EP2393611B1 - Produit de revêtement pour peintures résistantes à la corrosion - Google Patents

Produit de revêtement pour peintures résistantes à la corrosion Download PDF

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Publication number
EP2393611B1
EP2393611B1 EP10700303.0A EP10700303A EP2393611B1 EP 2393611 B1 EP2393611 B1 EP 2393611B1 EP 10700303 A EP10700303 A EP 10700303A EP 2393611 B1 EP2393611 B1 EP 2393611B1
Authority
EP
European Patent Office
Prior art keywords
basecoat
compounds
water
weight
basecoat material
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.)
Not-in-force
Application number
EP10700303.0A
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German (de)
English (en)
Other versions
EP2393611A1 (fr
Inventor
Michael Richert
Wolfgang Duschek
Michael Dornbusch
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BASF Coatings GmbH
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BASF Coatings GmbH
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Publication of EP2393611A1 publication Critical patent/EP2393611A1/fr
Application granted granted Critical
Publication of EP2393611B1 publication Critical patent/EP2393611B1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the present invention relates to coating compositions for corrosion-resistant coatings, in particular for multicoat color and / or effect paint systems.
  • Modern motor vehicles usually have multicoat color and / or effect paint systems.
  • these multicoat paint systems comprise an electrodeposition coating, a surfacer coating, antistonechip primer or functional coating, a color and / or effect basecoat and a clearcoat.
  • the multicoat paint systems are preferably produced by means of what are known as wet-on-wet processes, in which a clearcoat film is applied to a dried, uncured basecoat film, after which at least the basecoat film and the clearcoat film are thermally cured together.
  • the preparation of the electrodeposition coating and the surfacer coating, antistonechip primer or functional layer can also be included in this process.
  • the surfacer coats, antistonechip primers or functional coatings are crucial for such important technological properties as impact resistance and smoothness and course of the overall finish.
  • the quality of surfacer coats, antistonechip primers or functional coatings is therefore subject to particularly stringent requirements. They must also be able to be produced in a simple and excellently reproducible manner.
  • WO 2005/021168 A1 and WO 2006/062666 A1 made important contributions to known methods.
  • a substrate is coated with an electrodeposition paint.
  • the resulting electrocoating layer is baked.
  • the electrodeposition coating layer is coated with a first, physically or thermally curable, aqueous basecoat.
  • the resulting first basecoat film is coated with a second, thermally curable, aqueous basecoat without first curing completely.
  • the resulting second basecoat film is coated with a clearcoat without previously fully curing, thereby resulting in a clearcoat film.
  • the first and second basecoat films and the clearcoat film are baked together.
  • the first, physically or thermally curable, aqueous basecoat material contains as binder at least one water-dilutable polyurethane resin, in particular acrylated polyurethanes.
  • the first basecoat may contain, among other things, titanium dioxide as pigment, talc as filler and UV absorber.
  • the first basecoat provides a first basecoat or functional layer capable of substituting the conventional surfacer coatings, antistonechip primers, or functional coatings without loss of significant technological properties of the multi-layer coatings at dry film thicknesses ⁇ 35 microns, preferably about 15 microns.
  • UV absorbers in particular UV-absorbing pigments
  • WO 2005/021168 A1 and WO 2006/062666 A1 described that the UV stability of the relevant multi-layer coatings is guaranteed.
  • the anticorrosion agents must on the one hand have sufficiently high mobility in order to reach the exposed metallic substrate, on the other hand be well integrated in the layered composite in order to prevent unnecessary bleeding in moisture cycles by osmotic pressure.
  • the corrosion inhibitors commonly used in the electrodeposition coating layer are pigmented and are added with the binder. Low molecular corrosion inhibitors can only reach the interface between the substrate and the paint during the deposition process and thus be deposited if they bear a positive charge, with such corrosion protection agents generally impairing the properties of the entire paint pool and thus of the paint finish.
  • pigment-type anticorrosion agents have no or only very little mobility owing to their particle size.
  • coating compositions which may contain up to 5 wt .-%, based on the coating agent, water and / or solvents, which are according to the invention for the direct coating of metals, in particular for the coating of metal bands, determined, but also over a electrocoat film can be applied.
  • the coating compositions are cured with actinic radiation and contain low molecular weight organic corrosion inhibitors and preferably further inorganic anti-corrosive pigments. In addition to the corrosion inhibitors and / or pigments, color pigments can furthermore be present in the coating composition.
  • a multicoat paint system in automotive OEM finishing, as described in the introduction, will not be described.
  • the electrodeposition coating is sensitively damaged by photodegradation, which leads to markedly reduced adhesion of the electrodeposition coating layer and thus to increased corrosive infiltration of the layer Neighborhood leads to the bare metallic substrate, which is just to be avoided by the present invention.
  • the application properties of in DE 103 00 751 A1 can be adjusted to the application conditions only with great effort, in particular with regard to the rheology, as they are necessary for the above-described multicoat paint systems in automotive OEM finishing.
  • the coating composition according to the invention provided first basecoats (A) which even in a layer thickness of about 15 ⁇ m could fully replace conventional surfacer coats, antistonechip primers or functional layers without the performance properties of the multicoat paint systems, in particular the good adhesion to the adjacent lacquer layers as well as the Rockfall protection and UV stability, even after long-term exposure, were adversely affected.
  • the coating composition of the invention could be carried out in existing systems for the application of basecoats by electrostatic spray application and pneumatic spray application, without the need for conversions were necessary.
  • the binder (a.1) is the binder (a.1)
  • the preferably thermally curable and particularly preferably aqueous basecoat material (A) which is used for the multicoat system described below contains at least one binder as its essential constituent (a.1), which preferably has functional groups (Gr).
  • Particularly preferred functional groups (Gr) are hydroxyl, carbamate, epoxy, amino and / or isocyanate groups, with hydroxyl groups being very particularly preferred as functional groups (Gr).
  • Suitable binders (a.1) for use in the coating compositions of the invention are, for example in the Patent applications DE 44 38 504 A1 . EP 0 593 454 B1 . DE 199 48 004 A1 . EP 0 787 159 B1 and WO 2005/021168 A1 described. The preferred are in EP 0 593 454 B1 . EP 0 787 159 B1 . DE 199 48 004 A1 and or WO 2005/021168 A1 used binders described, wherein in addition to these binders even more binders can be used.
  • the binders (a.1) preferably contain combinations of at least 2 components selected from the group of preferably water-dilutable polyester resins (a.1.1), preferably water-dilutable polyurethane resins (a.1.2) and / or preferably water-dilutable polyacrylate resins (a.1.3).
  • the components (a.1.1.1) which are preferably used for the preparation of the water-dilutable polyester resins (a.1.1) are in EP 0 593 454 B1 on page 8, lines 26 to 51, the preferred components (a.1.1.2) in EP 0 593 454 B1 on page 8, line 52, to page 9, line 32 described.
  • the preparation of the polyester resins (a.1.1) and their neutralization are in EP 0 593 454 B1 on page 9, lines 33 to 42.
  • the components (a.1.2.1) which are preferably used for the preparation of the water-dilutable polyurethane resins (a.1.2) are disclosed in EP 0 593 454 B1 on page 6, lines 6 to 42, the preferred components (a.1.2.2) in EP 0 593 454 B1 on page 6, line 43, to page 7, line 13, very particular preference is given to using polyisocyanates based on isophorone diisocyanate and tetramethylxylene diisocyanate, the components preferably used (a.1.2.3) in EP 0 593 454 B1 on page 7, lines 14 to 30, the preferred components (a.1.2.4) in EP 0 593 454 B1 on page 7, lines 31 to 53, and the preferred components (a.1.2.5) in EP 0 593 454 B1 on page 7, lines 54 to 58 described.
  • the preparation of the polyurethane resins (a.1.1) and their neutralization are in EP 0 593 454 B1 on page 7, line 59, to page 8, line 2 described
  • the monomeric components (a.1.3.a.1), (a.1.3.a.2), (a.1.3.a.3), (a.1.3.b.1) and (a.1.3.b. 2) are selected in type and amount so that the polyacrylate resin obtained from the aforementioned components has an acid number according to DIN EN ISO 3682 of 20 to 100 mg KOH / g nonvolatile content and a hydroxyl value according to DIN EN ISO 4629 of 5 to 200, preferably 10 to 150 mg KOH / g nonvolatile content.
  • the preferred weight proportions of the aforementioned components are in EP 0 787 159 B1 on page 3, lines 4 to 6 described.
  • the components (a.1.3.1) which are preferably used for the preparation of the water-dilutable polyurethane-modified polyacrylate resins (a.1.3) are described in EP 0 787 159 B1 on page 3, line 38, to page 6, line 13, the preferred components (a.1.3.a.1) in EP 0 787 159 B1 on page 3, lines 13 to 20, the preferred components (a.1..3.a.2) in EP 0 787 159 B1 on page 3, lines 21 to 33, the components preferably used (a.1.3.a.3) in EP 0 787 159 B1 on page 3, lines 34 to 37, the preferred components (a.1.3.b.1) in EP 0 787 159 B1 on page 6, lines 33 to 39, and the preferred components (a.1.3.b.2) in EP 0 787 159 B1 on page 6, lines 40 to 42.
  • step (1) The preferred polyurethane prepolymers used in step (1) above are described in US Pat DE 199 48 004 A1 , Page 4, line 19, to page 8, line 4 described.
  • the preferred adducts used in step (2) above are described in U.S. Pat DE 199 48 004 A1 , Page 8, line 5, to page 9, line 40 described.
  • the graft copolymerization is as in DE 199 48 004 A1 , Page 12, line 62, to page 13, line 48, with the in DE 199 48 004 A1 , Page 11, line 30, to page 12, line 60, described monomers.
  • the graft copolymer (a.1.3) is partially or completely neutralized, whereby a part or all of the potentially anionic groups, ie the acid groups, are converted into an anionic group.
  • Suitable neutralizing agents are known from DE 44 37 535 A1 , Page 6, lines 7 to 16, or the DE 199 48 004 A1 , Page 7, lines 4 to 8, known.
  • the content of binder (a.1) in the basecoat (A) can vary very widely and depends on the requirements of the individual case.
  • the content of (a.1) in the basecoat (A), based on the solids of the basecoat (A), is preferably from 10 to 90% by weight, in particular from 15 to 85% by weight.
  • the pigment (a.2) of the basecoat (A) is the pigment (a.2) of the basecoat (A)
  • the basecoat (A) contains at least one color or effect pigment (a.2).
  • the pigment (a.2) may preferably be selected from the group consisting of organic and inorganic, coloring, optically effecting, color and optically effecting, fluorescent and phosphorescent pigments, in particular from the group consisting of organic and inorganic, coloring, optically effecting pigments , color and optical effect pigments, or mixtures thereof to be selected.
  • the pigment (a.2) has UV-absorbing constituents.
  • suitable effect pigments which may also be coloring
  • metal flake pigments such as commercial aluminum bronzes, according to DE 36 36 183 A1 chromated aluminum bronzes, and commercial stainless steel bronzes
  • non-metallic effect pigments such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which have shades of pink to brown-red, or liquid-crystalline effect pigments.
  • non-metallic effect pigments such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which have shades of pink to brown-red, or liquid-crystalline effect pigments.
  • Suitable inorganic color pigments are white pigments such as zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
  • white pigments such as zinc white, zinc sulfide or lithopone
  • Black pigments such as carbon black, iron manganese black or spinel black
  • Colored pigments such as chromium oxide
  • suitable organic coloring pigments are monoazo pigments, bisazo pigments, anthraquinone pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, Indanthrone pigments, isoindoline pigments, isoindolinone pigments, azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments or aniline black.
  • fluorescent and phosphorescent pigments are bis (azomethine) pigments.
  • the content of the pigments (a.2) in the basecoat (A) can vary very widely and depends primarily on the intensity of the effects, in particular the optical effects, and / or the hue that is or should be adjusted ,
  • the pigments (a.2) in the basecoat (A) are preferably in an amount of 0.5 to 60, preferably 0.5 to 45, particularly preferably 0.5 to 40, very particularly preferably 0.5 to 35 and in particular 0 , 5 to 30 wt .-%, based on the solids of the basecoat (A) included
  • the pigments (a.2) are preferably ground to facilitate incorporation into the coating composition with at least one constituent of the binder (a.1) described above. Particularly preferably, the component (a.1.2) of the binder (a.1) described above is used for the trituration.
  • the basecoat (A) particularly preferably contains at least one UV-absorbing pigment (a.2.1).
  • the UV-absorbing pigments (a.2.1) are selected from the group consisting of titanium dioxide pigments and carbon black pigments.
  • the content of UV-absorbing pigments, in particular of titanium dioxide and / or carbon black pigments (a.2.1) in the basecoat (A) can vary and depends on the requirements of the individual case, in particular on the degree of transmission of the UV radiation which is caused by the further pigments in the basecoat (A) and / or in the further layers of the multicoat paint system according to the invention.
  • the content of titanium dioxide pigment (a.2.1) in the basecoat (A) is preferably based on the solids of the basecoat material (A), at 0.1 to 50% by weight, in particular 0.5 to 40% by weight.
  • the content of carbon black pigment (a.2.1) in the basecoat (A), based on the solids of the basecoat (A), is preferably 0.005 to 5% by weight, in particular 0.01 to 2% by weight.
  • the water-soluble or water-dispersible oligomeric or polymeric component (a.3) has a main body (GK) with at least two repeating monomer units (ME) and at least one monodentate and / or polydentate potentially anionic ligand (L) with an electron-donating property, wherein the ligand (L) allows good adhesion to the metallic substrate, with which metal ions released upon corrosion of the substrate can form chelates (to " Chelates ", see Römpp Online, Georg Thieme Verlag, Stuttgart, New York, 2005, chapter” Chelates ") and in the thermal curing of the multi-layer coating does not lose its property as a chelating agent.
  • the ligands (L) inhibit corrosion by reducing and / or occupying the metal surface by reducing them for corrosion accessible proportion of the metal surface and / or cause a shift in the electrochemical potential of the half cell formed on the metal surface.
  • component (a.3) can additionally suppress, by means of a buffer effect, the shift in the pH of the aqueous medium at the interface with the metal which is necessary for the corrosion.
  • Component (a.3) preferably has a water solubility or water dispersibility of at least 20 g / liter of water, in particular of at least 50 g / liter of water and more preferably of at least 80 g / liter of water.
  • Water solubility or water dispersibility means that thermodynamically stable solutions or dispersions of component (a.3) are formed in water.
  • the specification of the water solubility in g / liter corresponds to the maximum concentration of dissolved component (a.3) in water at room temperature (cf. Rompp Online, Georg Thieme Verlag, 2008 ).
  • the specification of the water dispersibility in g / liter corresponds to the maximum concentration of dispersed component (a.3) in water at room temperature.
  • water-dispersible means that component (a.3) forms stable aggregates with an average particle diameter of ⁇ 500, preferably of ⁇ 100 nm and particularly preferably of ⁇ 50 nanometers, up to a certain concentration in the aqueous phase.
  • the basic body (GK) can, if the water solubility or water dispersibility is not sufficient, be hydrophilically modified in a known manner.
  • ionic and / or nonionic substituents are introduced into the main body (GK).
  • anionic substituents these are in particular carboxylate, sulfonate and / or sulfate groups, in the case of cationic substituents ammonium, sulfonium and / or phosphonium groups, and in the case of nonionic Groups oligo- or polyalkoxylated, particularly preferably ethoxylated, substituents.
  • the ligand (L) can additionally contribute to the hydrophilization of component (a.3), as is the case in particular with the anionic phosphonate groups and with the nonionic oligo- or polyalkoxylated, particularly preferably ethoxylated, substituents.
  • suitable monomer units (ME) for the main body (GK) of component (a.3) are optionally hydrophilically modified polyols which can be reacted with polyacids to polyesters and polyisocyanates to give polyurethanes, the polyester or polyurethane basic body usually being a lower weight average molecular weight Mw as the binder component (a.1).
  • the weight-average molecular weight M w (determinable by gel permeation chromatography according to standards DIN 55672-1 to -3) of the main body (GK) is preferably more than 400 daltons, more preferably more than 500 daltons and most preferably more than 600 daltons.
  • the main body of component (a.3) has at least two, preferably at least three and in particular at least five of the abovementioned monomer units (ME).
  • Polyethyleneimines having weight-average molecular weights Mw of more than 500 daltons, in particular more than 600 daltons, are very particularly preferably used as the main body (GK).
  • the ligands (L) are preferably prepared by reacting the functional groups of the main body (GK) with ligand formers (LB).
  • ligand formers (LB) carrying the ligands (L) and other functional groups which react with functional groups of the main body (GK) all compounds with monodentate and / or polydentate potentially anionic ligands (L) with electron-donating properties are suitable which allows good adhesion to the metallic substrate, which can form chelates with the metal ions released upon corrosion of the substrate, which do not lose their property as chelating agents during the thermal curing of the multicoat paint system, and preferably from the main body (GK) in only minor proportions, especially in proportions of less than 25 mol%, based on the totality of the ligands split off.
  • the component (a.3) is preferably in the basecoat (A) in amounts of 0.1 to 20, preferably 0.2 to 10, particularly preferably 0.5 to 5 wt .-%, each based on the total weight of the basecoat ( A).
  • the basecoat contains (A), preferably at least one talcum component (a.4).
  • the content of talc (a.4) can vary very widely and depends on the requirements of the individual case.
  • the content of (a.4), based on the solids of the basecoat material (A) is from 0.1 to 5% by weight, in particular from 0.5 to 2% by weight.
  • the basecoat (A) may contain at least one customary and known additive (a.5) in effective amounts.
  • the additive (a.5) or the additives (a.5) is selected from the group consisting of crosslinking agents other than component (a.3); from the binders (a.1) different, oligomeric and polymeric binders; from organic and inorganic, colored, transparent, opaque, organic and inorganic pigments, fillers and nanoparticles, organic solvents, drying agents, anti-settling agents, UV absorbers, light stabilizers, radical scavengers, which are different from components (a.2) to (a.4) , Deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, leveling agents, film-forming aids, as well as rheology-controlling additives and flame retardants selected.
  • suitable additives are disclosed in the German patent application DE 199 48 004 A 1 , Page 14, line 32, to page 17, line 5 described, wherein preferably amino resins as the predominant or sole of the component (a.3) different crosslinking agents in the basecoat (A) in the in DE 199 48 004 A1 , Page 16, lines 6 to 14, described amounts of 0.1 to 30, preferably 0.3 to 20, particularly preferably 0.5 to 10 wt .-%, each based on the total weight of the basecoat (A) are included ,
  • the preparation of the coating composition according to the invention has no peculiarities, but preferably takes place by mixing the constituents described above and homogenizing the resulting mixtures by means of customary and known mixing methods and apparatuses such as in particular stirred tank, stirred mills, Ultraturrax, in-line dissolvers, static mixers Sprocket dispersers, pressure relief nozzles and / or microfluidizers.
  • the multicoat system according to the invention can be applied by means of all customary and known methods for the application of liquid coating materials, it is advantageous for the process according to the invention for producing the multicoat systems if the basecoat (A) is prepared by means of the electrostatic spray application (ESTA), preferably with high rotation bells, is applied.
  • the basecoat material (A) is applied in such a wet layer thickness that, after curing of the resulting resist layer from the basecoat (A), a dry film thickness of 6 to 25 .mu.m, preferably 7 to 20 .mu.m, more preferably 8 to 18 .mu.m results.
  • the basecoat material (A) is immediately coated with the thermally curable, preferably aqueous basecoat material (B).
  • the basecoat film of the coating composition according to the invention is first flashed off or dried, but not or only partially cured, and then coated with the thermally curable, preferably aqueous basecoat material (B).
  • the thermally curable, aqueous basecoat (B) is a conventional and well-known aqueous basecoat, such as he for example from the patent application WO 2005/021168 , Page 24, lines 11 to 28 is known.
  • the aqueous basecoat material (B) like the basecoat material (A), contains component (a.3) in amounts of 0.1 to 20, preferably 0.2 to 10, particularly preferably 0.5 to 5 Wt .-%, each based on the total weight of the basecoat (B).
  • the basecoat (B) can be applied by means of all customary and known methods for the application of liquid coating materials, it is advantageous for the method according to the invention if it is applied with the aid of the ESTA high rotation. It is preferably applied in such a wet layer thickness that, after the curing of the resulting basecoat film (B), a dry film thickness of 4 to 25 .mu.m, preferably 5 to 15 .mu.m, particularly preferably 6 to 10 .mu.m, results.
  • the basecoat (A) and the basecoat (B) are applied with such a wet film thickness that after curing a total dry film thickness of basecoat (A) and basecoat (B) of 10 to 50 .mu.m, preferably 12 to 35 .mu.m , particularly preferably 14 to 28 microns results.
  • the coating of the basecoat (A) or preferably the basecoat (B) is immediately coated with the clearcoat (C). Or it is first flashed off or dried, but not or only partially cured, and then coated with the clearcoat (C).
  • the clearcoat material (C) is a transparent, in particular optically clear, thermally and / or actinic-radiation-curable coating material.
  • Suitable clearcoats (C) are all customary and known one-component (1K), two-component (2K) or multi-component (3K, 4K) clearcoats, powder clearcoats, powder slurry clearcoats or UV curable clearcoats.
  • the clearcoat material (C) selected for the process according to the invention is applied by means of the customary and known application processes, which are adapted to the physical state (liquid or pulverulent) of the clearcoat material (C).
  • Suitable clearcoats and methods for their application are, for example, from the patent application WO 2005/021168 , Page 25, line 27, to page 28, line 23 known.
  • the substrates can be constructed from a wide variety of materials and combinations of materials. Preferably, they are at least partially made of metals, wherein spatially next to the metallic substrates plastic substrates may be arranged, as may be the case, for example, in plastic attachments, which are joined together with the metal body. Most preferably, the substrates are composed of metals, in particular of steels.
  • the substrates can have a wide variety of uses.
  • the substrates are preferably bodies of motor vehicles, in particular cars, motorcycles, trucks and buses, and parts thereof; industrial hardware; Coils, containers and everyday items. In particular, the substrates are car bodies and parts thereof.
  • primers (G) all known inorganic and / or organic primers, in particular for metal or plastic, can be used per se.
  • customary and known electrodeposition coatings are used as primers (G).
  • the electrodeposition coatings (G) are prepared in a conventional manner from electrophoretically, in particular cathodically, electrodepositable coatings.
  • the resulting electrodeposition coating layers (G) are preferably thermally cured before the application of the basecoat material (A). However, they can also be merely dried and not or only partially cured, after which they are cured together with the other layers of coating material according to the invention, preferably basecoat (B) and clearcoat (C).
  • the applied layers of basecoat (A), basecoat (B) and clearcoat (C) are common thermally hardened. If the clearcoat (C) is also curable with actinic radiation, a postcure by irradiation with actinic radiation takes place. If the primer (G) is not yet cured, it is cured in this process step with.
  • Curing may take place after a certain period of rest, also referred to as venting, between and after application of the primer, the basecoat (A), the basecoat (B) and finally the clearcoat (C).
  • the rest period may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 to 45 minutes. It serves, for example, for the course and degassing of the paint layers or for the evaporation of volatile constituents.
  • the rest period can be supported and / or shortened by the application of elevated temperatures up to 90 ° C and / or by a reduced air humidity ⁇ 10 g water / kg air, in particular ⁇ 5 g / kg air, provided that no damage or changes in the paint layers occur, such as premature full networking.
  • the thermal curing has no special features, but takes place according to the usual and known methods such as heating in a convection oven or irradiation with IR lamps. Here, the thermal curing can also be done gradually.
  • Another preferred curing method is near infrared (NIR) curing. Particularly preferred is a method in which the component water is rapidly removed from the wet layers. Suitable methods of this kind are used, for example, by Roger Talbert in Industrial Paint & Powder, 04/01, pages 30 to 33, “Curing in Seconds with NIR” , or in Electroplating, Volume 90 (11), pages 3098 to 3100, »Painting Technology "NIR drying every second of liquid and powder coatings".
  • NIR near infrared
  • the thermal curing takes place at a temperature of 50 to 170, more preferably 60 to 165 and in particular 80 to 150 ° C for a time of 1 minute to 2 hours, more preferably 2 minutes to 1 hour and especially 3 to 45 minutes ,
  • the resulting finishes are of excellent automotive quality. In addition to excellent stone chip resistance, they have excellent adhesion to the primer (G) and to the subsequent varnish layers and, in particular, excellent resistance to corrosive infiltration and resulting blister corrosion of the multilayer composites in the vicinity of bare areas, such as those produced by rockfall
  • neopentyl glycol From 898 parts by weight of neopentyl glycol, 946 parts by weight of hexane-1,6-diol, 570 parts by weight of hexahydrophthalic anhydride, 2107 parts by weight of an oligomeric fatty acid (Pripol ® 1012 from Uniqema, dimer content at least 97 weight %, Trimers content at most 1 wt .-%, monomer content at most traces) and 946 parts by weight of trimellitic anhydride was in a common solvent of the polyester (a.1.1) with an acid number according to DIN EN ISO 3682 of 32 mg KOH / g nonvolatile content and a hydroxyl number according to DIN EN ISO 4629 is 72 mg KOH / g non-volatile content, prepared in deionized water and with dimethylethanolamine to a pH of 7.6 and with further deionized water to a non-volatile content of 60.0 wt. %,
  • the polyurethane with an acid number according to DIN EN ISO 3682 of 25 mg KOH / g non-volatile content was placed in deionized water, the solvent removed and with further deionized water and with dimethylethanolamine to a pH of 7.2 and a non-volatile content of 27.0% by weight.
  • neopentylglycol From 1173 parts by weight of neopentylglycol, 1329 parts by weight of hexane-1,6-diol, 2469 parts by weight of isophthalic acid and 1909 parts by weight of an oligomeric fatty acid (Pripol ® 1012 from Uniqema, dimer content at least 97 weight %, Trimer content at most 1% by weight, monomer content at most traces) in a common solvent was a polyester precursor having an acid number according to DIN EN ISO 3682 of 3 mg KOH / g nonvolatile content and a hydroxyl number according to DIN EN ISO 4629 of 75 mg KOH / g of nonvolatile matter and adjusted to a non-volatile content of 74.0% by weight.
  • the polyurethane with an acid number according to DIN EN ISO 3682 of 25 mg KOH / g non-volatile content was placed in deionized water, the solvent removed and with further deionized water and with dimethylethanolamine to a pH of 7.4 and a non-volatile content of 31.5% by weight.
  • neopentylglycol 1076 parts by weight of hexane-1,6-diol, 1325 parts by weight of isophthalic acid and 3277 parts by weight of an oligomeric fatty acid (Pripol ® 1012 from Uniqema, dimer content at least 97 weight %, Trimer content at most 1% by weight, monomer content at most traces) in a common solvent was a polyester precursor having an acid number according to DIN EN ISO 3682 of 3 mg KOH / g nonvolatile content and a hydroxyl number according to DIN EN ISO 4629 of 78 mg KOH / g of nonvolatile matter and adjusted to a non-substantial content of 73.0% by weight.
  • polyester pre-product 4085 parts by weight of the polyester pre-product were in a common solvent with 186 parts by weight of neopentyl glycol and 1203 parts by weight of m-tetramethylxylene diisocyanate (TMXDI ® (Meta), Cytec Ind.) was heated and the reaction was up to an isocyanate content of 1.65 wt .-%, based on the total weight, carried out. Thereafter, 214 parts by weight of diethanolamine (2,2'-iminobisethanol) were added and stirred until no more free isocyanate groups were detectable.
  • TXDI ® m-tetramethylxylene diisocyanate
  • the polyurethane precursor having an acid number according to DIN EN ISO 3682 of 0.1 mg KOH / g nonvolatile fraction and a hydroxyl number according to DIN EN ISO 4629 was 49 mg KOH / g nonvolatile content was reduced to a nonvolatile content of 59.5 wt .-%, discontinued.
  • 1017 parts by weight of the polyurethane precursor was in a first stage in a common solvent, a mixture of 1369 parts by weight of n-butyl acrylate, 919 parts by weight of hydroxyethyl acrylate, 581 parts by weight of cyclohexyl methacrylate and 509 parts by weight Styrene polymerized using common initiators for radical polymerization.
  • the polyurethane-modified polyacrylate having an acid number according to DIN EN ISO 3682 of 33.5 mg KOH / g nonvolatile fraction was introduced into deionized water and adjusted to a pH of 7.4 with dimethylethanolamine and to a non-volatile content of 35 with further deionized water , 5 wt .-%, adjusted.
  • Preparation Example 4 The preparation of component (a.3): Polyethyleneimine modified with hydroxyacetophenone:
  • the basecoat is adjusted to a spray viscosity of 90-100 mPas / 1000 s -1 using a commercial Rheomat.
  • Example 1 The preparation of the multicoat system of the invention and its testing
  • Example 1 the basecoat material (A) according to Preparation Example 5, an aqueous basecoat (B) (Metallic water-based paint Black Sapphire Fa. BASF Coatings AG), containing also the component (a.3.) According to Preparation Example 4 in a proportion of 2 wt .-%, based on the basecoat (B), and a commercially available one-component clearcoat (C) (Protect 2 from. Dupont) used.
  • the basecoat material (A) according to preparation example 5 and the above basecoat material (B) metallic waterborne basecoat Black Sapphire from BASF Coatings AG) were used in each case without component (a.3).
  • the substrates used were 20 x 20 cm galvanized steel test panels coated with a conventional and well-known electrocoating primer (G) with a dry film thickness of 20 ⁇ m.
  • G electrocoating primer
  • Example 1 and in Comparative Example C1 the basecoat material (A) according to Preparation Example 5 was first applied by electrostatic spray application (ESTA) in such a wet layer thickness that after curing a dry film thickness of 15 ⁇ m resulted.
  • the resulting layer of the basecoat (A) was flashed off for 4 minutes and then coated with the aqueous basecoat (B) by pneumatic spray application in such a wet film thickness that after curing, a dry film thickness of 7 microns resulted.
  • the paint layers of basecoat (A) and basecoat (B) were dried for 10 minutes at 80 ° C.
  • the clearcoat (C) was applied in such a wet layer thickness, that after curing, a dry film thickness of 40 microns resulted.
  • the clearcoat layer (C) was flashed off for 5 minutes.
  • the layers of basecoat (A), basecoat (B) and clearcoat (C) were cured in a convection oven for 30 minutes at 130 ° C.
  • the adhesion of the layer of the coating composition according to the invention to the underlying primer (G) and to the layer of base coat (B) is excellent.
  • Damage to the test panels was carried out according to the following procedure: The freshly painted specimens had to rest for at least 48 hours at room temperature after the last painting process before being bombarded.
  • the bombardment of the painted specimens was carried out with a stone impact tester Type 508 from Erichsen according to DIN 55996-1.
  • An aluminum tube (inner diameter of 3.4 cm, a length of 26.3 cm at the top and 27.8 cm below and a distance of 2.0 to 2.3 cm from the test specimen (the length of the tube section is on the passage tube of the stone impact tester to adapt to the respective stone impact tester) set to target the fire targeted and defined on a limited circular area.
  • the corrosion-induced growth rate of the area originally damaged by the rockfall was determined by image analysis. After 9 weeks, the weekly average growth rate was calculated.
  • Table 1 summarizes the results. It can be seen that the use of the components (a.3) according to the invention results in a significant reduction of the corrosion-induced increase in the damaged area in the samples loaded in the rockfall simulation.
  • Table 1 Results of the corrosion change tests (KWT) Component (a.3) KWT: Increase in damaged area in% per week example 1 Hydroxyacetophenone modified polyethylenimine 0,820 Comparative Example C1 - 2,300

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Claims (10)

  1. Revêtement de peinture multicouche colorant et/ou à effet, comprenant, superposés dans cet ordre,
    (1) au moins un premier revêtement de peinture de fond à base d'une peinture de fond (A),
    (2) de préférence un deuxième revêtement de peinture de fond colorant et/ou à effet à base d'une peinture de fond (B) et
    (3) au moins un revêtement de vernis transparent à base d'un vernis (C)
    caractérisé en ce que la peinture de fond (A) formant le premier revêtement de peinture de fond contient
    (a.1) au moins un liant,
    (a.2) au moins un pigment colorant ou à effet et
    (a.3) au moins un composant oligo- ou polymère anticorrosion hydrosoluble ou dispersable dans l'eau, qui comporte un corps de base (GK) comportant au moins deux motifs monomères (ME) répétitifs ainsi qu'au moins un ligand (L) potentiellement anionique mono- et/ou pluridenté, qui, inaltéré après le durcissement thermique du revêtement de peinture multicouche, est apte à la formation de complexes.
  2. Revêtement de peinture multicouche selon la revendication 1, caractérisé en ce que
    la peinture de fond (A) et/ou la peinture de fond (B) est/sont une/des peinture(s) de fond à l'eau.
  3. Revêtement de peinture multicouche selon l'une quelconque des revendications 1 et 2, caractérisé en ce qu'on utilise comme liant (a.1) des associations d'au moins 2 composants choisis parmi des résines polyester (a.1.1) de préférence diluables à l'eau, des résines polyuréthane (a.1.2) de préférence diluables à l'eau et/ou des résines polyacrylate (a.1.3) de préférence diluables à l'eau.
  4. Revêtement de peinture multicouche selon l'une quelconque des revendications 1 à 3, caractérisé en ce que
    le composant (a.3) présente une hydrosolubilité ou une dispersibilité dans l'eau à la température ambiante d'au moins 20 g/litre d'eau.
  5. Revêtement de peinture multicouche selon l'une quelconque des revendications 1 à 4, caractérisé en ce que
    les motifs monomères (ME) du composant (a.3) sont choisis dans le groupe
    - des motifs (méth)acrylate, en particulier en association avec d'autres motifs monomères, comme par exemple des motifs styrène, vinylimidazole, acide vinylphosphonique, acide acrylique, anhydride maléique, ou acide maléique,
    - des motifs alkylène- et/ou arylène-amide,
    - des motifs oxyde d'alkylène, en particulier des motifs oxyde d'éthylène et/ou oxyde de propylène, ainsi que
    - de façon particulièrement préférée des motifs alkylène-imine, en particulier des motifs éthylène-imine.
  6. Revêtement de peinture multicouche selon l'une quelconque des revendications 1 à 5, caractérisé en ce que
    le ligand (L) du composant (a.3) est choisi dans le groupe
    - des composés organophosphorés, comme en particulier des organophosphonates, de préférence des phosphonates à fonctionnalisation hydroxy, amino ou amido au niveau du substituant organique,
    - des composés organosulfurés, comme en particulier des composés thio fonctionnalisés, tels que des composés thiol, polythiol, acide thiocarboxylique, thioaldéhyde, thiocétone, dithiocarbamate, sulfonamide et/ou thioamide, de préférence des polythiols comportant au moins 2 groupes thiol, encore mieux au moins 3 groupes thiol, de façon particulièrement préférée des polyesterpolythiols comportant au moins 3 groupes thiol,
    - des urées et thiourées acylées, comme en particulier des composés benzoylurée et/ou -thiourée,
    - des di- et/ou polyamines, comme en particulier l'acide éthylènediaminetétraacétique (EDTA) ou de préférence des amines à plus haute fonctionnalité, comme par exemple les types Jeffcat® (société Huntsman), comme en particulier des trialkylamines, de préférence des diaminoalkyl-hydroxyalkylamines, comme de façon particulièrement préférée la N,N-bis(3-diméthyl-aminopropyl)-N-isopropanolamine (Jeffcat® ZR50),
    - des quinoléines, cholines et/ou benzimidazoles, comme en particulier des composés aminoquinoléine et/ou mercaptobenzimidazole,
    - des composés hydroxylés qui comportent en particulier en une position stériquement favorable, de préférence en position 1,3, d'autres groupes carbonyle, carboxy, thiocarbonyle et/ou imino, de façon tout particulièrement préférée des hydroxyacétophénones,
    - des composés carbonyle qui comportent en particulier en une position stériquement favorable, de préférence en position 1,3, d'autres groupes carbonyle, carboxy, thiocarbonyle et/ou imino, de façon particulièrement préférée des composés acétylacétonate,
    - des carbènes et/ou
    - des composés acétylène, comme en particulier des composés propargyle.
  7. Revêtement de peinture multicouche selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il est appliqué sur un subjectile métallique non muni d'un primaire et/ou de préférence sur un subjectile métallique au moins partiellement muni d'un primaire (G).
  8. Procédé pour la production de revêtements de peinture multicouches, comprenant
    (1) au moins un premier revêtement de peinture de fond colorant et/ou à effet à base d'une peinture de fond (A) à l'eau selon les revendications 1 à 6,
    (2) de préférence un deuxième revêtement de peinture de fond colorant et/ou à effet à base d'une peinture de fond (B) à l'eau et
    (3) au moins un revêtement de vernis transparent à base d'un vernis (C)
    par application des peintures de fond (A) et (B) et
    éventuellement du vernis (C)
    (i) sur un subjectile non muni d'un primaire,
    (ii) de préférence sur un subjectile revêtu avec au moins un primaire (G) non durci ou seulement partiellement durci ou
    (iii) de façon particulièrement préférée sur un subjectile revêtu avec au moins un primaire (G) complètement durci
    et durcissement simultané des couches humides de peinture de fond (A), de préférence peinture de fond (B) et vernis (C) ainsi qu'éventuellement du primaire (G) non durci.
  9. Procédé pour la production de revêtements de peinture multicouches selon la revendication 8, caractérisé en ce
    qu'on applique les peintures de fond (A) et (B) en une épaisseur de couche humide telle qu'après le durcissement il en résulte une épaisseur commune des couches sèches de la peinture de fond (A) et de la peinture de fond (B) de 10 à 50 µm au total.
  10. Procédé pour la production de revêtements de peinture multicouches selon l'une quelconque des revendications 8 et 9, caractérisé en ce
    qu'on applique la peinture de fond (A) en une épaisseur de couche humide telle qu'après le durcissement il en résulte une épaisseur de couche sèche de la peinture de fond (A) de 6 à 25 µm.
EP10700303.0A 2009-02-05 2010-01-14 Produit de revêtement pour peintures résistantes à la corrosion Not-in-force EP2393611B1 (fr)

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PCT/EP2010/000148 WO2010089017A1 (fr) 2009-02-05 2010-01-14 Produit de revêtement pour peintures résistantes à la corrosion

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CN102307678A (zh) 2012-01-04
US10137476B2 (en) 2018-11-27
JP5575153B2 (ja) 2014-08-20
ES2472693T3 (es) 2014-07-02
US20120003487A1 (en) 2012-01-05
US20160175886A1 (en) 2016-06-23
CN102307678B (zh) 2013-11-13
DE102009007632A1 (de) 2010-08-12
JP2012516768A (ja) 2012-07-26
WO2010089017A1 (fr) 2010-08-12
EP2393611A1 (fr) 2011-12-14

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