EP1417040B2 - 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
EP1417040B2
EP1417040B2 EP02730277A EP02730277A EP1417040B2 EP 1417040 B2 EP1417040 B2 EP 1417040B2 EP 02730277 A EP02730277 A EP 02730277A EP 02730277 A EP02730277 A EP 02730277A EP 1417040 B2 EP1417040 B2 EP 1417040B2
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Prior art keywords
aqueous
functional coating
coating materials
films
pigments
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German (de)
English (en)
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EP1417040A2 (fr
EP1417040B1 (fr
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Ekkehard Sapper
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BASF Coatings GmbH
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BASF Coatings GmbH
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    • 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 novel integrated wet-on-wet process for producing multicoat color and / or effect coatings which comprise 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 contain at least one clearcoat.
  • the present invention relates to novel aqueous functional coating materials for the production of multicoat color and / or effect paint systems.
  • Integrated wet-on-wet processes are coating processes in which at least two different coating materials are applied to one another in at least two layers, the lower layer or the lower layers merely being dried but not completely crosslinked, after which the layers are cured together
  • German patent application DE 44 38 504 A1 directed.
  • the aqueous functional coating materials used in this case are physically curable and contain as binder a water-dilutable polyurethane resin having an acid number of 10 to 60 and a number average molecular weight of 4,000 to 25,000.
  • the polyurethane resin can be prepared by aa) a polyester and / or polyether polyol having a number average molecular weight of from 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 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 and optionally dd) an organic compound containing hydroxyl and / or amino groups having a molecular weight of 40 to 400 or a mixture of such Compounds are reacted with each other and the resulting reaction product is at least partially neutralized.
  • the known aqueous functional coating materials allow the production of particularly thin surfacer finishes, antistonechip primers or functional layers, without the loss of stone chip resistance or deterioration of the coverage of the unevenness of the primed substrate occur.
  • the known wet-in-wet process is therefore economically and ecologically particularly favorable.
  • a disadvantage is that the known wet-in-wet process is limited to the use of a specific type of polyurethane and therefore offers no alternatives in this respect. Nevertheless one is because of the numerous economic, ecological and technical advantages, which from the DE 44 38 504 A1 offer known aqueous functional coating materials and the wet-in-wet process made possible hereby, strives to replace the usual and known so-called Einbrenn spaller by the aqueous functional coating materials.
  • the color and / or effect multicoat paint systems produced by these integrated processes can be repaired very well, and the composition of the functional coating materials (i) is also not materially limited. However, this does not apply to waterborne basecoats (ii), which are necessarily aqueous dispersions of (meth) acrylate copolymers based on components (x) and (y). Only this ensures that it is also possible to use clearcoats based on powder slurry clearcoats for the production of the multicoat paint systems without causing cracking ("mud cracking")
  • Aqueous functional coating materials containing at least one saturated, unsaturated and / or ionically and / or nonionically stabilized polyurethane grafted with olefinically unsaturated compounds as binders and pigments are known from the German patent applications DE 199 14 896 A1 . DE 199 53 445 A1 . DE 199 53 203 A1 or DE 199 53 446 A1 They can be cured thermally or 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 A1 and DE 199 53 2 03 A1 was essentially the object of providing aqueous and non-aqueous self-crosslinking functional coating materials, adhesives and sealants based on polyurethane with very good performance properties.
  • the self-crosslinking functional coating materials especially the aqueous self-setting functional coating materials, especially the setbstvernetzenden waterborne basecoats, in their processing in wet-on-wet process even when using powder clearcoat slurries no cracking (mud cracking) or digester or Cause needle sticks.
  • the new functional coating materials should show a very good storage stability, excellent application properties, such as a very good flow and a very low Läufeme Trent even at high film thicknesses.
  • the multicoat paint systems produced herewith are said to have an outstanding overall optical impression as well as a high resistance to chemicals, yellowing and weathering. Last but not least, no delamination of the layers after the water jet test should occur any more. All these advantages are to be achieved without an increase in the emission of organic compounds must be taken into account.
  • DE 199 53 203 A1 or DE 199 53 446 A1 can also be used as a filler. Preferably, however, they are used as water-based paints. Whether and, if so, to what extent the known aqueous functional coating materials as fillers are capable of substituting conventional and known stoving fillers in the context of a wet-on-wet process without an effect and / or hue shift occurring not known.
  • the known aqueous functional coating materials do not contain a separate, water-soluble and / or -dispersible crosslinking system, which in and / or on the matrix of wet, drying and / or dried layers of the aqueous functional coating materials for themselves partially or completely crosslinked before the layers completely crosslink completely.
  • the patent applications can be found no evidence that could stimulate the expert to enforce the aqueous functional coating materials such a system.
  • aqueous multicomponent systems based on hydroxyl-containing polyurethanes and polyisocyanates are known.
  • the aqueous multicomponent systems may contain radiation-curable binders, reactive diluents and photoinitiators.
  • radiation-curable binders reactive diluents
  • photoinitiators there are two separate networking systems next to each other.
  • the aqueous multicomponent systems can also be used as fillers.
  • the polyurethanes and the polyisocyanates begin to crosslink immediately after the application of the aqueous multicomponent systems because of their high reactivity, so that the curing with actinic radiation can not be carried out so that it is substantially completed before the complete thermal curing of the matrix of layers , Both injury mechanisms therefore run in parallel, or the curing with actinic radiation is carried out after the thermal curing
  • German patent application DE 199 04 317 A1 It was the object of the invention to provide aqueous multicomponent systems which, especially during prolonged storage, are attacked and destroyed by microorganisms to a lesser extent or not at all.
  • German patent application DE 198 155 125 A1 It was an object of the invention to provide aqueous multicomponent systems which are easy to prepare, homogeneous, easy to handle, low in solvents, safe to cook, splash-proof and stable in forced drying and which provide matt coatings which have no surface defects and gray haze, but are weather-stable and resistant to gasoline.
  • the object of the present invention is to provide a novel wet-on-wet process for the production of multicoat color and / or effect paint systems which has the economic, technical and ecological advantages of the German patent application DE 44 38 504 A1 or the European patent application EP 0 871 552 A1 has known method and which makes it possible to substitute Einbrennyogller without great material, apparatus and procedural effort, without this an effect and / or hue shift occurs in the water-based paints.
  • a novel aqueous functional coating material which is outstandingly suitable for the production of multicoat color and / or effect coatings, in particular for the production of functional layers, fillers, antistonechip primers, solid-color topcoats and basecoats Functional layers, can be used.
  • the new aqueous functional coating material should be suitable for the new wet-on-wet process.
  • the efindungshunte process is used to produce color and / or effect multi-layer coatings on primed or unprimed substrates.
  • the new multicoat color and / or effect paint systems contain 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.
  • Functional layers i. S. of the present invention are surfacers i. S. of the German patent application DE 44 38 504 A1 or the European patent application EP 0 871 552 A1 , which have a high stone impact protection even in unusually thin layer thicknesses 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.
  • inventive method and the functional coating materials according to the invention are not only outstandingly suitable for applications in the fields of automotive OEM finishing and automotive refinishing, but also for the coating of buildings in the interior and exterior and of doors, windows and furniture, for industrial coating , including coil coating, container coating and the impregnation and / or coating of electrical components, as well as for the painting of white goods, including household appliances, boilers and radiators, into consideration.
  • industrial coatings they are suitable for painting virtually all parts and articles for private or industrial use such as household appliances, small metal parts, such as nuts and bolts. Hub caps, rims, packaging, or electrical components, such as Motorwicktitch or transformer windings.
  • primers can be used, which are prepared in a conventional manner from electrocoating.
  • anodic and cathodic electrodeposition paints but especially cathodic electrodeposition paints, are considered.
  • they can also have a cathodically deposited electrodeposition coating layer which is not thermally cured but only dried or partially cured.
  • the electrodeposition coating or the electrodeposition coating layer can then be combined with the functional components according to the invention. Coating materials or to be used according to the invention to be used coating materials. These can then be cured together with the electrodeposition coating layer (wet-in-wet process).
  • non-functionalized and / or non-polar plastic surfaces they may be subjected to a pre-treatment, such as with a plasma or with flames, or provided with a hydro-primer prior to coating in a known manner.
  • At least one, in particular one, functional coating material according to the invention is applied to a substrate.
  • the functional coating material according to the invention comprises at least one, in particular one, binder (A).
  • the binders (A) are not limited in their material composition. In addition, they may be oligomers or polymers.
  • Oligomers are understood as meaning resins which contain at least 2 to 15 monomer units in their molecule. By polymers are meant resins which contain at least 10 recurring monomer units in their molecule. In addition to these terms Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomers", page 425 , referenced.
  • the binders (A) are preferably selected from the group consisting of physically, thermally, currently or thermally curable and with actinic radiation curable or crosslinkable, random, alternating and / or block-like, linear and / or branched and / or comb-like (Co) polymers of ethylenically unsaturated monomers, and polyaddition resins and polycondensation resins, selected These terms are supplementary Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition” and “Polyaddition Resins (Polyadducts)” , such 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.
  • Suitable 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, and therefore they are preferably used.
  • the polyurethanes (A) are particularly preferably selected from the group consisting of saturated, unsaturated and grafted with olefinically unsaturated compounds, ionic or nonionic and ionic and nonionic stabilized polyurethanes
  • the content of the functional coating materials according to the invention on binders (A) can vary widely and depends on the requirements of the individual case.
  • the content is preferably from 10 to 80, preferably from 15 to 78, particularly preferably from 20 to 76, very particularly preferably from 25 to 74 and in particular from 30 to 72,% by weight, based in each case on the solids of the functional coating material.
  • the term "separate" makes it clear that the crosslinking system is independent or substantially independent of the crosslinking of the binder (A). It is essential here that the separate crosslinking system (B) in and / or on the matrix of wet, drying and / or dried layers of the functional coating materials according to the invention for themselves partially or completely crosslinked before the binder (A), in particular the Fully crosslinking polyurethanes (A) and thus completely crosslinking the layers as a whole.
  • the separate crosslinking system (B) to be used according to the invention can be of any desired composition, as long as it fulfills the requirement essential to the invention.
  • the separate crosslinking system (B) to be used in the present invention can be selected based on the composition of the aqueous functional coating materials based on the above-described binders (A), especially the polyurethanes (A).
  • the separate crosslinking system (B) is a thermally curable crosslinking system.
  • the separate crosslinking systems (B) may further comprise at least one of the complementary reactive functional groups for thermal crosslinking described below and / or at least one reactive functional group described below containing at least one bond activatable with actinic radiation. These reactive functional groups can then serve to crosslink the separate crosslinking systems (B) with the matrix of the layers of the functional coating materials according to the invention.
  • 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, are preferably used as the actinic radiation.
  • NIR near infrared
  • UV radiation or X-radiation in particular UV radiation
  • / or corpuscular radiation in particular electron radiation
  • the separate crosslinking system (B) is externally crosslinking or self-crosslinking.
  • the term "self-crosslinking” refers to the property of the crosslinking system (B) to be used according to the invention "by itself” crosslinking reactions.
  • the prerequisite for this is that at least one constituent already contains both types of complementary reactive functional groups which are necessary for crosslinking, or reactive functional groups which can react with themselves.
  • such externally crosslinking systems are those separate crosslinking systems (B) in which one type of the complementary reactive functional groups is present in a binder and the other type in a hardener or crosslinking agent.
  • Rompp Lexikon Lacke and printing inks Georg Thieme publishing house, Stuttgart, New York, 1998, "hardening", pages 274 to 276, in particular page 275 , below, directed.
  • 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.
  • the selection of the complementary reactive functional groups depends on the temperature range in which the complete curing of the matrix of the layers of the functional coating materials according to the invention, which also includes the binders (A), in particular the polyurethanes (A), takes place.
  • the thermal curing of the separate crosslinking system (B) must take place at lower temperatures, since the functional coating materials according to the invention are thermally or thermally and actinic radiation-curable functional coating materials.
  • the person skilled in the art can therefore, for a given group of functional coating materials according to the invention, easily select the appropriate complementary reactive functional groups on the basis of their general knowledge, if appropriate with the aid of simple orienting experiments.
  • the curing with actinic radiation is carried out with the aid of reactive functional groups containing at least one, in particular one, activatable with actinic radiation bond.
  • a bond which can be activated by actinic radiation is understood to mean a bond which becomes reactive upon irradiation with actinic radiation and undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its type which proceed by free-radical and / or ionic mechanisms.
  • suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds.
  • the carbon-carbon double bonds are particularly advantageous and are therefore very particularly preferably used according to the invention. For the sake of brevity, they will be referred to as "double bonds" in the following
  • the preferred group according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds may be conjugated. According to the invention, however, it is advantageous if the double bonds are present in isolation, in particular each terminally, in the group in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
  • Suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinylester, dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, alfyl or butenyl groups; Dicyclopentadienyl, norbornyl, 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 crosslinking systems (B) depends primarily on the wavelength range in which activatable with actinic bonds bonds are activated. This wavelength range should be outside the range with which the functional coating materials according to the invention are cured. The person skilled in the art can therefore easily select suitable actinic radiation curable separate crosslinking systems (B) for a given actinic radiation curable functional coating material of the present invention, optionally with the aid of simple orienting experiments.
  • the externally crosslinking separate crosslinking system (B) contains at least one constituent (B 1) containing on statistical average at least two, preferably at least three, keto groups in the molecule.
  • the separate crosslinking system (B) contains at least one constituent (B 2) which is included in the statistical Agent contains at least two hydrazide groups in the molecule.
  • the separate crosslinking system (B) consists of a component (B 1) and a component (B 2).
  • the ratio of the two constituents (B 1) and (B 2) can vary very widely and depends on the functionality of the two complementary constituents.
  • the component (B 1) is selected from the group consisting of oligomers and polymers containing terminal or lateral or terminal and lateral keto groups.
  • Suitable oligomers and polymers are derived from the polymer classes described above for the binders (A), where (meth) Acrylate copolymers (B 1) are particularly advantageous and are therefore particularly preferably used.
  • the components (B 2) are selected from the group consisting of low molecular weight compounds having at least two hydrazide groups and oligomers and polymers, the terminal or lateral or terminal and lateral hydrazide groups.
  • Suitable oligomers and polymers are derived from the polymer classes described below.
  • the low molecular weight compounds having two hydrazide groups in the molecule are preferably used.
  • suitable low molecular weight compounds having 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 self-crosslinking, separate crosslinking systems (B) contain at least one constituent (B 3) selected from the group consisting of oligomers and polymers which on statistical average have at least two, in particular at least three, terminal or lateral or terminal keto groups and at least two, in particular at least three, terminal or lateral or terminal and lateral hydrazide groups contained in the molecule, or they consist of this component (B 3).
  • the separate crosslinking systems (B) are commercially available 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 the BASF Aktiengesellschaft, under the brand name Viacryl®, in particular Viacryl® VSC 6270, 6286 or 6295, from the company Solutia or under the brand Setalux®, in particular Setalux® 6810 AQ-25 or XL 1141, by Akzo.
  • the adipic acid dihydrazide content of the aqueous dispersions is 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 on the separate crosslinking systems (B) can vary very widely and depends on the requirements of the individual case.
  • the functional coating materials of the invention contain, based in each case on the solid, 1 to 50, preferably 2 to 48, particularly preferably 3 to 44, very particularly preferably 4 to 42 and in particular 5 to 40 wt .-% of (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
  • the content of the functional coating materials according to the invention on the pigments (C) can vary widely.
  • the content is selected so that the quantitative ratio of pigments (C) to binders (A) and to the optionally present in the separate crosslinking systems (B) oligomers and polymers (pigment-binder ratio) at 0.1: 1 to 3 : 1, preferably 0.2: 1 to 2.8: 1, more preferably 0.3: 1 to 2.5: 1, most preferably 0.3: 1 to 2: 1 and especially 0.3: 1 to 1.5: 1 is.
  • suitable effect pigments are metal flake pigments such as commercial aluminum bronzes, according to DE 36 36183 A1 chromated aluminum bronzes, and commercial stainless steel bronzes and non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which has a hue of pink to brown-red, or liquid-crystalline effect pigments.
  • metal flake pigments such as commercial aluminum bronzes, according to DE 36 36183 A1 chromated aluminum bronzes
  • non-metallic effect pigments such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide, which has a hue of pink to brown-red, or liquid-crystalline effect pigments.
  • Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998 pages 176, "Effect pigments” and pages 380 and 381 "Metal oxide mica pigments” to "Metallpigmente”
  • Suitable inorganic color 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; 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
  • suitable organic color pigments are monoazo pigments, disazo 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 examples include pigments based on 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 sulfates, barium sulfate, silicates such as talc, mica or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular of polyamide or polyacrylonitrile.
  • silicates such as talc, mica or kaolin
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as plastic powder, in particular of polyamide or polyacrylonitrile.
  • mica and talc are used when the scratch resistance of the coatings prepared from the powder coatings of the invention is to be improved.
  • platelet-shaped inorganic fillers such as talc or mica
  • non-platelet inorganic fillers such as chalk, dolomite calcium sulfates, or barium sulfate
  • Suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide.
  • Suitable nanoparticles are selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, nanoparticin based on silica, alumina, zinc oxide, zirconium oxide and the polyacids and heteropolyacids of transition metals, preferably of molybdenum and tungsten, having a primary particle size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
  • the hydrophilic nanoparticles have no matting effect. Particular preference is given to using nanoparticles based on silicon dioxide.
  • hydrophilic pyrogenic silicon dioxides whose agglomerates and aggregates have a chain-like structure and which can be prepared by the flame hydrolysis of silicon tetrachloride in an oxyhydrogen flame. These are marketed, for example, by Degussa under the Aerosil® brand.
  • precipitated water glasses such as nanohektorites, which are sold, for example, by Südchemie under the Optigel® brand or by Laporte under the Laponite® brand
  • the functional coating materials according to the invention may also contain at least one additive (D), as is commonly used in the field of functional coating materials.
  • Suitable additives are molecularly soluble dyes, light stabilizers, 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 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 agents; as described, for example, in the textbook »Lackadditive« by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, or in the German patent application DE 199 14 896 A1 , Column 14, page 26, to column 15, line 46, will be described in detail.
  • HALS reversible radical scavengers
  • the preparation of the functional coating materials according to the invention has no special features, but takes place by mixing the constituents described above in customary and known mixing units, such as stirred tank, Ultraturrax, inline dissolver, extruder or kneader.
  • the application of the functional coating materials of the invention also has no special features, but can by all conventional application methods, such as. Spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • spray application methods are used, such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air hot spraying.
  • ESA electrostatic spray application
  • these application methods can also be used for the application of solid-color topcoats, aqueous basecoats and clearcoats.
  • the layers of the functional coating materials according to the invention are dried without curing them completely.
  • temperatures of from 20 to 80, preferably from 20 to 70 and in particular from 20 to 65 ° C. are used.
  • the drying can be assisted by laminar air flows.
  • drying times of 30 seconds to two hours, preferably one minute to one hour, and more preferably one minute to 45 minutes are used
  • the separate, water-soluble and / or dispersible crosslinking system (B) partially or completely crosslinks on and / or in the matrix of the wet, dry and / or dried layers before the binders (A) crosslink completely. If the separate crosslinking systems (B) are curable also or exclusively with actinic radiation, the layers are irradiated with actinic radiation
  • Radiation sources such as high pressure or low pressure mercury vapor lamps optionally doped with lead to open a beam window up to 405 nm, or electron beam sources are contemplated for irradiation with actinic radiation. Further examples of suitable methods and apparatus for curing with actinic radiation are disclosed in US Pat German patent application DE 198 18 735 A1 , Column 10, lines 31 to 61 described.
  • the dried layer of the functional coating material according to the invention is coated with at least one, in particular one, aqueous solid-color topcoat, resulting in a solid-color topcoat layer.
  • aqueous solid-color topcoat examples are described in the patent applications cited above, in particular in the German patent application DE 199 14 896 A1 , Column 1, lines 29 to 49 described.
  • the solid-color topcoat layer and the dried layer and, optionally, the dried electrodeposition coating layer are cured together thermally or thermally and with actinic radiation.
  • the curing methods described above are used.
  • the thermal curing can be carried out in customary and known circulating air ovens or with the aid of IR lamps. This results in a multi-layer coating according to the invention which comprises at least one, in particular one, functional layer and at least one, in particular one, color and / or effect solid-color topcoating.
  • the dried layer is coated with at least one, in particular a water-based lacquer, resulting in a water-based lacquer layer.
  • a water-based lacquer examples include water-based paints, in the patent applications cited above, in particular in the German patent application DE 199 14 896 A1 , Column 1, lines 29 to 49 described.
  • the waterborne basecoat is then dried without fully curing. The drying methods described above can be used.
  • At least one, in particular one, clearcoat is applied to the dried aqueous basecoat, thereby resulting in a clearcoat.
  • suitable clearcoat materials are described in the patent applications cited above, in particular in the German patent application DE 199 14 896 A1 , Column 17, line 57, to column 18, line 30 described. Unless they are powder coatings, the application methods described above can be used. Examples of suitable application methods for powder coatings are described, for example, in the product information of the company Lacke + Weg AG, "Powder coatings", 1990.
  • the dried layer of the functional coating material according to the invention, the aqueous basecoat layer and the clearcoat layer and optionally the electrodeposition coating layer are cured thermally or thermally and with actinic radiation, wherein the methods and apparatuses described above can be used.
  • the dried layer of the functional coating material according to the invention and the waterborne basecoat layer are cured together. Then at least one clearcoat is applied to the resulting waterborne finish, after which the resulting clearcoat (s) are cured, using the methods described above and devices can be applied. This also results in an inventive color and / or effect multi-layer coating of the structure described above
  • the multicoat color and / or effect paint systems according to the invention produced by the process according to the invention have an excellent flow, a uniformly smooth surface, a high intercoat adhesion and excellent optical properties (appearance).
  • multicoat color and / or effect paint systems which do not have a functional layer i. S. of the present invention, but only have a Einbrenn spallerlacktechnik occur when using one and the same water-based paint little or no effect and / or hue shifts.
  • 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.
  • Table 1 The composition of the functional coating materials 1 and 2 according to the invention (Examples 1 and 2) and of the noninventive functional coating material V1 (Comparative Experiment V1) ingredients
  • Electrodeposition coating For the production of multi-layer roofing, steel panels were coated with a customary and known cathodic electrodeposition coating. On the electrodeposition coating, a commercially available filler (Ecoprime® 130 from BASF Coatings AG) was pneumabsch applied and then baked for 30 minutes at 130 ° C, so that a surfacer coating resulted.
  • Ecoprime® 130 from BASF Coatings AG
  • the coated surface of the steel panels was in each case half coated with the functional coating materials of Examples 1 and 2 (Examples 3 and 4) and Comparative Experiment V1 (Comparative Experiments V2), so that always half of the conventional surfacer coating remained visible.
  • the resulting layers of the functional coating materials of Examples 1 and 2 and Comparative Experiment V1 were dried at 60 ° C for 10 minutes
  • the entire coated surfaces of the steel panels were coated with a commercially available water-based paint in the shade of brilliant silver from BASF Coatings AG and dried for 10 minutes at 60 ° C. Thereafter, the two layers were baked for 30 minutes at 130 ° C in a convection oven.

Landscapes

  • 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 (10)

  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,
    et le système de réticulation (B) contenant ou étant 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.
  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 l'une quelconque des revendications 1 ou 2, 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.
  4. Procédé selon l'une quelconque des revendications 1 à 3, 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.
  5. 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.
  6. Enduits fonctionnels aqueux selon la revendication 5, 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.
  7. Enduits fonctionnels aqueux selon la revendication 5 ou 6, 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.
  8. Enduits fonctionnels aqueux selon l'une quelconque des revendications 5 à 7, caractérisés en ce que le rapport pigment-liant est compris entre 0,1:1 et 3:1.
  9. Utilisation des enduits fonctionnels aqueux selon l'une quelconque des revendications 5 à 8 pour réaliser des peintures en plusieurs couches qui apportent une couleur et/ou un effet.
  10. Utilisation selon la revendication 9, 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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DE10124576 2001-05-28
DE10124576A DE10124576B4 (de) 2001-05-28 2001-05-28 Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen, wäßrige Funktions-Beschichtungsstoffe und deren Verwendung
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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ES2255613T5 (es) 2011-02-23
DE50205367D1 (de) 2006-01-26
DE10124576A1 (de) 2002-12-12
US6942902B2 (en) 2005-09-13
CA2442545C (fr) 2008-07-22
EP1417040A2 (fr) 2004-05-12
CA2442545A1 (fr) 2002-12-05
WO2002096572A3 (fr) 2004-03-04
EP1417040B1 (fr) 2005-12-21
US20040077750A1 (en) 2004-04-22
ES2255613T3 (es) 2006-07-01
ATE313389T1 (de) 2006-01-15
WO2002096572A2 (fr) 2002-12-05
MXPA03009170A (es) 2004-02-17
DE10124576B4 (de) 2006-03-16

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