EP2393612A1 - Produit de revêtement pour peintures résistantes à la corrosion - Google Patents

Produit de revêtement pour peintures résistantes à la corrosion

Info

Publication number
EP2393612A1
EP2393612A1 EP10700498A EP10700498A EP2393612A1 EP 2393612 A1 EP2393612 A1 EP 2393612A1 EP 10700498 A EP10700498 A EP 10700498A EP 10700498 A EP10700498 A EP 10700498A EP 2393612 A1 EP2393612 A1 EP 2393612A1
Authority
EP
European Patent Office
Prior art keywords
basecoat
weight
coating
pigments
clearcoat
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.)
Granted
Application number
EP10700498A
Other languages
German (de)
English (en)
Other versions
EP2393612B1 (fr
Inventor
Michael Richert
Wolfgang Duschek
Michael Dornbusch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP2393612A1 publication Critical patent/EP2393612A1/fr
Application granted granted Critical
Publication of EP2393612B1 publication Critical patent/EP2393612B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention relates to coating compositions for corrosion-resistant coatings, in particular for color and / or effect multi-layer coatings.
  • Modern motor vehicles usually have colored and / or effect multicoat paint systems.
  • these multi-layer coatings comprise an electrodeposition coating, a surfacer coating, stain-resistant primer or functional coating, a color and / or effect basecoat and a clearcoat.
  • the multicoat paint systems are preferably prepared 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 decisive for such important technological properties as impact resistance and smoothness and the course of the overall coating.
  • the quality of surfacer coatings, stone chip protection primers or functional coatings therefore has to meet particularly stringent requirements. They must also be able to be produced in a simple and excellently reproducible manner.
  • the automotive industry is also endeavoring to reduce the dry film thicknesses of surfacer coats, antistonechip primers or functional layers in order to reduce raw material and energy costs, without this leading to a deterioration of the application technology. see property profile of the multi-layer coatings, in particular to a deterioration of UV stability comes.
  • 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 material.
  • 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. Subsequently, 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 which, for dry film thicknesses ⁇ 35 .mu.m, preferably of about 15 .mu.m, the conventional surfacer coaters, antistonechip primers. or functional layers without loss of essential technological properties of the multi-layer coatings can replace.
  • UV absorbers in particular UV-absorbing pigments, as described in WO 2005/021168 A1 and WO 2006/062666 A1, ensures that the UV stability of the relevant multicoat paint systems is ensured. If the above-described multicoat paint systems are exposed to a load caused by stone chipping, flaking off of the entire layer composite occurs in spite of their high resistance to chipping. chem the bare metallic substrate is exposed and exposed to attack by corrosion. This corrosion manifests itself in the formation of blisters, that is to say bubble-like elevations of the multicoat paint system, accompanied by a progressive enlargement of the area exposed by the stone impact, which is due to the corrosive infiltration of the multicoat paint system starting from the corrosion on the bare metallic substrate.
  • 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 added as pigment pastes. Low-molecular corrosion inhibitors can only reach the interface between the substrate and the lacquer during the deposition process and thus be deposited if they carry a positive charge, with such anticorrosive agents generally impairing the properties of the entire lacquer basin and thus of the coating. Due to their particle size, pigment-type corrosion protection agents generally have no or only very little mobility.
  • coating compositions which may contain up to 5% by weight, based on the coating agent, of water and / or solvents which, according to the invention, are used for the direct coating of metals, in particular for the coating of metal strips. but which are also applied over an electrodeposition coating layer. could be brought.
  • 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 may continue to 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 the coating compositions described 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 is necessary for the above-described multicoat systems in automotive OEM coating.
  • At least one transparent varnish of clearcoat (C), preferably preparable by successive application of at least one thermally curable, preferably aqueous basecoat material (A), preferably at least one thermally curable, preferably aqueous basecoat material (B) and at least one clearcoat material (C) to a non-primed substrate or preferably to one with at least one or not only partially hardened primer (G) or particularly preferably on a substrate at least partially coated with at least one fully cured primer (G), which no longer have the disadvantages of the prior art.
  • the multi-layer coating according to the invention should have a good adhesion to the adjacent paint layers and in particular a significantly reduced corrosion after impact, which is triggered by corrosive infiltration of the multi-layer composite starting from exposed bare metallic substrate.
  • the improvement in corrosion resistance should be achieved, in particular with components which can be easily incorporated in the basecoat (A).
  • the physically or thermally curable, preferably aqueous basecoat material (A) should be able to be provided in a simple manner on the basis of commercially available, preferably aqueous, basecoats and provide first basecoats which, even in a layer thickness of about 15 .mu.m, are conventional surfacer coats, antistonechip primers or functional layers can be fully replaced without adversely affecting the performance properties of the multi-layer coatings, in particular the stone chip protection and the UV stability even after long-term exposure.
  • the new process should be able to be carried out in existing systems for the application of basecoats by electrostatic spray application and pneumatic application, without the need for conversions.
  • GK1 Basic body (GK1) selected from the group of low molecular weight alkyl, aryl, aralkyl, cycloalkyl radicals and / or heterocyclic radicals. At least one phosphoric acid group as
  • GK2 main body
  • the thermally curable, aqueous basecoat material (A) used according to the invention could be prepared in a simple manner on the basis of commercially available aqueous basecoats and provided first, color and / or effect basecoats (A) which, even in a layer thickness of ⁇ 15 .mu.m, were conventional surfacer coatings , Stone chip protection primers or functional layers could be completely replaced without adversely affecting the performance properties of the multi-layer coatings, in particular the stone chip protection and the UV stability even after long-term exposure.
  • the aqueous basecoat (A) in existing systems for the application of basecoats by electrostatic spray application and pneumatic spray application could be carried out without this conversions were necessary.
  • the binder (a.1) of the basecoat (A) contains as its essential constituent at least one binder (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 according to the invention are described, for example, in the patent applications DE 44 38 504 A1, EP 0 593 454 B1, DE 19948 004 A1, EP 0 787 159 B1 and WO 2005/021168 A1.
  • the binders described in EP 0 593 454 B1, EP 0 787 159 B1, DE 199 48 004 A1 and / or WO 2005/021168 A1 are preferably used, it being possible to use further binders in addition to these binders.
  • 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 ).
  • polyester resins described in EP 0 593 454 B1, page 8, line 3 to page 9, line 42 are particularly preferably used as component (a.1.1).
  • Such polyester resins (a.1.1) are obtainable by (a.1.1.1) polyols or a mixture of polyols and (a.1.1.2) polycarboxylic acids or polycarboxylic acid anhydrides or a mixture of polycarboxylic acid and / or polycarboxylic anhydrides to a polyester resin having an acid number according to DIN EN ISO 3682 of 20 to 70, preferably 25 to 55 mg KOH / g non-volatile content and a hydroxyl value according to DIN EN ISO 4629 from 30 to 200, preferably 45 to 100 mg KOH / g non-volatile content to be implemented.
  • 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 593454 B1 on page 8, lines 26 to 51, the components (a.1.1.2) preferably used 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 described in EP 0 593 454 B1 on page 9, lines 33 to 42.
  • polyurethane resins (a.1.2) are obtainable by (a.1.2.1) a polyester and / or polyether polyol or a mixture of such polyester and / or polyether polyols, (a.1.2.2) a polyisocyanate or a mixture of Polyisocyanates, (a.1.2.3) a compound which has at least one isocyanate-reactive group and at least one group capable of forming anions in the molecule or a mixture of such compounds, (a.1.2.4) optionally at least one hydroxyl group and / or amino groups containing organic compound having a molecular weight of 40 to 600 daltons or a mixture of such compounds and (a.1.2.5) optionally a compound having at least one isocyanate-reactive group and at least one polyoxyalky lenate in the molecule or a
  • the polyurethane resin produced in this way preferably has an acid number according to DIN EN ISO 3682 of 10 to 60 mg KOH / g non-volatile 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 components (a.1.2.1) which are preferably used for the preparation of the water-dilutable polyurethane resins (a.1.2) are in EP 0 593 454 B1 on page 6, lines 6 to 42, the components (a.1.2.2) preferably used in EP 0 593 454 B1 on page 6, line 43, to page 7, line 13, very particular preference to use polyisocyanates based on isophorone diisocyanate and tetramethylxylene diisocyanate, the preferably used components (a.1.2.3) in EP 0 593 454 B1 on page 7, lines 14 to 30, the components (a.1.2.4) preferably used in EP 0 593 454 B1 on page 7, lines 31 to 53, and the components (a.1.2.5) preferably used in EP 0 593454 B1 on page 7, lines 54 to 58 described.
  • the preparation of the polyurethane resins (a.1.1) and their neutralization are described in EP 0 593454 B1 on page 7, line 59, to page
  • Water-dilutable polyacrylate resins as described, for example, in EP 0 593 454 B1, can be used as component (a.1.3). Preference is given as components (a.1.3) to water-dilutable polyacrylate resins which are prepared in the presence of polyurethane prepolymers (a.1.3.1) which optionally have units with polymerizable double bonds.
  • water-dilutable polyurethane-modified polyacrylates (a.1.3) according to EP 0 787 159 B1 are used.
  • Such water-dilutable polyurethane-modified polyacrylates are obtainable in a preferred embodiment in which, in a first stage, in the presence of a solution of a polyurethane prepolymer (a.1.3.1) which has substantially no polymerizable double bonds, a mixture of (a .1.3.a.1) a substantially carboxyl-free (meth) acrylic acid ester or a mixture of (meth) acrylic acid esters, (a.1.3.a.2) an ethylenically unsaturated monomer which has at least one hydroxyl group per molecule and which is essentially carbo- xyl phenomenon or a mixture of such monomers and (a.1.3.a.3) a substantially carboxyl-free of (a.1.3.a.1) and (a.1.3.a.2) different monomers or a mixture of such monomers is polymerized, wherein the polyurethane prepolymer (a.1.3.1) is not a crosslinked polyurethane resin, wherein then
  • a substantially carboxyl group-free ethylenically unsaturated monomer or a mixture of such monomers is further polymerized after at least 80 wt .-% of the monomers added in the first stage have been reacted, and in a final stage after Termination of the polymerization, the polyurethane-modified polyacrylate (a.1.3) is neutralized and then dispersed in water.
  • 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 quantity so that the polyacrylate resin obtained from the abovementioned components has an acid number according to DIN EN ISO 3682 of 20 to 100 mg KOH / g nonvolatile content and a hydroxyl number according to DIN EN ISO 4629 of 5 to 200, preferably 10 to 150 mg KOH / g nonvolatile content.
  • the preferred proportions by weight of the abovementioned components are described in EP 0 787 159 B1 on page 3, lines 4 to 6.
  • the components (a.1.3.1) 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 components (a .1.3.a.1) in EP 0 787 159 B1 on page 3, lines 13 to 20, the components (a.1..3.a.2) preferably used in EP 0 787 159 B1 on page 3, lines 21 to 33, the components (a.1.3.a.3) preferably used in EP 0 787 159 B1 on page 3, lines 34 to 37, the components (a.1.3.b.1) preferably used in EP 0 787 159 B1 on page 6, lines 33 to 39, and the components preferably used (a.1.3.b.2) described in EP 0787159 B1 on page 6, lines 40 to 42.
  • water-thinnable polyurethane-modified polyacrylates (a.1.3) which are prepared in the presence of polyurethane prepolymers (a.1.3.1) which have units with polymerizable double bonds are used.
  • Such graft copolymers and their preparation are known, for example, from EP 0 608 021 A1, DE 196 45 761 A1, DE 197 22 862 A1, WO 98/54266 A1, EP 0 522 419 A1, EP 0 522 420 A2 and DE 100 39 262 A1 ,
  • water-dilutable polyurethane-modified polyacrylates (a.1.3) based on graft copolymers are preferably used as described in DE 199 48 004 A1.
  • the polyurethane prepolymer component (a.1.3.1) is prepared by (1) at least one polyurethane prepolymer containing at least one free isocyanate group, with
  • the preferred polyurethane prepolymers used in step (1) above are described in DE 199 48 004 A1, page 4, line 19, to page 8, line 4.
  • the preferred adducts used in step (2) above are described in DE 19948 004 A1, page 8, line 5, to page 9, line 40.
  • the graft copolymerization is preferably as described in DE 199 48 004 A1, page 12, line 62, to page 13, line 48, with those described 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. H. of the acid groups, to be converted into an anionic group.
  • Suitable neutralizing agents are known from DE 44 37 535 A1, page 6, lines 7 to 16, or 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 material (A) preferably contains at least one colorant or effect pigment (a.2).
  • the pigment (a.2) 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, color and optically effect pigments, and / or whose mixtures are selected.
  • the pigment (a.2) has UV-absorbing constituents.
  • Suitable effect pigments which may also be coloring
  • metal flake pigments such as commercially available aluminum bronzes, aluminum chromates chromated according to DE 36 36 183 A1, 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 from 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 color pigments are pigments monoazo, disazo pigments, anthraquinone pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, isoindoline pigments, isoindolinone pigments, azo methine 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 to be adjusted or should.
  • 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 in the basecoat (A) with at least one constituent of the binder (a.1) described above.
  • the component (a.1.2) of the binder (a.1) described above is used for the trituration.
  • the basecoat (A) 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 titanium dioxide and / or carbon black pigments (a.2.1) in the basecoat (A) may 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 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 corrosion-inhibiting component (a.3) comprises at least one phosphoric acid group bound to a base body (GK1) as ligand (L1) and / or at least one phosphonic acid group attached to a base body (GK2) as ligand (L2), which has good adhesion to the metal Substrate and can form chelates with the metal ions released during the corrosion of the substrate (for "chelates” see Rompp Online, Georg Thieme Verlag, Stuttgart, New York, 2005, Chapter “Chelates”)
  • the ligand (L) does not lose its chelating properties during the thermal curing of the multicoat paint system
  • the ligand (L) by complexing and / or covering the metal surface, inhibits corrosion by reduction of corrosion inhibition
  • the component (a.3) can additionally, by means of a buffer effect, reduce the pH of the aqueous medium at the interface which is necessary for the corrosion to suppress the metal.
  • Basic bodies (GK1) according to the invention which carry at least one phosphoric acid group as ligand (L1) are low molecular weight optionally substituted alkyl, aryl, aralkyl, cycloalkyl and / or heterocyclic radicals, in particular pyridines, pyrimidines, pyrazoles, pyrroles, thiophenes , Furans, benzimidazoles, benzothiazoles, benzotriazoles, benzoxazoles, quinolines, isoquinolines, indanes, indenes, benzpyrones, and particularly preferably triazines.
  • main body Preference is given to optionally substituted alkyl radicals as main body (GK1), particularly preferably those having 3 to 30, in particular those having 4 to 20 carbon atoms.
  • Low molecular weight basic bodies (GK1) preferably have a molecular weight of less than 750 daltons, more preferably less than 500 daltons.
  • Basic bodies (GK2) which carry at least one phosphonic acid group as ligand (L2) are low molecular weight alkyl, aryl, aralkyl, cycloalkyl radicals, heterocyclic radicals and / or polymers which contain monomer units with phosphonic acid groups and weight average molecular weights Mw (determinable by means of gelper - Meation chromatography according to standards DIN 55672-1 to -3) of preferably more than 400 daltons, more preferably more than 600 daltons and most preferably more than 800 daltons.
  • Low molecular weight basic bodies (GK2) preferably have a molecular weight of less than 750 daltons, more preferably less than 500 daltons.
  • Polymers of monoethylenically unsaturated monomer units which contain at least one monoethylenically unsaturated building block having a phosphonic acid group as the ligand (L), particularly preferably vinylphosphonic acid, are preferred as the basic body (GK2).
  • L ligand
  • GK2 vinylphosphonic acid
  • Such polymers are described, for example, in WO 2007/125028 A2, where the copolymers described therein, containing, in addition to the phosphono group-carrying monoethylenically unsaturated monomers, monoethylenically unsaturated monomers with aromatic nitrogen heterocycles, are very particularly preferred for the purposes of the invention.
  • the main bodies (GK1) or (GK2) can be hydrophilically modified in a known manner.
  • additional ionic and / or nonionic substituents are introduced into the main body (GK) for this purpose.
  • anionic substituents these are in particular phenolate, carboxylate, thiolate, 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 , Wherein the substituents may also function as additional ligands (L).
  • the component (a.3) is in the basecoat (A) in amounts of 0.1 to 20, preferably 0.2 to 10, more preferably 0.5 to 5 wt .-%, each based on the total weight of the basecoat (A), included.
  • the basecoat contains (A), preferably at least one talcum component (a.4).
  • the content of talcum (a.4) can vary widely and depends on the 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 various crosslinking agents; from the binders (a.1) different, oligomeric and polymeric Bindemit- teln; 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 described in the German patent application DE 199 48 004 A 1, page 14, line 32, to page 17, line 5, wherein preferably amino resins as the predominant or sole crosslinking agent in the basecoat (A) in the in DE 19948 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 special features, but is preferably carried out 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 dissolver, static mixers, Sprocket dispersers, pressure relief nozzles and / or Microfluidi- zer.
  • the multicoat system according to the invention can be applied using all customary and known methods for the application of liquid coating materials, it is advantageous for the process according to the invention to produce the multicoat systems if the basecoat (A) is used with the aid of electrostatic spray application (ESTA), preferably with high-rotation bells, is applied.
  • the brushing agent according to the invention is applied in such a wet layer thickness that after curing of the resulting lacquer layer from the basecoat (A) results in a dry film thickness of 6 to 25 .mu.m, preferably 7 to 20 .mu.m, particularly preferably 8 to 18 microns 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 vented off or dried, but not or only partially cured, and then coated with the thermally curable, preferably aqueous basecoat (B).
  • the thermally curable, aqueous basecoat (B) is preferably a customary and known aqueous basecoat material, as is known, for example, from the patent application WO 2005/021168, page 24, lines 11 to 28.
  • 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).
  • 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.
  • the basecoat material (A) and the basecoat material (B) are preferably applied with a wet layer thickness such that, after curing, a total dry film thickness of basecoat material (A) and basecoat material (B) of 10 to 50 .mu.m, preferably 12 to 35 microns, more preferably 14 to 28 microns results.
  • the preferred multicoat systems according to the invention are obtained by successive application of the basecoat material (A), preferably at least one thermally curable, preferably aqueous basecoat material (B) and at least one clearcoat material (C) (i) to a non-primed substrate, (ii) preferably to at least one unhardened or only partially cured primer (G) coated substrate; or (iii) particularly preferably a substrate coated with at least one fully cured primer (G) and co-curing (a) the resulting wet films of basecoat (A), basecoat (B ) and the clearcoat (C) or
  • 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 (IK), 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 processes for their application are known, for example, from the patent application WO 2005/021168, page 25, line 27, to page 28, line 23.
  • the substrates can be constructed from a wide variety of materials and combinations of materials. Preferably, they consist at least partially of metals, it being possible for plastic substrates to be arranged spatially next to the metallic substrates, as may be the case, for example, in the case of plastic attachment parts 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.
  • 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 electrocoating (G) are prepared in a customary and known manner from electrophoretically, in particular cathodically, depositable electrocoating lacquers.
  • 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 thermally cured together. 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, after a certain period of rest, also known as venting, take place between and after the order, if necessary, tion, 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 use 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 there are 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.
  • the thermal curing can also be done gradually.
  • Another preferred curing method is near infrared (NIR) curing.
  • NIR near infrared
  • Particularly preferred is a method in which the component water is rapidly removed from the wet layers. Suitable methods of this kind are, 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 «.
  • the thermal curing is carried out at a temperature of 50 to 170, more preferably 60 to 165 and in particular 80 to 150 0 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 outstanding automotive quality. They have, in addition to excellent stone chip resistance, excellent adhesion to the primer (G) and to the following the paint layers and in particular an outstanding resistance to corrosive infiltration and resulting blister corrosion of the multi-layer composites in the vicinity of bare areas, as they are generated in particular by rockfall on.
  • 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 non-volatile portion prepared and adjusted to a non-volatile content of 74.0 wt .-%.
  • 2179 parts by weight of the polyester precursor were propionic acid in a common solvent with 137 parts by weight of dimethylolpropionic, 24 parts by weight of neopentyl glycol and 694 parts by weight of m-tetramethylxylene diisocyanate (m-TMXDI TMXDI ® (Meta), Cytec Ind.) And the reaction was carried out to an isocyanate content of 1, 35 wt .-%, based on the total weight. Thereafter, 111 parts by weight of trimethylolpropane were added and stirred until no more free isocyanate groups were detectable.
  • m-TMXDI TMXDI ® Metal
  • 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-volatile content of 73.0% by weight.
  • polyester precursor 4085 parts by weight of the polyester precursor were heated in a common solvent with 186 parts by weight of neopentyl glycol and 1203 parts by weight of m-tetramethyl xylene diisocyanate (TMXDI ® (Me ta), Cytec Ind.) was heated and the reaction was up to a Isocyana- natgehalt 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-tetramethyl xylene 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.
  • 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 nonvolatile content of 35.5 wt. -%, set.
  • the basecoat is then adjusted to a spray viscosity of 90-100 mPas / 1000 s -1 using a commercial Rheomat.
  • the basecoat material (A) according to Preparation Example 4 containing corrosion-inhibiting substances (a.3.1) and (a.3.2), an aqueous basecoat material (B) (Metallic waterborne basecoat Black Sapphire from BASF Coatings AG), also containing the respective component (a.3.1) and (a.3.2) in a proportion of 2 wt .-%, based on the basecoat (B), and a commercially available one-component clearcoat (C) (Protect 2 Fa. Du - pont) used.
  • B Metallic waterborne basecoat Black Sapphire from BASF Coatings AG
  • C one-component clearcoat
  • the basecoat material (A) according to Preparation Example 4 and the above basecoat material (B) were used in each case without component (a.3.x).
  • 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
  • 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 with the aqueous basecoat (B) by coated 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 at 80 ° C. for 10 minutes.
  • 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 0 C.
  • the adhesion of the base coat (A) layer to the underlying undercoat (G) and to the overlying base coat (B) layer is excellent.
  • 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
  • bombardment was carried out with 50 g of hard-cast shotblasting diamond 4-5 mm from Eisentechnik Würth GmbH Bad Friedrichshall at a pressure of 2 bar To stretch to about 10 seconds, you gave the blasting medium accordingly slow in the running stone impact device.
  • the samples were subjected to a KWT climate change test according to VDA-Prüfblatt 621-415 (February 1982), whereby the test subjects went through 15 week cycles and where 1 week cycle was
  • 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.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne une peinture multicouche comprenant, dans l'ordre d'application suivant, (1) au moins une première peinture de base constituée d'une laque de base (A), (2) de préférence une deuxième peinture de base (B) colorante et/ou à effet et (3) au moins une peinture transparente constituée d'un vernis clair (C). La laque de base formant la première peinture de base (A) présente au moins un liant (a.1), au moins un pigment (a.2) coloré et/ou à effet, et un constituant anticorrosion (a.3) doté d'un corps de base (GK1) qui est sélectionné dans le groupe des restes alkyle, aryle aralkyle cycloalkyle et/ou des restes hétérocycliques à faible poids moléculaire et qui porte au moins un groupe d'acide phosphorique en tant que ligand (L1), et/ou au moins un constituant anticorrosion doté d'un corps de base (GK2) qui est sélectionné dans le groupe des restes alkyle, aryle aralkyle cycloalkyle, hétérocycliques et/ou des polymères et qui porte au moins un groupe d'acide phosphonique en tant que ligand (L2).
EP10700498.8A 2009-02-05 2010-01-14 Produit de revêtement pour peintures résistantes à la corrosion Not-in-force EP2393612B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200910007629 DE102009007629A1 (de) 2009-02-05 2009-02-05 Beschichtungsmittel für korrosionsstabile Lackierungen
PCT/EP2010/000147 WO2010089016A1 (fr) 2009-02-05 2010-01-14 Produit de revêtement pour peintures résistantes à la corrosion

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EP2393612A1 true EP2393612A1 (fr) 2011-12-14
EP2393612B1 EP2393612B1 (fr) 2014-04-30

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EP (1) EP2393612B1 (fr)
JP (1) JP5575152B2 (fr)
CN (1) CN102300646A (fr)
DE (1) DE102009007629A1 (fr)
ES (1) ES2475615T3 (fr)
WO (1) WO2010089016A1 (fr)

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JP2012516767A (ja) 2012-07-26
WO2010089016A1 (fr) 2010-08-12
JP5575152B2 (ja) 2014-08-20
US20120135245A1 (en) 2012-05-31
ES2475615T3 (es) 2014-07-11
CN102300646A (zh) 2011-12-28
EP2393612B1 (fr) 2014-04-30
DE102009007629A1 (de) 2010-08-12

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