WO2008092528A1 - Prétraitement pour métaux contenant des pigments luminescents - Google Patents

Prétraitement pour métaux contenant des pigments luminescents Download PDF

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Publication number
WO2008092528A1
WO2008092528A1 PCT/EP2007/063648 EP2007063648W WO2008092528A1 WO 2008092528 A1 WO2008092528 A1 WO 2008092528A1 EP 2007063648 W EP2007063648 W EP 2007063648W WO 2008092528 A1 WO2008092528 A1 WO 2008092528A1
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WIPO (PCT)
Prior art keywords
composition according
concentrate
water
luminescence
metallic surface
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PCT/EP2007/063648
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German (de)
English (en)
Inventor
Ina KRÜGERMANN
Christian Rosenkranz
Stefanie Küch
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Henkel Ag & Co. Kgaa
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Priority to JP2009547552A priority Critical patent/JP2010518185A/ja
Publication of WO2008092528A1 publication Critical patent/WO2008092528A1/fr

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    • 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
    • C23C22/06—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
    • C23C22/36—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 containing also phosphates
    • C23C22/361—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 containing also phosphates containing titanium, zirconium or hafnium compounds
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
    • 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
    • C23C22/73—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 characterised by the process
    • C23C22/77—Controlling or regulating of the coating process

Definitions

  • the invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium or their alloys.
  • the present invention relates to a substantially chromium-free aqueous agent for the corrosion-protective treatment of metal surfaces containing a particulate inorganic pigment, wherein the pigment luminesces when irradiated with ultraviolet light and the pH of the aqueous agent is not greater than 4 and not less than 1 ,
  • concentrates according to the invention are included which either serve as a concentrate for the agent according to the invention or which can be used directly for the treatment of the metallic surface.
  • the method according to the invention comprises treating a metallic surface with such a means and visually assessing the quality of the treatment process on the basis of a luminescence of the metal surface which is as homogeneous as possible, caused by the inorganic pigment according to the invention immobilized in the protective layer against corrosion of the metallic substrate and / or superficially immobilized ,
  • Such an optical assessment of the anticorrosive treatment wherein the luminescence of the treated metal surface is preferably in the visible range of the light and is perceptible to the human eye, opens up various possibilities of aftertreatment, which are without the presence of the luminescent pigments in the corrosion-protecting organic-inorganic hybrid layer, are not possible in the technical coating process and therefore represent a further aspect of this invention.
  • the chemical treatment of metallic surfaces to impart corrosion protection essentially comprises phosphating and conversion processes, the latter forming extremely thin and amorphous mostly inorganic cover layers which do not cause any visible change of the metallic surface to the human eye.
  • the occurrence of interference colors can usually only be observed for layer thicknesses above 100 nm, wherein due to the strong dependence of the interference color on the viewing angle, no uniform overall impression of the corrosion-protected treated metal surface results.
  • Only the chromating as a passivating conversion treatment produces intensely colored metal surfaces. From many years of experience with the chromating of metal surfaces, it is therefore familiar to the person skilled in the art to obtain a colored layer as a result of the conversion treatment. He can then immediately visually recognize whether the treatment has brought the desired success.
  • the conversion bath usually contains organic polymeric compounds which usually have complexing properties, but do not exclusively have a stabilizing effect on the bath components, but are also selected such that they exert a positive influence on the adhesion of further applied organic coating systems as a constituent of the conversion layer.
  • Conversion layers therefore represent organic-inorganic hybrid layers, wherein the organic content of the respective composition of the conversion agent and the method of application thereof within a wide range is adjustable.
  • WO 00/71626 discloses a chromium-free corrosion inhibitor containing water and a) 0.5 to 100 g / l hexafluoroanion of titanium (IV), silicon (IV) and / or zirconium (IV) b) 0 to 100 g / l Phosphoric acid c) 0 to 100 g / l of one or more compounds of cobalt, nickel, vanadium, iron, manganese, molybdenum or tungsten.
  • the conversion treatment is carried out here in the "dry-in-place" process, so that the proportion of organic polymers in the conversion layer can be adjusted with the polymer content in the treatment agent.
  • WO 2005/1 16294 discloses a conversion treatment agent which takes place in the presence of an organic polymer which, on the one hand, enhances the anticorrosive effect and the lacquer adhesion of the conversion layer and, on the other hand, carries the coloring substituent, so that the presence of this polymer on the metal surface can be recognized by the naked eye.
  • the luminescent marker substituents are selected from Tuloidin Blue and from Neutral Red. The advantage of such a treatment agent is that the luminescent so causing the color impression Marker molecule is firmly bound to the polymer backbone. The luminescence is thus clearly attributable to the presence of a conversion layer, so that, if appropriate, it is also possible to deduce the layer thickness of the conversion coating.
  • particulate inorganic pigments as an additional component in a conversion treatment.
  • Such pigments insofar as these are also present as nanoscale particles, give the conversion layer as well as the polymer constituents improved lacquer adhesion and corrosion resistance.
  • DE 10161383 discloses particulate inorganic systems selected from compounds of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc or zirconium having an average particle size of 6 to 150 nm as a further constituent of a corrosion-protecting treatment agent for layer formation in the "dry-in-place" method is applied.
  • the object of the present invention is therefore to provide chromium-free compositions and processes for the anticorrosive treatment of metal surfaces, wherein coating coatings with high corrosion resistance and good paint adhesion, which luminesce upon irradiation with ultraviolet light, are produced in a single step.
  • the ratio of organic to inorganic content of the anticorrosion coating layer should be variably adjustable over a wide range and the intensity of the luminescence thereof should be largely independent.
  • a chromium-free aqueous agent for the corrosion-protective treatment of metallic surfaces containing at least one particulate inorganic pigment characterized in that the particulate inorganic pigment in the case of Luminescent with ultraviolet light and the pH of the agent is not greater than 4 and not less than 1.
  • the treatment solution is free of chromium, i. contains no intentionally added chromium compounds.
  • traces of chromium can not be excluded as impurities, for example, as a result of leaching out of container material.
  • Luminescence the skilled person generally understands the radiative relaxation from electronically excited atomic, molecular and / or solid state states with the emission of light quanta.
  • Luminescence types preferred according to the invention are the fluorescence and / or phosphorescence caused by irradiation with ultraviolet light.
  • the ultraviolet light typically used in the present invention for electronically exciting the particulate inorganic pigment should not be shorter than 200 nm, preferably not shorter than 280 nm, and most preferably not shorter than 320 nm. ultraviolet light ”) is about 400 nm, but may also extend into the visible region of the light.
  • the inorganic luminescent pigments which can be used according to the invention comprise a "host material” and at least one doping element.
  • a "host material” is defined according to the invention as a material whose elements are partly replaced by small amounts of so-called doping elements. Doping elements are different from the elements forming the host material.
  • the particulate inorganic pigments used according to the invention are at least partially crystalline or have crystalline regions in which the lattice elements (for example atoms or ions) are arranged spatially in regularly repeating unit cells to form a three-dimensional lattice.
  • These crystalline domains within the inorganic pigment particles to be used according to the invention represent the crystalline skeleton hereinafter referred to as "host lattice.”
  • the doping of such a host lattice with suitable foreign atoms causes the luminescence upon irradiation with light of suitable wavelength, the individual impurity atoms initially receiving light energy change into an excited electronic atomic state, then under emission of a light quantum of lesser energy to relax back into the electronic ground state.
  • the host material of the luminescence pigment is selected from oxides, sulfides or oxide sulfides of a metal or a semimetal.
  • the metal or the semimetal from at least one member of the group which is formed from aluminum (preferably Al 3+ ), germanium (preferably Ge 4+ ), silicon (preferably Si 4+ ), scandium (preferably Sc 3+ ), yttrium (preferably Y 3+ ), lanthanum (preferably La 3+ ), cerium (preferably Ce 3+ ), praseodymium (preferably Pr 3+ ), neodymium (preferably Nd 3+ ), samarium (preferred Sm 3+ ), europium (preferably Eu 3+ ), gadolinium (preferably Gd 3+ ), terbium (preferably Tb 3+ ), dysprosium (preferably Dy 3+ ), holmium (preferably Ho 3+ ), erbium (preferably Er 3 + ), Thulium
  • host lattices which are derived from the lattice structures of the perovskite, such as, for example, Mg 2 GeO 6 , BaMgAl 10 Oi 7 , CeMgAl 10 Oi 9 and Y 2 O 3 , and the analogous sulfidic or mixed oxidic-sulfidic host lattices are preferred.
  • the host material is preferably doped with doping elements selected from at least one metal cation of a metal of the transition metals of the 3rd and 4th period or of the rare earth metals (lanthanides). It is of course according to the definition of a doping element that the metal chosen as the doping element is different from the metal of the host material.
  • the doping element is selected from at least one metal cation of Mn 2+ , Mn 4+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+ , Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ or Lu 3+ .
  • doped host materials in the form of particulate inorganic pigments which luminesce upon irradiation with ultraviolet light in the visible range of the light, and in particular those which are recognizable to the human eye with sufficient intensity to luminesce. neschirden properties of the pigment itself and not the agent or concentrate according to the invention are to be evaluated.
  • the size of the "primary particles" is taken as the basis for the classification of the particle or particle size.
  • Primary particles are particles which are held together due to primary ionic or covalent forces, for example in the form of a crystal lattice
  • secondary particles are understood to be agglomerates of two or more primary particles which adhere to one another due to weak ionic or other polarity-based forces on the outer surfaces or grain boundaries of the primary particles and require little energy, for example a simple mechanical one Dispersion and / or by adding a dispersant which causes the splitting of the particles by eliminating or reducing the weak binding forces between the primary particles.
  • the particulate inorganic luminescent pigments as marker material with good paint adhesion and corrosion protection properties, effective incorporation or generally good film-forming properties of these particles are a prerequisite. Therefore, in the agent or concentrate on which the invention is based, preferably at least 1 per cent, preferably at least 10 per cent, of inorganic pigment particles which have a particle size of not more than 2 ⁇ m, preferably not more than 0.2 ⁇ m and more preferably not have more than 0.02 microns.
  • the size distribution of the pigment particles basically all particle measuring methods are suitable, preferably measuring methods based on the principle of light diffraction.
  • the particle size data given in the context of the present invention relate to measurements with the MASTERSIZER X instrument, by Malvern Instruments, Herrsching, Germany, (version 1.2b).
  • the operation of this apparatus is based on the diffraction of a light beam by the particle size is associated with the diffraction angle.
  • the measurement of the light diffraction is possible directly and at any time in the agent or concentrate according to the invention.
  • the means or concentrate according to the invention are used for such a sedimentation analysis for particle size determination. From the relationship between size and density of the particles assumed to be spherical and their sinking rate according to the Stokes law, it is possible to deduce the percentage distribution of the particle sizes over the time course of the sedimentation.
  • the method of ultracentrifugation in which sedimentation can be carried out at up to 10 5 times the gravitational force, also makes it possible to determine particle size distributions of nanoscale dispersions. Further methods for determining the particle size are microscopy, electron microscopy, sieve analysis, determination of the density of the surface and the like.
  • the agent or concentrate according to the invention is present either mainly as a suspension or mainly as a dispersion of the inorganic pigment, a timely determination of the particle size distribution immediately after the formulation of the agent or concentrate is meaningful. Sedimentation and / or agglomeration processes define the stability of such suspensions or dispersions, so that there are defined maximum service lives or processing times for the particular agent or concentrate according to the invention. A control of the aforementioned preferred particle size distribution of the particulate inorganic luminescence pigment in the composition or concentrate via a continuous measuring method is therefore necessary for an optimal solution of the object underlying this invention.
  • At least 50% by weight of the pigment fraction initially used should always be suspended and / or dispersed in the composition or concentrate according to the invention, where at least 1 per hundred, preferably at least 10 per cent, of the inorganic pigment particles present have a particle size of not more than 2 ⁇ m, preferably not more than 0.2 ⁇ m and more preferably not more than 0.02 ⁇ m.
  • the percentage number fraction of pigment particles up to a defined particle size in the dispersion and / or suspension is calculated as follows from the experimentally determined particle size distribution N (D):
  • D max the upper limit for the particle diameter for which the number fraction of particles is to be determined, which is below and equal to this diameter D max .
  • the proportion of particulate inorganic pigments which luminesce upon irradiation with ultraviolet light is in the composition according to the invention, which at the same time represents an application solution, in particular for immersion methods, so-called “rinse” methods, preferably at least 0.05 g / l, more preferably 0.5 g / l, and is preferably not larger than 10 g / l.
  • the particulate inorganic pigments present in the composition according to the invention are deposited from the aqueous phase at the predetermined pH of not more than 4 and at least 1 on the metallic surface by contacting with the agent in a layer-forming manner. This happens due to the destabilization and agglomeration of the primary particles in close proximity to the metal surface.
  • This layer-forming destabilization of the dispersed pigment particles is in turn caused by an increase in the pH at the metal surface caused by a corrosive stain of the metallic substrate.
  • the increase in pH may extend several micrometers (10 "4 cm) into the interior of the treatment solution.
  • the agent according to the invention which at the same time represents an application solution, in particular for immersion processes, so-called “rinse” processes, preferably contains a total of at least 0.01 g / l, preferably at least 0.025 g / l, and up to 2 g / l, preferably up to 1 g / l, in particular up to 0.5 g / l of the elements titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron and at least such an amount of fluoride that the atomic ratio Ti to F and / or Zr to F and / or Si to F in the range from 1: 1 to 1: 6.
  • the said Ti, Zr and / or Si ions may be completely in the form of hexafluorocomplexes such as, for example, the hexafluoroacids or their water-soluble in the concentration range mentioned Salts such as the sodium salts are used, in this case the atomic ratio is 1: 6.
  • complex compounds in which in each case less than six fluoride ions are connected to the central elements Ti, Zr or Si. These can form themselves in the treatment solution if hexafluoro complexes of at least one of the central elements Ti, Zr or Si and also at least one further compound of one of these central elements are added to this.
  • further compounds are, for example, nitrates, carbonates, hydroxides and / or oxides thereof or another of the three mentioned central elements into consideration.
  • the agent according to the invention for more effective bonding of the luminescent pigments and increasing the paint adhesion of the otherwise purely inorganic corrosion-protective coating can also contain water-dispersible and / or water-soluble polymers or a polymer mixture with likewise layer-forming properties.
  • the result of the treatment with a polymer-containing aqueous agent is the formation of an organic-inorganic layer coating on the metal surface.
  • the respective organic or inorganic portion of the layer can be adjusted variably on the one hand on the composition of the composition according to the invention and on the other hand on the application method in a wide range.
  • the water-dispersible and / or water-soluble polymer or polymer mixture can consist of different groups, inter alia, epoxy resins, amino resins, phenol-aldehyde resins, polymers carrying carboxylic acid groups, polymeric alcohols, esterification products of polymeric alcohols with polymers carrying carboxylic acid groups, polymers carrying amino groups, homopolymers. or copolymers of vinylpyrrolidone and of polymers having phosphinic, phosphonic or phosphoric ester groups.
  • the phenol-aldehyde resins used are, in particular, amino-substituted poly (vinylphenol) compounds which are obtainable as Mannich adducts of poly (vinylphenols) with aldehydes and organic hydroxyl-containing amines.
  • poly (vinylphenols) with aldehydes and organic hydroxyl-containing amines.
  • poly-4-vinylphenol compounds can be found in WO 00/26437 and in the literature cited therein, in particular US Pat. No. 5,281,282.
  • Further preferred water-soluble and / or water-dispersible organic polymers are selected from:
  • polyvinyl alcohol or water-soluble or water-dispersible partial esters thereof b) polymers or copolymers of unsaturated mono- or dicarboxylic acids or their amides, c) esters of the polymers of groups a) and b), d) polymers or copolymers of vinylpyrrolidone, e) polymers of the diglycidyl ether of bisphenol A, f) copolymers of alkylenephosphonic or alkylenephosphinic acids and one or more unsaturated carboxylic acids.
  • a "partial ester” is understood to mean that only a part of the alcohol groups is esterified, the ester formation taking place with non-polymeric carboxylic acids.
  • the ester formation can be carried out with monobasic carboxylic acids having 1 to 4 carbon atoms.
  • the polymers or copolymers of group b) may be selected, for example, from homopolymers or copolymers of acrylic acid and / or methacrylic acid whose acid groups may be partially replaced by amide groups or esterified with alcohols, in particular with simple alcohols having 1 to 4 carbon atoms.
  • Specific examples are homo- or copolymers of or with methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and Glycerinpropo- xitriacrylat. These specific examples are known, for example, from WO 95/141 17.
  • the polymers of group b) can furthermore be selected from those which contain maleic acid monomers. A specific example of this is a maleic acid-methyl vinyl ether copolymer.
  • Polymers of group a) generally contain free alcohol groups, those of group b) free carboxylic acid groups. Therefore, one can use these two polymers not only in a mixture with each other, but in a form in which between the alcohol groups of the polymer a) and the carboxylic acid groups of the polymer b) at least partially a Esterbil- occurred. This is explained in more detail in WO 94/12570. The teaching described therein can also be used in the context of the present invention.
  • the treatment solution may contain polymers of group d).
  • polymers of group d Such polymers and their use in treatment solutions for the conversion treatment are described in more detail in DE-A-100 05 1 13 and DE-A-101 31 723.
  • additional polymers can be selected from those of group e), as described in more detail in US Pat. No. 5,356,490.
  • the average molecular weight of the organic polymers is preferably at least 10,000 daltons.
  • the upper limit of the molecular weight is not critical as long as the polymer is soluble or dispersible in the preferably acidic treatment solution in the desired concentration range.
  • the upper limit of the molecular weight may be 50,000,000, especially 20,000,000, and more preferably 10,000,000 daltons. An upper limit of 5,000,000 daltons may be sufficient.
  • the average molecular weight is preferably greater than 50,000 daltons and in particular greater than 100,000 daltons.
  • the average molar masses can be determined, for example, by gel permeation chromatography using a polyethylene glycol standard.
  • the proportion of water-dispersible and / or water-soluble polymers or of the polymer mixture in the composition according to the invention which at the same time represents an application solution, in particular for immersion processes, so-called “rinse” processes, is preferably at least 1 ppm, particularly preferably 50 ppm and is preferably at most 1000 ppm.
  • the pH of the composition according to the invention should not be significantly lower than 1, since lower pH values lead to an increasingly stronger pickling attack on the metal surface.
  • the pH is not less than 2 and especially not less than 2.5.
  • the formation of a conversion layer and / or the layer-forming deposition of the inorganic luminescent particles is no longer to the desired extent.
  • various auxiliaries or additives may be present in the composition according to the invention which further improve the corrosion resistance and / or paint adhesion of the coating resulting from the treatment with the agent according to the invention.
  • acid-stable particulate inorganic pigments which do not luminesce in the visible range of light, preferably silicates and particularly preferably SiC> 2 , the proportion of acid-stable particulate inorganic pigments being at least 0.05 g / l and at most 10 g / l.
  • inorganic compounds in particulate form which can be added to the composition according to the invention are carbonates, oxides, a silicate or a sulphate, in particular colloidal or amorphous particles based on at least one compound of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium , Yttrium, zinc or / and zirconium particularly preferred, in particular particles based on alumina, barium sulfate, ceria, rare earth, oxide, silica, silicate, titanium oxide, yttria, zinc oxide or zirconia.
  • the acid-stable particulate inorganic pigment which does not luminesce upon irradiation with ultraviolet light has a particle size distribution such that at least 1 of hundreds, preferably at least 10, of the acid-stable inorganic pigment particle has a particle size of not more than 2 ⁇ m, preferably not more more than 0.2 .mu.m, and more preferably not more than 0.02 .mu.m.
  • inorganic pigment compounds in particle form with higher or higher electrical conductivity use in particular those of oxides, phosphates, phosphides or sulfides of aluminum, iron or molybdenum, in particular aluminum phosphide or iron oxide, iron phosphide, at least one molybdenum compound such as molybdenum sulfide, graphite or / and carbon black, these particles then also have such an average particle size can, that they possibly protrude somewhat stronger from the layer produced according to the invention.
  • the agent according to the invention may additionally contain cations of copper and / or oxoanions of molybdenum, tungsten and / or vanadium in a proportion of at least 5 ppm and at most 200 ppm.
  • Oxoanions of phosphorus may also be present in the composition according to the invention with a proportion of the oxoanions, based on the element phosphorus, of at least 0.5 g / l and at most 20 g / l.
  • the inventive agent fluoride ions may be additionally contained in the inventive agent fluoride ions, wherein the proportion of fluoride Ions is at least 0.05 g / l and at most 5 g / l.
  • a further aspect of this invention is also the provision of concentrates which, when appropriately diluted, give the composition according to the invention or as a concentrated aqueous composition directly for use, ie for the treatment of the metallic Surface, can be used.
  • the direct use of such concentrates according to the invention is particularly suitable for so-called “no-rinse” processes in which a defined liquid film is applied to the metal substrate (eg via roller application or spray application with squeezing) and then dried to form a layer "Concentrate a high proportion of water-soluble and / or water-dispersed polymers which form a homogeneous closed film coating at a suitable specific temperature (" film forming temperature ").
  • the present invention therefore comprises an aqueous concentrate for the anticorrosive treatment of metallic surfaces, characterized in that by dilution with water by a factor of at least 10 and at most 200 the agent according to the invention results according to the preferred compositions described above.
  • a concentrate which, when diluted by a factor of at least 10 and at most 200, either contains the agent according to the invention: a) fluorocomplexes of the elements titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron with a total content of at least 0, 01 g / l, preferably at least 0.025 g / l, and up to 2 g / l, preferably up to 1 g / l, in particular up to 0.5 g / l; b) at least one water-dispersible and / or water-soluble polymer having a proportion of at least 1 ppm, particularly preferably 50 ppm and preferably at most 1000 ppm; or c) both a) and b), wherein the particulate inorganic pigments which luminesce upon irradiation with ultraviolet light, in the concentrate in a proportion of at least 0.05 g / l, more preferably of 0.5 g /
  • the invention likewise encompasses a concentrate which, when diluted by a factor of at least 10 and not more than 200, either contains the agent according to the invention comprising: a) the particulate inorganic pigments which luminesce when irradiated with ultraviolet light, in a proportion of at least 0.05 g / 1, particularly preferably 0.5 g / l and preferably not more than 10 g / l; b) at least one water-dispersible and / or water-soluble polymer having a proportion of at least 1 ppm, particularly preferably 50 ppm and preferably at most 1000 ppm; or c) both a) and b), wherein the fluorocomplexes of the elements titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron in a proportion of at least 0.01 g / l, preferably at least 0.025 g / l , and up to 2 g / l, preferably up to 1 g
  • the invention comprises a concentrate which, when diluted by a factor of at least 10 and at most 200, contains the agent according to the invention comprising: a) the particulate inorganic pigments which luminesce upon irradiation with ultraviolet light, in a proportion of at least 0.05 g / l , more preferably 0.5 g / l, and preferably not greater than 10 g / l; b) at least one water-dispersible and / or water-soluble polymer having a proportion of at least 1 ppm, particularly preferably 50 ppm and preferably at most 1000 ppm; and c) the fluorocomplexes of the elements titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron in a proportion of at least 0.01 g / l, preferably at least 0.025 g / l, and up to 2 g / l, preferably up to 1 g / l, in particular up to 0.5
  • the concentrate of the invention contains largely no chromium compounds and the content of chromium compounds based on the element chromium is preferably less than 100 ppm.
  • the pH of the concentrate according to the invention is such that when diluted by a factor of at least 10 and at most 200, a pH of not greater than 4 and not less than 1 results.
  • the pH of the concentrate may therefore also be below 1, but should not be less than 0.3.
  • the method according to the invention comprises treating a metallic surface with such a means and visually assessing the quality of the treatment process on the basis of a luminescence of the metal surface which is as homogeneous as possible, caused by the inorganic pigment according to the invention immobilized in the protective layer against corrosion of the metallic substrate and / or superficially immobilized , And therefrom derived further process steps to optimize the treatment process and / or the layer quality.
  • the present invention therefore also encompasses a metal substrate treated according to one or more of the methods described herein ("rinse” / "no-rinse” method), wherein the substrate thus treated luminesces upon irradiation with ultraviolet light, and preferably luminescence in the visible region of the light is visible to the human eye.
  • Such a treated or coated metal substrate can be used in the body shop in automotive manufacturing, shipbuilding, construction and for the production of white goods.
  • the metal surfaces that can be treated with the agent, concentrate and method of the invention are preferably selected from zinc and zinc alloy surfaces, galvanized or alloy galvanized steel, aluminum and aluminum alloys, magnesium and magnesium alloys, titanium and titanium alloys.
  • the metal surfaces may be surfaces of the metals mentioned or their alloys as such, but also surfaces of a substrate such as steel, which is coated with the metals or their alloys. Examples of the latter are electrolytically galvanized or hot dip galvanized steel, aluminized steel, or coated steels such as Galvalume or Galfan, which carry a coating of zinc / aluminum alloys.

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  • 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)
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Abstract

La présente invention concerne un agent aqueux dans une large mesure dépourvu de chrome, destiné au traitement anti-corrosion de surfaces métalliques et contenant un pigment minéral particulaire, le pigment devenant luminescent lorsqu'il est exposé à un rayonnement de lumière ultraviolette, et le pH de l'agent aqueux étant inférieur ou égal à 4 et supérieur ou égal à 1. L'invention concerne aussi des concentrés qui soit servent de concentrés pour l'agent de l'invention, soit sont utilisés directement pour le traitement de surfaces métalliques. Le procédé de l'invention comprend le traitement d'une surface métallique avec un tel agent et l'évaluation optique de la qualité du processus de traitement grâce à une homogénéité optimale de la luminescence de la surface métallique rendue possible par le pigment minéral de l'invention immobilisé en surface et/ou intégré à la couche de protection du substrat contre la corrosion; ainsi que d'autres opérations dérivées de celui-ci permettant d'optimiser le processus de traitement et/ou la qualité de la couche.
PCT/EP2007/063648 2007-02-01 2007-12-11 Prétraitement pour métaux contenant des pigments luminescents WO2008092528A1 (fr)

Priority Applications (1)

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JP2009547552A JP2010518185A (ja) 2007-02-01 2007-12-11 発光顔料により前処理された金属

Applications Claiming Priority (2)

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DE200710005943 DE102007005943A1 (de) 2007-02-01 2007-02-01 Metall-Vorbehandlung mit lumineszierenden Pigmenten
DE102007005943.6 2007-02-01

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CN111373074B (zh) * 2017-11-24 2021-12-21 日本制铁株式会社 化学转化处理合金材料的制造方法和化学转化处理合金材料的制造方法中使用的化学转化处理液再生装置
CN108676412A (zh) * 2018-04-24 2018-10-19 中国石油化工集团公司 一种水性蓄光性发光防锈涂料及其制备方法

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WO2000071626A1 (fr) * 1999-05-20 2000-11-30 Henkel Kommanditgesellschaft Auf Aktien Agent anticorrosif depourvu de chrome et procede de protection contre la corrosion
WO2001051681A2 (fr) * 2000-01-11 2001-07-19 C+C Cours Gmbh Surfaces metalliques brillantes
JP2004083771A (ja) * 2002-08-28 2004-03-18 Nippon Hyomen Kagaku Kk 金属保護被膜形成用組成物

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