms, and wherein both carboxy groups are preferably terminal;
4) acid anhydrides of dibasic acids having from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms;
5) a mercapto functional carboxylic acid having from 2 to 18 carbon atoms, preferably 2 to 6 carbon atoms; and
6) 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:
[Al2(OR10)aA Bc]x[LIG]y[ZrAdBc]z wherein A and B are as above-defined, and a,b,c,d and e are as defined above, except that, in order to form the bonds depicted, the substituents attached to the metal groups are appropriately reduced, i.e. 2a + b + c = 4 (2a + b + c = 5 when the aluminium moiety is a terminal grou ) , and d + e =
-S-
2 (d + e = 3 when the zirconium moiety is a terminal group) . When the aluminium moiety or the zirconium moiety terminates the above formula, one of the A or B groups may be replaced by a (Ci-Cςjalkoxy- group, x, y and z are independantly at least
1 and may vary from 1 to 100 or more. 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.
Methods for the preparation of the above described complexes are described in United States Patent
Specifications No. 4539048 and '4539049, the disclosures of which are incorporated herein by reference.
Very suitably 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 H2-(CH2)2"COOH, or 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. Preferably, however, 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. 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
-fe- 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.
Preferably, a substantial proportion of a silane, for example from 2 to 15% by weight of a commercial silane composition which may for example contain from 50% to 95% active material, based on the weight of the total aqueous composition, is included in the composition of this invention to increase the adhesion of subsequent organic surface coatings to the treated metal surface. Preferably the silane has alkoxy groups, preferably 2 or 3 such groups, hydrolysis of which will permit reaction with active sites on the metal substrate, and 1 or more organic groups capable of giving compatability with the film-forming polymer and/or polymers present in subsequent surface coatings. Examples of suitable silanes are 3-aminopropyl-triethoxysilane, N- aminoethyl-3-aminopropyl trimethoxysilane and vinyl triethoxysilane which may suitably be in the form of 50% to 95% concentration products.
A small quantity of a defoamer and/or surfactant is also preferably included. A suitable quantity of each is about 0.01% to 0.5% by weight of the total composition may be used. Suitable materials may be that available under the trade name Bevaloid 6575M, polyoxyethylene-polyoxypropylene block copolymers, fluorosurfactants or non-ionic hydrocarbon surfactants.
When prepared for use in a dip tank, 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 and from 1 to lOOg (polymer solids), preferably from 30 to 95g, of film-forming polymer.
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.
The coatings attained by the use 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. a) Salt spray corrosion test (ASTM B.117)
b) Humidity test (1) BS.3900:Part F2:1973(1983) .
-resistance to humidity-cyclic condensation.
(2) BS.3900:Part F9:1982(1985) -resistance to humidity-continuous condensation.
c) Stack test (Butler Building Test).
Stacking under artificially humid conditions provided by interleaved wetted filter paper for a number of days followed by a determination of the proportion of the area covered by white rust.
d) Adhesion test. BS.3900:Part E6:1974. Cross cut test.
The invention will now be illustrated by reference to the following Examples and the drawings in which:
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.
Example I
Galvanised steel panels were treated with a composition according to the invention comprising water, 15% by weight of Haloflex vinylidene chloride copolymer (ICI), 10% by weight of a commercial vinyl triethoxysilane product, 5% by weight of Manchem APG-X zircoaluminate product and 0.5% by weight of Synperonic PE/L61 polyoxyethylene block copolymer (ICI). The composition was applied at 5%v/v concentration at 20 C by roller application to give an even film with a thickness of 5+/-2 microns (10-6m) after drying. The panels were (a) left unpainted or were coated with (b) a polyester or (c) an alkyd paint.
The panels were tested with the following results:
b)(l) 162 Hours
Humidity <10% White
- \- rust
b)Stack 30 Days-pass b test <10% White rust (ga1vanised tube.
c)Cross cut test Class 0 Class 1 Acceptable
Claims (11)
1. An aqueous composition for coating metal, eg zinc, copper, steel or aluminium, surfaces comprising:
l)an aluminium-zirconium complex which is the reaction product of a chelated aluminium moiety, a zirconium oxyhalide and an organofuctional ligand, the organofunctional ligand being complexed with and chemically bound to the chelated aluminium moiety and the zirconium moiety, the aluminium moiety having the general formula: Al2(ORlθ)aAbBc (I) wherein
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,
"b" is a numerical value of from 0.05 to 5.5, preferably from 1 to 5 ,
"c" is a numerical value of from 0.05 to 5.5, preferably from 1 to 5, provided that 2a + b + c = 6, and
-0R10- is either an alpha-beta or alpha-gamma glycol group in which R1 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 alpha-hydroxy carboxylic acid residue of the formula -0CH(R3)-C00H, where
R3 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, having the general formula:
ZrAdBe (II) wherein
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 "d" and "e" independantly have numerical values of from 0.05 to 4, provided that d + e = 4; and the organofunctional ligand (LIG) being 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;
(2) 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;
(3) a dibasic carboxylic acid having from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms, and wherein both carboxy groups are preferably terminal;
(4) acid anhydrides of dibasic acids having from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms;
(5) a mercapto functional carboxylic acid having from 2 to 18 carbon atoms, preferably 2 to 6 carbon atoms; and
(6) an epoxy functional carboxylic acid having from 2 to 18 carbon atoms, preferably from 2 to 6 carbon atoms;
2) a film-forming polymer; and optionally
3) a silane.
2. A composition as claimed in Claim 1, wherein component 1) is present in the composition in an amount of from 0.2 to 20% by weight of the total composition.
3. A composition as claimed in any one of the preceding claims, wherein component 2) is present in an amount of from 2 to 20 % by weight polymer solids of the total composition. - 11-.-
4. A composition as claimed in any one of the preceding claims , wherein component 2) is selected from the group consisting of vinyl polymers or copolymers, (meth)acrylic polymers or copolymers, (meth)acrylate polymers or copolymers, and mixtures thereof.
5. Use of a composition as claimed in any one of claims 1 to 4 in or as a dip tank fluid for preventing corrosion of metal surfaces.
6. Use of a composition as claimed in any one of claims 1 to 4 in or as a metal primer.
7. A dip tank fluid, suitable for preventing corrosion of zinc galvanised steel, comprising an aqueous composition, each litre of composition comprising from 20 to 200g, preferably 30 to 150g, of an aluminium-zirconium complex as defined in claim 1, and from 1 to lOOg (polymer solids), preferably from 30 to 95g, of a film- forming polymer.
8. A zinc galvanised steel article, e.g. panel, wire, tube, or plate, coated with a composition as claimed in any one of claims 1 to 4.
9. An aluminium article, e.g. panel, wire, tube, or plate, coated with a composition as claimed in any one of claims 1 to 4.
10. A metal primer comprising a composition as claimed in any one of claims 1 to 4.
11. A composition, method of application of a composition or use of a composition subsantially as hereinbefore defined with reference to the examples.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909024474A GB9024474D0 (en) | 1990-11-10 | 1990-11-10 | Coating composition and process |
| GB9024474 | 1990-11-10 | ||
| GB9120440 | 1991-09-25 | ||
| GB919120440A GB9120440D0 (en) | 1990-11-10 | 1991-09-25 | Coating composition and process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU8871391A true AU8871391A (en) | 1992-06-11 |
Family
ID=26297931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU88713/91A Withdrawn AU8871391A (en) | 1990-11-10 | 1991-11-07 | Coating composition and process |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0556250A1 (en) |
| AU (1) | AU8871391A (en) |
| CA (1) | CA2095810A1 (en) |
| WO (1) | WO1992008822A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9120442D0 (en) * | 1991-09-25 | 1991-11-06 | Laporte Industries Ltd | Coating composition and process |
| DE19516765A1 (en) * | 1995-05-06 | 1996-11-07 | Henkel Kgaa | Chromium and fluoride free treatment of metal surfaces |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191596A (en) * | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| US4650526A (en) * | 1986-03-18 | 1987-03-17 | Man-Gill Chemical Company | Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes |
| US4978399A (en) * | 1988-01-04 | 1990-12-18 | Kao Corporation | Metal surface treatment with an aqueous solution |
| DE3829154A1 (en) * | 1988-08-27 | 1990-03-01 | Collardin Gmbh Gerhard | CHROME-FREE METHOD FOR PRE-TREATING METALLIC SURFACES BEFORE COATING WITH ORGANIC MATERIALS |
-
1991
- 1991-11-07 EP EP19910919619 patent/EP0556250A1/en not_active Withdrawn
- 1991-11-07 WO PCT/GB1991/001958 patent/WO1992008822A1/en not_active Ceased
- 1991-11-07 CA CA 2095810 patent/CA2095810A1/en not_active Abandoned
- 1991-11-07 AU AU88713/91A patent/AU8871391A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992008822A1 (en) | 1992-05-29 |
| EP0556250A1 (en) | 1993-08-25 |
| CA2095810A1 (en) | 1992-05-11 |
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