EP1417040B1 - Matieres d'enduction fonctionnelles aqueuses et procede integre de production de peintures multicouches produisant une couleur et / ou un effet - Google Patents

Matieres d'enduction fonctionnelles aqueuses et procede integre de production de peintures multicouches produisant une couleur et / ou un effet Download PDF

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Publication number
EP1417040B1
EP1417040B1 EP02730277A EP02730277A EP1417040B1 EP 1417040 B1 EP1417040 B1 EP 1417040B1 EP 02730277 A EP02730277 A EP 02730277A EP 02730277 A EP02730277 A EP 02730277A EP 1417040 B1 EP1417040 B1 EP 1417040B1
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EP
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Prior art keywords
functional coating
aqueous
coating materials
films
pigments
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EP02730277A
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German (de)
English (en)
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EP1417040B2 (fr
EP1417040A2 (fr
Inventor
Ekkehard Sapper
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BASF Coatings GmbH
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BASF Coatings GmbH
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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
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • 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
    • B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
    • 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
    • B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/007—Processes for applying liquids or other fluent materials using an electrostatic field
    • 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
    • B05D7/58—No clear coat specified

Definitions

  • the present invention relates to a new integrated wet-on-wet process for the production of color and / or effect Multicoat paint systems comprising at least one functional layer and at least one color and / or effect solid-color topcoat or alternatively at least one color and / or effect basecoat and at least one clearcoat.
  • the concerns present invention new aqueous functional coating materials for the Production of multicoat color and / or effect paint systems.
  • German patent application DE 44 38 504 A 1 directed.
  • the aqueous functional coating materials used here are physically curable and included as a binder water-dilutable polyurethane resin with an acid number of 10 to 60 and a number average molecular weight of 4,000 to 25,000.
  • the Polyurethane resin can be produced by aa) a polyester and / or Polyether polyol having a number average molecular weight of 400 to 5,000 or a mixture of such polyester and / or Polyether polyols, bb) a polyisocyanate or a mixture of Polyisocyanates, cc) a compound which is at least one opposite Isocyanate-reactive and at least one for anion formation having a competent group in the molecule, or a mixture of such Compounds and optionally dd) a hydroxyl and / or amino groups containing organic compound having a molecular weight of 40 to 400 or a mixture of such compounds with one another be reacted and the resulting reaction product at least partially neutralized.
  • the known aqueous functional coating materials allow the Production of particularly thin surfacer coatings, Rockfall protection primers or functional layers, without a Loss of stone chip resistance or deterioration of the stone Covering the unevenness of the primed substrate.
  • the known wet-in-wet process is therefore economical and ecological very cheap.
  • Aqueous functional coating materials containing at least one saturated, unsaturated and / or with olefinically unsaturated compounds grafted, ionically and / or nonionically stabilized polyurethane as Binders as well as pigments are from the German Patent applications DE 199 14 896 A1, DE 199 53 445 A1, DE 199 53 203 A 1 or DE 199 53 446 A 1 known You can thermally or be cured thermally and with actinic radiation. The thermal Curing can be carried out by self-crosslinking or external crosslinking.
  • the patent applications DE 199 53 445 A 1 and DE 199 53 2 03 A 1 was essentially based on the task, aqueous and non-aqueous Self-crosslinking functional coating materials, adhesives and Polyurethane based sealants with very good to provide application properties.
  • the self-crosslinking functional coating materials in particular the aqueous self-setting functional coating materials, especially the self-setting waterborne basecoats, in their processing in the wet-on-wet process also in the Use of powder clearcoat slurries no cracking (mud cracking) or cook or pinch.
  • the new Functional coating materials a very good storage stability, excellent application properties, such as a very good course and a very low track pitch even at high layer thicknesses demonstrate.
  • the multicoat paint systems produced herewith are said to have a excellent overall appearance and high chemical, Yellowing and weathering resistance. Last but not least no delamination of the layers after the water jet test more occur. All these advantages should be achieved without a Increase in the emission of organic compounds accepted must become.
  • the aqueous functional coating materials of DE 199 53 445 A1, DE 199 53 203 A1 or DE 199 53 446 A1 can also be described as Filler can be used. Preferably, however, they are as Waterborne basecoats used. If and, if so, to what extent the known aqueous functional coating materials are suitable as fillers in the Under a wet-in-wet process usual and well-known Substitute Einbrenn colller, without causing an effect and / or Hue shift occurs, is not known.
  • the included known aqueous functional coating materials no separate, water-soluble and / or -dispersible crosslinking system which in and / or on the matrix of wet, dry and / or dried ones Layers of the aqueous functional coating materials for themselves even partially or fully networked before the layers total fully networked.
  • the patent applications can be no Take notes that could stimulate the expert to the aqueous functional coating materials enforce such a system.
  • aqueous multicomponent systems based on hydroxyl-containing polyurethanes and polyisocyanates known
  • the aqueous multicomponent systems can be radiation-curable Binders, Reakiwerschreibner and photoinitiators included. Thus lie two separate networking systems next to each other.
  • the aqueous Multi-component systems can also be used as fillers.
  • the polyurethanes and polyisocyanates already begin after the application of aqueous multicomponent systems due to their high reactivity immediately crosslinked, so that the curing with actinic Radiation can not be performed so that it is before the complete thermal curing of the matrix of layers in the essentially finished. Both injury mechanisms are therefore running parallel, or the curing with actinic radiation is after the performed thermal curing
  • German patent application DE 199 04 317 A 1 was the task to provide aqueous multicomponent systems which especially during prolonged storage to a lesser extent or not at all more infested and destroyed by microorganisms.
  • German patent application DE 198 155 125 A 1 was the task to provide aqueous multicomponent systems that are light in weight can be produced, homogeneous, easy to handle, low-solvent, cooker-proof, splash-proof and stable when forced drying and which are matte Coatings provided no surface defects and greyness have, but are weather-resistant and gasoline resistant.
  • the object of the present invention is to provide a novel wet-on-wet process for the production of color and / or effect
  • To provide multicoat paint systems that enhance the economic, technical and environmental benefits of the German Patent application DE 44 38 504 A 1 or the European Patent application EP 0 871 552 A 1 known method and that allows it, without much material, apparative and procedural effort to substitute Einbrennyogller without that Here, an effect and / or hue shift in the Water-based paints occurs.
  • aqueous functional coating material which is excellent for the production of color and / or effect Multicoat paint systems, where it is for the production of Functional layers, fillers, antistonechip primers, Solid topcoats and basecoats, but especially Functional layers, can be used.
  • the new should aqueous functional coating material for the new wet-on-wet process be suitable.
  • inventive method and in particular the inventive Functional coating materials provided functional coatings that are also available in for fillers unusually small layer thicknesses a high Have stone chip resistance.
  • the new ones showed Functional layers an excellent intercoat adhesion between the primers and waterborne basecoats.
  • the efindungshunte process is used to produce color and / or effect multicoat paint systems on primed or ungrounded substrates.
  • the new color and / or effect multicoat paint systems contain at least one functional layer and at least one color and / or effect unidot finish or alternatively at least a color and / or effect basecoat and at least one Clearcoat.
  • Functional layers i. S. of the present invention are surfacers i. S. German Patent Application DE 44 38 504 A1 or European Patent Application EP 0 871 552 A 1, which also have unusually thin layer thicknesses have a high rockfall protection effect and also often make a contribution to the color and / or effect.
  • Suitable substrates are all those whose surface is not damaged by the application of heat and / or actinic radiation during the curing of the layers present thereon.
  • the substrates of metals, plastics, wood, ceramics, stone, textile, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, and composites of these materials.
  • the inventive method and the Functional coating materials according to the invention not only for Applications in the fields of automotive OEM finishing and Automotive refinish excellent, but also come for the coating of buildings in interior and Exterior and doors, windows and furniture, for the industrial Coating, including coil coating, container coating and the Impregnation and / or coating of electrical components, as well as for the lacquering of white goods, including household appliances, Boilers and radiators, into consideration.
  • industrial Coating including coil coating, container coating and the Impregnation and / or coating of electrical components, as well as for the lacquering of white goods, including household appliances, Boilers and radiators, into consideration.
  • Objects for private or industrial use such as Household appliances, small parts made of metal, such as nuts and bolts.
  • primers can be used be made in the usual and well-known way from electrocoats getting produced.
  • anodic and cathodic electrodeposition paints but especially cathodic Electrocoating, but you can also do a cathodic having deposited electrodeposition coating layer, which is not thermal Hardened, but only dried or partially cured Die Electrocoating or the electrodeposition coating can then with the functional coating materials according to the invention or the Functional coating materials to be used according to the invention be overlaid. These can then be shared with the Electrodeposition paint layer are cured (wet-in-wet process).
  • cathodic electrodeposition paints and optionally wet-on-wet processes including electrocoating layers in Japanese Patent Application 1975-142501 (Japanese Patent Laid-Open JP 52-065534 A 2, Chemical Abstracts Division No. 87: 137427) or the patents US 4,375,498 A 1, US 4,537,926 A 1, No.
  • the first step of the method according to the invention is applied to a substrate at least one, especially one, inventive functional coating material applied.
  • the functional coating material according to the invention contains at least in particular, binder (A).
  • binder (A) are in their material composition is not limited. Besides, they can Be oligomers or polymers.
  • Oligomers are understood as meaning resins which have at least 2 to 15 Contain monomer units in their molecule. Be under polymers Resins understood that have at least 10 recurring monomer units contained in their molecule. In addition to these terms Römpp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomers," page 425.
  • the binders (A) are selected from the group consisting of physically, thermally, with actinic radiation or thermally and with actinic radiation curable or crosslinkable, statistically, alternating and / or block-like, constructed, linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, and polyaddition resins and Polycondensation resins, selected These terms will be used supplementary to Römpp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition” and “Polyaddition resins (polyadducts)", as well as pages 463 and 464, »Polycondensates «, »polycondensation « and »polycondensation resins « directed.
  • suitable (co) polymers (A) are (Meth) acrylate copolymers and partially saponified polyvinyl esters, in particular (meth) acrylic) copolymers.
  • Examples of well-suited polyaddition resins and / or Polycondensation resins (A) are polyesters, alkyds, polyurethanes, Polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, Polyureas, polyamides or polyimides.
  • polyurethanes (A) are advantageous, which is why they are preferred be used.
  • the polyurethanes (A) are particularly preferably made the group consisting of saturated, unsaturated and with olefinic unsaturated compounds grafted, ionic or nonionic as well ionic and nonionic stabilized polyurethanes selected
  • Binders (A) can vary widely and depends on the Requirements of the individual case.
  • the content is 10 to 80, preferably 15 to 78, more preferably 20 to 76, especially preferably 25 to 74 and in particular 30 to 72 wt.%, in each case based on the solid body of the functional coating material.
  • the functional Be Anlagenchtstoffen invention contain furthermore at least one, in particular one, separate, water-soluble and / or dispersible crosslinking system (B).
  • the term "separate" makes it clear that that the networking system is independent or substantially regardless of the crosslinking of the binder (A) takes place.
  • Essential is here that the separate network system (B) in and / or on the Matrix of wet, drying and / or dried layers of the Functional coating materials according to the invention partially for themselves or completely crosslinked before the binders (A), in particular the Polyurethane (A) completely crosslink and so the layers in total completely network.
  • the separate crosslinking system (B) to be used according to the invention can be of any composition, as long as it is essential to the invention fulfilled.
  • that can Separate crosslinking system to be used according to the invention (B) based on the composition of the aqueous functional coating materials based on the above Binders (A), in particular of the polyurethanes (A) can be selected.
  • the separate crosslinking system (B) is selected from the group consisting of physical, thermal, with actinic radiation as well thermal and actinic radiation curable crosslinking systems, selected
  • actinic radiation is electromagnetic Radiation, preferably near infrared (NIR), visible light, UV radiation or X-radiation, in particular UV radiation, and / or Corpuscular radiation, in particular electron radiation used
  • the separate crosslinking system (B) is selected from the group consisting of thermal or thermal and actinic radiation curable crosslinking systems, selected Crosslinking systems (B) thermally self-crosslinking and / or externally crosslinking be.
  • the term means "physical cure” the curing of the invention to using separate crosslinking system (B) by filming for example, on the surface of the matrix of the layers of the functional coating materials according to the invention, wherein the Linkage via loop formation of the polymer molecules of the binders (on the term see Römpp Lexikon Lacke and Druckmaschine, Georg Thieme publishing house, Stuttgart, New York, 1998, “binder”, pages 73 and 74). Or the filming takes place via the coalescence of Particles from the separate crosslinking system (B) (see Römpp Lexikon Paints and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening," pages 274 and 275). Usually these are not Crosslinking agent necessary.
  • the physical Curing by atmospheric oxygen, heat or by irradiation with actinic Radiation are supported.
  • the selection of a physically curing separate crosslinking system (B) depends on the temperature at which the inventive Functional coating material itself filmed or thermally crosslinked are selected physically curing separate crosslinking systems (B), their minimum film forming temperature (MFT) (see Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998 »Minimum Film-forming Temperature«, page 391) below the Minimum film forming temperature or the crosslinking temperature of the functional coating materials according to the invention or the binder (A) is.
  • MFT minimum film forming temperature
  • the skilled person can therefore suitable physical curing separate networking systems (B) for a given physical, thermally or thermally and with actinic radiation curing Function coating material according to the invention easily based on his general knowledge, possibly with the help of easier Determine preliminary tests.
  • the term denotes "self-crosslinking” the property of the invention to using the networking system (B) "with itself” To enter into crosslinking reactions.
  • the prerequisite for this is that in At least one component already has both types of complementary contain reactive functional groups that are responsible for crosslinking necessary, or reactive functional groups that are with themselves can react.
  • externally cross-linking are such separate crosslinking systems (B), wherein the one type of complementary reactive functional groups in a binder and the other type are in a hardener or crosslinking agent.
  • Römpp Lexikon Lacke and printing inks Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening," pages 274 to 276, especially page 275, below.
  • variable R is an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R 'and R "stand for identical or different aliphatic radicals or are linked together to form an aliphatic or heteroaliphatic ring.
  • complementary reactive functional groups are directed depending on the temperature range in which the complete hardening of Matrix of the layers of the functional coating materials according to the invention, which also contains the binders (A), in particular the Polyurethanes (A), takes place. So must the thermal cure of the separate crosslinking system (B) at lower temperatures Expire when it comes to the functional coating materials of the invention thermally or thermally and with actinic Radiation curable functional coating materials is.
  • the expert therefore, for a given inventive groups functional coating material the respectively suitable complementary reactive functional groups slightly due to its general expertise optionally with the aid of simple orienting experiments choose.
  • the curing with actinic radiation takes place with the help of reactive functional groups containing at least one, in particular one, with actinic radiation activatable bond included.
  • actinic Radiation activatable bond understood a bond at Irradiation with actinic radiation becomes reactive and with others activated bonds of their type polymerization reactions and / or Crosslinking reactions that after radical and / or ionic Mechanisms expire.
  • suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon Oxygen, carbon-nitrogen, carbon-phosphorus -or Carbon-silicon single bonds or double bonds.
  • carbon-carbon double bonds are particularly advantageous and are therefore very particularly preferred according to the invention used. For the sake of brevity, they will be referred to as "Double bonds"
  • the preferred group according to the invention contains a Double bond or two, three or four double bonds. Getting more used as a double bond, the double bonds be conjugated. According to the invention, however, it is advantageous if the Isolated double bonds, in particular each terminally, in the present group in question. According to the invention it is of particular advantage two, in particular one, double bond to use.
  • Suitable groups are (meth) acrylate, ethacrylate, crotonate, Cinnamate, vinyl ether, vinylester, dicyclopentadienyl, norbornyl, Isoprenyl, isopropenyl, alfyl or butenyl groups; dicyclopentadienyl, Norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.
  • actinic radiation curable separate Networking systems depends mainly on what, in which Wavelength range activatable with actinic radiation Bindings are activated. This wavelength range is supposed to be outside lie the area with which the functional coating materials of the invention be hardened. The expert can therefore for a given actinic radiation curable invention Function coating material suitable curable with actinic radiation separate networking systems (B) due to its general Expertise, where appropriate, with the aid of simple-orientated Select trials easily.
  • crosslinking systems (B) are in particular those of Advantage that thermally crosslinkable via keto groups and hydrazide groups are. They are therefore particularly preferred according to the invention used.
  • the aqueous functional coating materials are, as already mentioned as the functional coating materials according to the invention designated.
  • the most preferred separate crosslinking system (B) is externally crosslinking or self-crosslinking.
  • the particularly preferred externally crosslinking separate Crosslinking system (B) contains at least one constituent (B 1), which in the statistical mean at least two, preferably at least three, It also contains keto groups in the molecule preferred externally crosslinking separate crosslinking system (B) at least one component (B 2), the statistical average of at least contains two hydrazide groups in the molecule.
  • the Ratio of the two components (B 1) and (B 2) can be very broad vary and depends on the functionality of the two complementary components.
  • the component (B 1) is selected from the group consisting of Oligomers and polymers, the terminal or lateral or terminal and contain lateral keto groups, selected suitable oligomers and Polymers originate from the above for the binders (A) described polymer classes, where (meth) acrylate copolymers (B 1) are particularly advantageous and therefore used with particular preference become.
  • the components (B 2) are selected from the group consisting from low molecular weight compounds having at least two Hydrazide groups and oligomers and polymers, the terminal or contain lateral or terminal and lateral hydrazide groups, selected.
  • Suitable oligomers and polymers come from the Polymer classes described below. Preference is given to low molecular weight compounds with two hydrazide groups in the molecule used.
  • suitable low molecular weight compounds with two Hydrazide groups are the dihydrazides of organic dicarboxylic acids, such as Phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid, sebacic acid or adipic acid.
  • Adipic dihydrazide is particularly preferably used
  • the most preferred self-crosslinking separate Crosslinking systems (B) contain in a further preferred Embodiment at least one constituent (B 3) selected from the group consisting of consisting of oligomers and polymers, in statistical average at least two, in particular at least three, terminal or lateral or terminal and lateral keto groups and at least two, in particular at least three, terminal or lateral or terminal and containing lateral hydrazide groups in the molecule, or they consist of this component (B 3).
  • the preferred ones may be separate Crosslinking systems (B) at least one of the above described complementary reactive functional groups for the thermal crosslinking and / or at least one of the above described reactive functional group containing at least one with actinic radiation activatable bond include. These reactive functional groups can then be used to crosslink the separate crosslinking systems (B) with the matrix of the layers of the Functional Beschichiungsstoffen invention serve.
  • crosslinking systems (B) over Are able to crosslink keto groups and hydrazide groups commercial substances and are used for example in the form of aqueous dispersions under the trademark Acronal ®, in particular Acronal ® A 603 or A 627, or under the trademark Luhydran ®, in particular Luhydran® LR 8950 or 8975, from BASF Aktiengesellschaft, under the trademark Viacryl®, in particular Viacryl® VSC 6270, 6286 or 6295, from Solutia or under the brand Setalux®, in particular Setalux® 6810 AQ-25 or XL 1141, from Akzo to be expelled.
  • Acronal ® in particular Acronal ® A 603 or A 627
  • Luhydran ® in particular Luhydran® LR 8950 or 8975
  • Viacryl® in particular Viacryl® VSC 6270, 6286 or 6295
  • Solutia or under the brand Setalux® in particular Setalux® 6810 AQ-25 or X
  • the aqueous dispersions are in particular with Adipic dihydrazide crosslinked
  • Adipic acid dihydrazide content of the aqueous dispersions at up to 10 % By weight, based on the solids content of the aqueous dispersions.
  • the content of the functional coating materials according to the invention to the separate networking systems (B) can vary and judge very broad according to the requirements of the case.
  • the contain functional coating materials according to the invention each based on the solid, 1 to 50, preferably 2 to 48, particularly preferably 3 to 44, most preferably 4 to 42 and in particular 5 to 40 wt .-% on (B).
  • the functional coating materials according to the invention contain at least one pigment (C).
  • the pigments (C) are selected from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetically shielding pigments, metal powders, organic and inorganic, transparent and opaque fillers and nanoparticles selected
  • the content of the functional coating materials according to the invention to the Pigments (C) can vary widely.
  • the content becomes so chosen that the quantity ratio of pigments (C) to binders (A) and to those in the separate crosslinking systems (B) optionally present oligomers and polymers (pigment-binder ratio) at 0.1: 1 to 3: 1, preferably 0.2: 1 to 2.8: 1, particularly preferably 0.3: 1 to 2.5: 1, very particularly preferably 0.3: 1 to 2: 1 and especially 0.3: 1 to 1.5: 1.
  • suitable effect pigments are metal flake pigments such as Commercially available aluminum bronzes, chromated according to DE 36 36183 A 1 Aluminum bronzes, and commercial stainless steel bronzes as well
  • Non-metallic effect pigments such as pearlescent or Interference pigments, platelet-shaped effect pigments based on Iron oxide, which has a color from pink to brown-red or liquid crystalline effect pigments.
  • Suitable inorganic coloring pigments are White pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron manganese black or spinel black; Color 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 sulphoselenide, molybdate red or ultramarine red; Brown iron oxide, Mixed brown, spinel and corundum phases or chrome orange; or Iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, Cadmium zinc sulfide, chrome yellow or bismuth vanadate
  • suitable organic coloring pigments are Monoazo pigments, bisazo pigments, anthraquinone pigments, Benzimidazole 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 pigments are Bis (azomethine) pigments.
  • Suitable electrically conductive pigments are Titanium dioxide / tin oxide pigments.
  • magnétiqueally shielding pigments are pigments on the Base of iron oxides or chromium dioxide.
  • suitable metal powders are powders of metals and Metal alloys aluminum, zinc, copper, bronze or brass.
  • Suitable organic and inorganic fillers are chalk, Calcium sulphates, barium sulphate, silicates such as talc, mica or kaolin, Silicic acids, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular Polyamide or polyacrylonitrile.
  • Suitable organic and inorganic fillers are chalk, Calcium sulphates, barium sulphate, silicates such as talc, mica or kaolin, Silicic acids, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular Polyamide or polyacrylonitrile.
  • mica and talc are used when the Scratch resistance produced from the powder coatings according to the invention Coatings should be improved.
  • platelet-shaped inorganic fillers such as talc or mica
  • non-platelet inorganic fillers such as chalk, dolomite Calcium sulfate, or barium sulfate
  • Suitable transparent fillers are those based on Silica, alumina or zirconia.
  • Suitable nanoparticles are selected from the group consisting hydrophilic and hydrophobic, in particular hydrophilic, Nanoparticles based on silica, alumina, zinc oxide, Zirconia and the polyacids and heteropolyacids of Transition metals, preferably of molybdenum and tungsten, with a Primary article size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
  • the hydrophilic nanoparticles have no Matting. Nanoparticles are particularly preferred on the Base of silicon dioxide used.
  • hydrophilic pyrogenic silicon dioxides used their agglomerates and aggregates a chain-like structure and by the flame hydrolysis of silicon tetrachloride in a blast gas flame can be produced.
  • These are, for example, by Degussa sold under the brand Aerosil ®.
  • precipitated water glasses such as Nanohektorite, the for example, from the company Südchemie under the brand Optigel ® or sold by Laporte under the name of Laponite®, used
  • the functional coating materials of the invention can still contain at least one additive (D), such as He usually in the field of functional coating materials is used.
  • D additive
  • Suitable additives are molecularly soluble Dyes, sunscreens, such as UV absorbers and reversible Radical scavengers (HALS); antioxidants; low and high boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Catalysts for crosslinking; thermolabile radical initiators; thermally and with actinic Radiation curable reactive thinner; Adhesion promoters; Leveling agents; film-forming aids; Rheology aids (thickeners); Flame retardants; Corrosion inhibitors; waxes; driers; biocides and / or matting agent; as for example in the textbook “Paint Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, or in the German patent application DE 199 14 896 A 1, column 14, page 26, to column 15, line 46, will be described in detail.
  • UV absorbers and reversible Radical scavengers HALS
  • the preparation of the functional coating materials according to the invention no special features on, but is done by Mixing the above-described ingredients in conventional and known mixing units, such as stirred tank, Ultraturrax, inline dissolver, Extruder or kneader.
  • the application of the functional coating materials according to the invention also no special features on, but can through all common application methods, e.g. Spraying, doctoring, painting, Pouring, dipping, trickling or rolling, done.
  • Spritzappükationsmethoden applied such as Compressed air spraying, airless spraying, high rotation, electrostatic Spray application (ESTA), if necessary combined with hot spray application such as hot air hot spraying.
  • ESA electrostatic Spray application
  • the layers of the invention Functional coating materials dried without fully closing them cure.
  • temperatures of 20 to 80, preferably 20 to 70 and especially 20 to 65 ° C applied The Drying can be assisted by laminar airflows.
  • drying times are from 30 seconds to two Hours, preferably one minute to one hour and especially one Minute applied to 45 minutes
  • the crosslinks separate, water-soluble and / or -dispersible crosslinking system (B) on and / or in the matrix of wet, dry and / or dried Layers partially or completely before the binder (A) completely network. If the separate networking systems (B) also or are curable exclusively with actinic radiation, the Layers irradiated with actinic radiation
  • Radiation sources are used for the irradiation with actinic radiation such as high pressure or low pressure mercury vapor lamps, which optionally doped with lead to a beam window up to 405 nm or electron beam sources into consideration. Further examples suitable methods and apparatus for curing with actinic Radiation are described in the German patent application DE 198 18 735 A 1, Column 10, lines 31 to 61 described.
  • the dried layer of the functional coating material according to the invention with at least one, in particular one, coated aqueous uncoated topcoat, creating a solid-color topcoat results.
  • the above-described Application methods are applied. Examples of suitable aqueous Solid-color topcoats are described in the patent applications cited above, in particular in the German patent application DE 199 14 896 A 1, Column 1, lines 29 to 49 described.
  • the Solid topcoat and the dried layer and optionally the dried electrodeposition coating together physically, thermally or thermally and with actinic radiation, in particular thermally or thermally cured with actinic radiation Curing method described above. It can the thermal curing in conventional and known convection ovens or with help done by IR lamps. It thus results in an inventive Multilayer coating comprising at least one, in particular one, Functional layer and at least one, in particular one, color and / or effect-imparting solid-color finish.
  • the dried layer with at least one, in particular coated with a water-based paint creating a Waterborne basecoat results.
  • suitable water-based paints be in the patent applications cited above, in particular in German Patent Application DE 199 14 896 A 1, column 1, lines 29 to 49, described.
  • the waterborne basecoat layer is then, without them completely cured, dried. The above described drying methods are used.
  • the dried layer from the functional coating material according to the invention, the Waterborne basecoat and the clearcoat and optionally the Electrocoating preferably thermally or thermally and with cured actinic radiation, the above-described Methods and devices can be applied. hereby results in a color and / or effect according to the invention Multicoat paint, the at least one functional layer, at least a color and / or effect waterborne finish and at least a clearcoat
  • Multilayer coatings have an excellent course, a even smooth surface, a high interlayer adhesion and excellent optical properties (appearance) on.
  • Opposite color and / or effect multicoat paint systems that no Functional layer i. S. of the present invention, but only one Have Einbrenn spallerlacktechnik occur in the use of and the same water-based paint little or no effect and / or Hue shifts on.
  • the functional coating materials 1 and 2 according to the invention and the functional coating material V1 not according to the invention were prepared by mixing the constituents specified in Table 1 in the order given and homogenizing.
  • the coated surface of the steel panels was in each case with half the functional coating materials of Examples 1 and 2 (Examples 3 and 4) and Comparative Experiment V1 (Comparative Experiments V2) coated, so that always half of the conventional surfacer paint remained visible.
  • the resulting layers of the functional coating materials Examples 1 and 2 and the comparative experiment V1 were dried at 60 ° C for 10 minutes

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

Claims (14)

  1. Procédé humide-humide de réalisation de peintures en plusieurs couches qui apportent une couleur et/ou un effet et qui contiennent au moins une couche fonctionnelle et au moins une peinture en une seule couche qui apporte une couleur et/ou un effet ou, en variante, au moins une peinture de base qui apporte une couleur et/ou un effet et au moins un vernis, le procédé comportant les étapes qui consistent à:
    (1) appliquer des enduits fonctionnels aqueux sur des supports recouverts ou non d'une couche de base,
    (2) sécher ensuite, sans les durcir complètement, les couches d'enduits fonctionnels aqueux ainsi obtenues,
    (3) revêtir les couches séchées (2) d'enduits fonctionnels aqueux de peintures aqueuses en une seule couche et
    (4) durcir ensemble les couches (2) et (3) pour obtenir les couches fonctionnelles et les peintures en une seule couche
    ou, en variante,
    (3) appliquer des peintures à base d'eau sur les couches séchées (2) d'enduits fonctionnels aqueux,
    (4) appliquer ensuite du vernis sur les couches (3) de peintures à base d'eau ainsi obtenues, sans durcir complètement celles-ci et
    (5) durcir ensuite ensemble les couches (2), (3) et (4) pour obtenir les couches fonctionnelles, les peintures de base et les vernis
    ou, en variante,
    (3) revêtir de peintures à base d'eau les couches séchées (2) d'enduits fonctionnels aqueux,
    (4) durcir ensemble les couches (3) de peintures à base d'eau ainsi obtenues et les couches séchées (2) pour obtenir les couches fonctionnelles et les peintures de base,
    (5) appliquer du vernis sur les peintures à base d'eau et
    (6) durcir ensuite les couches de vernis qui en résultent (5) pour obtenir les vernis,
    caractérisé en ce que l'on utilise des enduits fonctionnels aqueux qui contiennent:
    (A) au moins un liant réticulable,
    (B) au moins un système de réticulation séparé, soluble dans l'eau et/ou dispersible dans l'eau, qui réticule partiellement ou totalement de lui-même dans et/ou sur la matrice des couches (2) humides, en cours de séchage et/ou sèches d'enduits fonctionnels aqueux avant que les liants (A) réticulent et
    (C) au moins un pigment.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on sélectionne les liants (A) dans le groupe constitué des polyuréthanes saturés ou insaturés et stabilisés en conditions ioniques ou non ioniques ainsi qu'ioniques et non ioniques et greffés sur des composés oléfiniquement insaturés.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on sélectionne le système de réticulation (B) dans le groupe constitué des systèmes de réticulation durcissables physiquement, thermiquement, par rayonnement actinique ainsi que thermiquement et par rayonnement actinique.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que l'on sélectionne le système de réticulation (B) dans le groupe constitué des systèmes de réticulation durcissables thermiquement ou thermiquement et par rayonnement actinique.
  5. Procédé selon la revendication 4, caractérisé en ce que l'on sélectionne le système de réticulation (B) dans le groupe constitué des systèmes de réticulation thermiquement hétéroréticulants et autoréticulants.
  6. Procédé selon la revendication 5, caractérisé en ce que l'on réticule thermiquement le système de réticulation (B) au moyen de groupes cétone et de groupes hydrazide.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que l'on sélectionne les pigments (C) dans le groupe constitué des pigments, poudres métalliques, charges organiques ou minérales, transparentes ou opaques et nanoparticules qui apportent une couleur et/ou un effet, sont fluorescents, électriquement conducteurs ou offrent une protection magnétique.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que pour réaliser la couche de fond, on applique sur les supports une peinture par électrophorèse, on recouvre sans les durcir complètement les couches de peinture d'électrophorèse obtenues par les enduits fonctionnels aqueux et les peintures en une seule couche ou, en variante, avec les enduits fonctionnels aqueux, les peintures à base d'eau et les vernis, et ensuite on durcit ensemble toutes les couches ou on durcit les couches de peinture d'électrophorèse, les couches d'enduits fonctionnels et les couches de peintures à base d'eau, d'une part, et les couches de vernis, d'autre part.
  9. Enduit fonctionnel aqueux qui contient:
    (A) au moins un liant,
    (B) au moins un système de réticulation séparé, soluble dans l'eau et/ou apte à être dispersé dans l'eau, qui réticule partiellement ou totalement de lui-même dans et/ou sur la matrice des couches (2) humides, en cours de séchage et/ou sèches d'enduits fonctionnels aqueux avant que les liants (A) réticulent et
    (C) au moins un pigment.
    et dans lequel le système de réticulation (B) contient ou est constitué
    (B1) d'au moins un composant dont la molécule contient au moins deux groupes cétone en moyenne statistique et
    (B2) d'au moins un composant dont la molécule contient au moins deux groupes hydrazide en moyenne statistique
    et/ou
    (B3) d'au moins un composant dont la molécule contient en moyenne statistique au moins deux groupes cétone et au moins deux groupes hydrazide.
  10. Enduits fonctionnels aqueux selon la revendication 9, caractérisés en ce qu'on sélectionne les liants (A) dans le groupe constitué des polyuréthanes saturés ou insaturés et stabilisés en conditions ioniques ou non ioniques ainsi qu'ioniques et non ioniques et greffés sur des composés oléfiniquement insaturés.
  11. Enduits fonctionnels aqueux selon la revendication 9 ou 10, caractérisés en ce que l'on sélectionne les pigments (C) dans le groupe constitué des pigments, poudres métalliques, charges organiques ou minérales, transparentes ou opaques et nanoparticules qui apportent une couleur et/ou un effet, sont fluorescents, électriquement conducteurs ou offrent une protection magnétique.
  12. Enduits fonctionnels aqueux selon l'une quelconque des revendications 9 à 11, caractérisés en ce que le rapport pigment-liant est compris entre 0,1:1 et 3:1.
  13. Utilisation des enduits fonctionnels aqueux selon l'une quelconque des revendications 9 à 12 pour réaliser des peintures en plusieurs couches qui apportent une couleur et/ou un effet.
  14. Utilisation selon la revendication 13, caractérisée en ce qu'on utilise les enduits fonctionnels aqueux pour réaliser des couches fonctionnelles, des charges, des peintures de fond qui protègent contre les impacts de gravillons, des peintures en une seule couche et des peintures de base.
EP02730277A 2001-05-28 2002-05-24 Matieres d'enduction fonctionnelles aqueuses et procede integre de production de peintures multicouches produisant une couleur et / ou un effet Expired - Lifetime EP1417040B2 (fr)

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DE10124576A DE10124576B4 (de) 2001-05-28 2001-05-28 Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen, wäßrige Funktions-Beschichtungsstoffe und deren Verwendung
DE10124576 2001-05-28
PCT/EP2002/005707 WO2002096572A2 (fr) 2001-05-28 2002-05-24 Matieres d'enduction fonctionnelles aqueuses et procede integre de production de peintures multicouches produisant une couleur et / ou un effet

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US20040077750A1 (en) 2004-04-22
ES2255613T3 (es) 2006-07-01
CA2442545C (fr) 2008-07-22
DE10124576A1 (de) 2002-12-12
CA2442545A1 (fr) 2002-12-05
DE50205367D1 (de) 2006-01-26
EP1417040B2 (fr) 2010-09-15
MXPA03009170A (es) 2004-02-17
DE10124576B4 (de) 2006-03-16
WO2002096572A2 (fr) 2002-12-05
EP1417040A2 (fr) 2004-05-12
US6942902B2 (en) 2005-09-13
ES2255613T5 (es) 2011-02-23
WO2002096572A3 (fr) 2004-03-04
ATE313389T1 (de) 2006-01-15

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