EP0881955B1 - Procede permettant de recouvrir des substrats de plusieurs couches de substance de trempage electro-phoretique et de poudre pour revetement electrostatique - Google Patents

Procede permettant de recouvrir des substrats de plusieurs couches de substance de trempage electro-phoretique et de poudre pour revetement electrostatique Download PDF

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Publication number
EP0881955B1
EP0881955B1 EP97903348A EP97903348A EP0881955B1 EP 0881955 B1 EP0881955 B1 EP 0881955B1 EP 97903348 A EP97903348 A EP 97903348A EP 97903348 A EP97903348 A EP 97903348A EP 0881955 B1 EP0881955 B1 EP 0881955B1
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Prior art keywords
coating material
powder coating
electrodeposition
acid
powder
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EP97903348A
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German (de)
English (en)
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EP0881955A1 (fr
Inventor
Udo Reiter
Rolf Boysen
Josef Rademacher
Thomas BRÜCKEN
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • 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
    • B05D2451/00—Type of carrier, type of coating (Multilayers)

Definitions

  • the present invention relates to a method for multilayer Coating of substrates with a primer layer Electrocoat and a top coat of powder paint.
  • Electro dip coating has been a common process for many years.
  • the Electrodeposition paint is an (aqueous) dispersion in one Bath.
  • the substrate to be coated is one of two electrodes switched and immersed in this bath. Then it comes to electrophoretic deposition of the electrocoat on the Substrate. After reaching a sufficiently thick layer of lacquer the coating process ended and the paint layer dried and in usually branded.
  • Resins that can be electrodeposited on the cathode are e.g. in the U.S. Patent 3,617,458. It is cross-linkable Coating masses that are deposited on the cathode. This Coating compositions are derived from an unsaturated polymer, the Contains amine groups and carboxyl groups, and an epoxidized Material off.
  • cationic-electrical deposits are made Compositions described, the mixtures of certain Amine-aldehyde condensates and a variety of cationic are resinous materials, one of these materials being through Reaction of an organic polyepoxide with a secondary amine and solubilization can be made with acid.
  • Aqueous dispersions are known from US Pat. No. 3,640,926 let the cathode deposit electrically and from an epoxy resin ester, Water and tertiary amino acids exist.
  • the epoxy is that Reaction product of. a glycidyl polyether and a basic unsaturated oleic acid.
  • the amine salt is the reaction product of one aliphatic carboxylic acid and a tertiary amine.
  • Epoxy and polyurethane based binders for the use of Binder dispersions and pigment pastes are also in numerous configurations known. For example, be on the DE-27 01 002, EP-A-261 385, EP-A-004 090 and DE-PS 36 30 667.
  • the coating of fabrics with powder coatings is also common Method.
  • the powdery dry paint is evenly applied the substrate to be coated is then applied by Heating the substrate melted and baked the paint.
  • the Special advantages of powder coatings include that they are solvent-free get along and that the losses occurring with conventional paints through Overspray can be avoided, since non-stick powder coating is almost can be completely recycled.
  • the application of the powder coating the substrate is preferably made by electrostatic adhesion by applying high voltage or by friction charging is produced.
  • the combination of the coating is also state of the art known with electrocoat and with powder coating.
  • a powder coating layer is first sintered on and then applied an electrocoat.
  • From the JP 63274800 is also known to apply an electrocoat and at Dry at 110 ° C, apply a powder coating and finally both Burn layers together.
  • Priming with electrocoat may also be required are used for substrates that are made of material technology or geometrical Reasons for powder coating are difficult to access.
  • a typical one The application of this multi-layer coating is the coating of Heating radiators. The procedure is such that after the Coating of the substrate with the electro-dip lacquer only in this lacquer burned in a dryer.
  • the method according to the invention accordingly dispenses with one separate drying and baking step for the electrocoat, before the powder coating is applied. Instead, both paints branded in a common step. This procedure means a considerable simplification of the coating process. By the Omitting a burn-in process reduces both Investment and operating costs. Only one is needed Baking oven provided and operated. hereby there is also a saving in heating energy. In addition, the total processing time for the coating process is shorter, so that the productivity of the system is increased.
  • Electrocoating is pre-primed primarily around an electrically conductive substrate.
  • it can is a metal, preferably iron or zinc.
  • step a the substrate described is treated according to the invention Liquid paint applied. All are state of the art for this known coating methods can be used.
  • Electrodeposition paints are one example usable, the epoxy resins, which are preferably amine-modified, and / or blocked aliphatic polyisocyanate, pigment paste and possibly contain further additives.
  • the process is the electrocoat after the removal of the Substrate from the bath, preferably by air drying, e.g. with help of a blower pre-dried. It can preferably be in the air dry air, e.g. Compressed air, act.
  • the Substrate made, however, a bleeding or baking of the lacquer is to be avoided. Rather, its purpose is primarily at Use of the usual aqueous electrodeposition paints on these remove any remaining water film. Therefore temperatures of ⁇ 100 ° C preferred. Temperatures of ⁇ 80 ° C, particularly preferably ⁇ 60 ° C, most preferably ⁇ 40 ° C be respected.
  • the drying process does not extend over a period of time more than 60 min.
  • the drying time is preferably ⁇ 40 min., particularly preferred at ⁇ 30 min., most preferred at ⁇ 20 min ..
  • the pre-drying of the electrocoat layer is carried out until their solvent content has decreased in such a way that in the subsequent stoving the substance of the layer around less than 20%, preferably less than 13%. Because with Burning in of an electrocoat layer always occurs Substance loss due to evaporation of residual solvents and through the release of fission products during the crosslinking of the paint arise. By outgassing these substances it can be too Bubbles form, so that the lacquer layer is destroyed as a whole becomes. However, if the predrying is up to the above Maximum limits of the solvent content is carried out, that leads Outgassing the remaining solvents and the fission products to none Deterioration in product quality.
  • the aforementioned electrocoating paint is used Powder paint applied.
  • the crosslinking temperatures of the powder coating are higher lie than those of the electrocoat.
  • the Temperature difference at 5 to 60 ° C, particularly preferably at 10 to 40 ° C, very particularly preferably at 10 to 30 ° C, most preferably at 10 up to 20 ° C.
  • all known paint formulations are suitable, e.g. those described in EP-509 392, EP-509 393, EP-322 827, EP-517 536, U.S. 5,055,524 and U.S. 4,849,283.
  • the powder coating consist of epoxy resins, also epoxidized Novolaks, from crosslinking agents, preferably phenolic or amine hardeners or bicyclic guanidines, catalysts, Fillers and, if necessary, auxiliaries and additives.
  • the powder coatings used according to the invention preferably contain Epoxy resins, phenolic crosslinking agents, catalysts, auxiliaries as well as auxiliaries and typical powder additives, flow aids.
  • Suitable solid epoxy resins are all solid epoxy resins with one Epoxy equivalent weight between 400 and 3,000, preferably 600 to 2000. These are mainly epoxy resins based on Bisphenol A and Bisphenol F. Expoxidized are preferred Novolak. These preferably have an epoxy equivalent weight from 500 to 1,000.
  • the epoxy resins based on bisphenol A and bisphenol F have in generally a functionality of less than 2 that epoxidized Novolac resins have a functionality greater than 2. Particularly preferred are epoxidized in the powder coatings according to the invention Novolac resins with an average functionality in the range from 2.4 to 2.8 and with an epoxy equivalent weight in the range of 600 to 850.
  • Novolac resins with an average functionality in the range from 2.4 to 2.8 and with an epoxy equivalent weight in the range of 600 to 850.
  • the epoxidized novolac resins are the phenolic Hydroxyl groups etherified with alkyl, acrylic or similar groups. By reacting the phenolic hydroxyl groups with Epichlorohydrides are introduced into the molecule by epoxy groups. Starting from novolaks, the so-called epoxy novolak is formed.
  • Epoxidized novolaks are structurally related to bisphenol A resins.
  • Epoxidized novolac resins can be made by Epoxidation of novolaks, e.g. from 3 to 4 phenol cores, which are connected to each other via methylene bridges.
  • Novolak resins can also be alkyl-substituted phenols Formaldehyde can be used.
  • Suitable epoxy resins are, for example, those under the following names commercially available products:
  • suitable epoxy group-containing polyacrylate resins which by Copolymerization of at least one ethylenically unsaturated Monomer containing at least one epoxy group in the molecule with at least one other ethylenically unsaturated monomer, the contains no epoxy group in the molecule, can be produced, wherein at least one of the monomers is an ester of acrylic acid or Is methacrylic acid.
  • Polyacrylate resins containing epoxy groups are known (cf. e.g. EP-A-299 420, DE-B-22 14 650, DE-B-27 49 576, US-A-4, 091,048 and US-A-3, 781, 379).
  • glycidyl acrylate As examples of the ethylenically unsaturated monomers that are at least contain an epoxy group in the molecule, glycidyl acrylate, Glycidyl methacrylate and allyl glycidyl ether called.
  • alkyl esters of acrylic and Methacrylic acid which contain 1 to 20 carbon atoms in the alkyl radical, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, butyl acrylate, butyl methyl acrylate, 2-ethylhexyl acrylate and Called 2-ethylhexyl methacrylate.
  • acids e.g. Acrylic acid and methacrylic acid.
  • Acid amides such as e.g.
  • Acrylic acid and methacrylic acid amide vinyl aromatic compounds, such as styrene, methyl styrene and vinyl toluene, nitriles such as acrylonitrile and methacrylonitrile, vinyl and vinylidene halides such as vinyl chloride and Vinylidene fluoride, vinyl esters, e.g. Vinyl acetate and hydroxyl groups Monomers such as Hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • vinyl aromatic compounds such as styrene, methyl styrene and vinyl toluene
  • nitriles such as acrylonitrile and methacrylonitrile
  • vinyl and vinylidene halides such as vinyl chloride and Vinylidene fluoride
  • vinyl esters e.g. Vinyl acetate and hydroxyl groups
  • Monomers such as Hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • the epoxy group-containing polyacrylate resin usually has Epoxy equivalent weight of 400 to 2,500, preferably 500 to 1,500, particularly preferably 600 to 1,200, a number average molecular weight (Gel permeation chromatography using a Polystyrene standards determined) from 1,000 to 15,000, preferably from 1,200 to 7,000, particularly preferably from 1,500 to 5,000 and one Glass transition temperature (TG) from 30 to 80, preferably from 40 to 70, particularly preferably from 50 to 70 ° C (measured using the differential scanning calometry (DSC)).
  • Epoxy equivalent weight 400 to 2,500, preferably 500 to 1,500, particularly preferably 600 to 1,200, a number average molecular weight (Gel permeation chromatography using a Polystyrene standards determined) from 1,000 to 15,000, preferably from 1,200 to 7,000, particularly preferably from 1,500 to 5,000 and one Glass transition temperature (TG) from 30 to 80, preferably from 40 to 70, particularly preferably from 50 to 70 ° C (measured using the differential scanning
  • the epoxy group-containing polyacrylate resin is generally good known methods prepared by radical polymerization become.
  • hardeners for the epoxy group-containing polyacrylate resin for example polyanhydrides of polycarboxylic acids or of Mixtures of polycarboxylic acids, especially polyanhydrides from Dicarboxylic acids or mixtures of dicarboxylic acids.
  • Such polyanhydrides can be produced by the polycarboxylic acid or water is withdrawn from the mixture of polycarboxylic acids, where implemented two carboxyl groups to form an anhydride group become. Such manufacturing processes are well known and need therefore not to be explained in more detail.
  • the invention contains Powder coating phenolic or amine hardener. Are used can also use bicyclic guanidines.
  • phenolic resin can be used, for example, as long as it has the methylol functionality required for reactivity having.
  • Preferred phenolic resins are under alkaline conditions reaction products of phenol, substituted phenols and Bisphenol A with formaldehyde. Under such conditions, the Methylol group either ortho or para with the aromatic Ring linked.
  • Such phenolic Crosslinking agents are produced by reacting bisphenol-A or bisphenol-F with components containing glycidyl groups, e.g.
  • Phenolic crosslinking agents of this type are available, for example, under the trade name DEH 81, DEH 82 and DEH 87 from Dow DX 171 from Shell-Chemie and XB 3082 from Ciba Geigy.
  • the epoxy resins and the phenolic crosslinking agents are in such a ratio that the number of epoxy groups the number of phenolic OH groups is approximately 1: 1.
  • the powder coatings according to the invention contain one or more suitable catalysts for epoxy resin curing.
  • suitable Catalysts are phosphonium salts of organic or inorganic Acids, imidazole and imidazole derivatives, quaternary ammonium compounds as well as amines.
  • the catalysts are generally in proportions of 0.001% by weight to about 10% by weight, based on the total weight of the Epoxy resin and the phenolic crosslinking agent used.
  • Suitable phosphonium salt catalysts are Ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, Ethyltriphenylphosphonium thiocyanate, ethyltriphenylphosphonium acetate-acetic acid complex, Tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and tetrabutylphosphonium acetate-acetic acid complex.
  • This and other suitable phosphonium Catalysts are e.g. described in U.S. Patent Nos. 3,477,990 and U.S. Patent 3,341,580.
  • Suitable imidazole catalysts are, for example, 2-styrylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2-butylimidazole. This and further imidazole catalysts are e.g. described in the Belgian Patent No. 756,693.
  • Powder coatings based on polyesters containing carboxyl groups and Low molecular weight crosslinking agents containing epoxy groups are in a large number are known and are described, for example, in EP-A-389 926, EP-A-371 522, EP-A-326 230, EP-B-110 450, EP-A-110 451, EP-B-107 888, US 4,340,698, EP-B-119 164, WO 87/02043 and EP-B-10 805.
  • the carboxyl groups used as component A) Polyesters have an acid number in the range of 10-150 mg KOH / g, preferably in the range of 30-100 mg KOH / g.
  • the hydroxyl number of the Polyester resins should be ⁇ 30 mg KOH / g.
  • To be favoured Polyester with a carboxy functionality of ⁇ 2 is used.
  • the Polyesters are made according to the usual methods (compare e.g. Houben Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/2, Georg Thieme Verlag, Stuttgart 1961).
  • polyester aliphatic, cycloaliphatic and aromatic di- and Suitable polycarboxylic acids e.g. Phthalic acid, terephthalic acid, Isophthalic acid, trimellitic acid, pyromellitic acid, adipic acid, Succinic acid, glutaric acid, pimelic acid, suberic acid, Cyclohexanedicarboxylic acid,ginaic acid, sebacic acid and the like.
  • This Acids can also be in the form of their esterifiable derivatives (e.g. anhydrides) or their transesterifiable derivatives (e.g. Dimethyl ester) can be used.
  • an alcohol component for the production of the carboxyl groups Containing polyester A are the usually used di and / or Suitable polyols, e.g. Ethylene glycol, 1,2-propanediol and 1,3-propanediol, butanediols, diethylene glycol, triethylene glycol, Tetraethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-dimethylolcyclohexane, Glycerin, trimethylolethane, trimethylolpropane, Pentaerythritol, ditrimethylolpropane, dipentaerythritol, diglycerin and the like
  • di and / or Suitable polyols e.g. Ethylene glycol, 1,2-propanediol and 1,3-propanediol, butanediols, diethylene glycol, triethylene glycol, Tetraethylene glyco
  • polyesters thus obtained can be used individually or as a mixture different polyester can be used.
  • the as component A) suitable polyesters generally have a Glass transition temperature above 30 ° C.
  • polyesters examples include those under following brand names commercially available products: Crylcoat 314, 340, 344, 2680, 316, 2625, 320, 342 and 2532 from UCB, Drug bos, Belgium; Grilesta 7205, 7215, 72-06, 72-08, 72-13, 72-14, 73-72, 73-93 and 7401 from Ems-Chemie; Neocrest P670, P671, P672, P678, P662 from ICI and Uralac P2400, P2450, P5980, PS 998, P 3561 Uralac P3400 and Uralac P5000 from DSM.
  • the acidic polyester component A) also includes unsaturated, Polyester resins containing carboxyl groups in question. These will obtained by polycondensation, for example of maleic acid, Fumaric acid or other aliphatic or cycloaliphatic Dicarboxylic acids with an ethylenically unsaturated double bond, optionally together with saturated polycarboxylic acids, as Polycarboxylic.
  • the unsaturated groups can also by the alcohol component, e.g. by Trimethylolpropane monoallyl ether, into which polyester is introduced.
  • the powder coatings according to the invention contain 0.8 - as component B) 20.1% by weight of low molecular weight epoxy groups Curing agent.
  • a particularly suitable one is a low molecular weight curing agent containing epoxy groups Triglycidyl isocyanurate (TGIC).
  • TGIC is commercially available at, for example the name Araldit PT 810 (manufacturer: Ciba Geigy).
  • Other suitable low molecular weight epoxy groups are 1,2,4-triglycidyltriazolin-3,5-dione, diglycidyl phthalate and the diglycidyl ester of hexahydrophthalic acid.
  • Polyacrylate Resins Containing Epoxy Groups are understood to be polymers which are obtained by copolymerization of at least one ethylenically unsaturated monomer, the at least contains an epoxy group in the molecule, with at least one other ethylenically unsaturated monomer that does not contain an epoxy group, can be produced, at least one of the monomers being an ester of Acrylic acid or methacrylic acid.
  • Polyacrylate resins containing epoxy groups are known (cf. e.g. EP-A-299 420, DE-B-22 14 650, US-A-4,091,048 and US-A-3,781,379).
  • the at least one Epoxy group in the molecule glycidyl acrylate, Glycidyl methacrylate and allyl glycidyl ether called.
  • alkyl esters of acrylic and Methacrylic acid which contain 1 to 20 carbon atoms in the alkyl radical, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate and the corresponding methacrylates, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate called.
  • More examples of ethylenic unsaturated monomers that do not contain epoxy groups in the molecule are acids, e.g.
  • Acrylic acid and methacrylic acid acid amides, such as e.g. Acrylic acid and methacrylic acid amide, vinyl aromatic Compounds such as styrene, methyl styrene and vinyl toluene, nitriles such as Acrylonitrile and methacrylonitrile, vinyl and vinylidene halides, such as Vinyl chloride and vinylidene fluoride, vinyl esters such as e.g. Vinyl acetate and Vinyl propionate, and monomers containing hydroxyl groups, e.g. Hydroxyethyl acrylate and hydroxyethyl methacrylate.
  • vinyl aromatic Compounds such as styrene, methyl styrene and vinyl toluene
  • nitriles such as Acrylonitrile and methacrylonitrile
  • vinyl and vinylidene halides such as Vinyl chloride and vinylidene fluoride
  • vinyl esters such as e.g. Vinyl acetate and
  • the polyacrylate resin (component C) containing epoxy groups has an epoxy equivalent weight of 350 to 2000.
  • the polyacrylate resins containing epoxy groups usually have a number average molecular weight (determined by gel permeation chromatography using a polystyrene standard) from 1000 to 15000 and a glass transition temperature (T G ) from 30 to 80 (measured using differential scanning calorimetry (DSC)).
  • the acrylic resin containing epoxy groups is generally good known methods prepared by radical polymerization become.
  • epoxy groups are commercially available Polyacrylate resins, for example, are available under the name Almatex PD 7610 and Almatex PD 7690 (manufacturer: Mitsui Toatsu).
  • the powder coatings according to the invention contain as binders as Component D) 0.5-13.6% by weight of low molecular weight di- and / or Polycarboxylic acids and / or di- and / or polyanhydrides.
  • Prefers are as component D) saturated, aliphatic and / or cycloaliphatic dicarboxylic acids used, e.g. glutaric, Adipic acid, pimelic acid, suberic acid,fugic acid, Cyclohexanedicarboxylic acid, sebacic acid, malonic acid, dodecanedioic acid and succinic acid.
  • too aromatic di- and polycarboxylic acids are suitable, e.g.
  • phthalic acid Terephthalic acid, isophthalic acid, trimellitic acid and pyromellitic acid, of course also in the form of their anhydrides, insofar as they exist.
  • the amounts of the powder coating components A) to D) are such chosen that the ratio of the epoxy groups from B) and C) to the Sum of the carboxyl and anhydride groups from A) and D) 0.75-1.25: 1 is. This ratio is preferably 0.9-1, 1: 1.
  • the Puiverlacke contain 50 to 90%, preferably 60 to 80 wt .-% Binder and 10 to 50 wt .-%, preferably 20 to 40 wt .-% fillers.
  • Glycidyl group-functionalized crystalline fillers are used Silicic acid modifications into consideration. Usually they are in the mentioned range from 10 to 50 wt .-%, based on the Total weight of the powder coating used. In some cases, however filler contents of more than 50% by weight are also possible.
  • the crystalline silica modifications include quartz, cristobalite, tridymite, keatite, stishovite, melanophlogite, coesite and fibrous silica.
  • the crystalline silica modifications are glycidyl group functionalized, the glycidyl group functionalization being achieved by a surface treatment. These are, for example, silica modifications based on quartz, cristobalite and fused silica, which are produced by treating the crystalline silica modifications with epoxysilanes.
  • the glycidyl group-functionalized silica modifications are available on the market, for example, under the names Silbond R 600 EST and Silbond R 6000 EST (manufacturer: Quarzwerke GmbH) and are produced by reacting crystalline silica modifications with epoxysilanes.
  • the powder coatings advantageously contain 10 to 40% by weight, based on on the total weight of the powder coating glycidyl group functionalized crystalline silica modifications.
  • the powder coatings can also contain other inorganic fillers, for example titanium oxide, barium sulfate and fillers based on silicate, such as e.g. Talc, kaolin, magnesium, aluminum silicates, mica and similar included.
  • silicate such as e.g. Talc, kaolin, magnesium, aluminum silicates, mica and similar included.
  • the powder coatings may still Tools and additives included. Examples of these are leveling agents, Trickle aids and degassing agents, such as benzoin.
  • degassing agents are added to powder coating.
  • concentrations of this degassing agent are ⁇ 2% by weight, particularly preferably 0.1 to 0.8% by weight, very particularly preferably at 0.2 to 0.5% by weight, most preferably at ⁇ 0.4% by weight.
  • R is an alkanol with 1-6 C atoms.
  • R 1 and R 2 are benzoyl or phenyl groups.
  • R 1 and R 2 can also be the same or different. That is, R 1 and R 2 can equally be benzoyl or phenyl groups.
  • one residue can be a benzoyl group, while the other residue is a phenyl group.
  • Examples of a compound which can preferably be used is benzoylphenylmethanol (benzoin).
  • the powder coatings are produced by known methods (cf. e.g. Product information from BASF Lacke + Maschinen AG, "Powder coatings", 1990) by homogenization and dispersion, for example by means of an extruder, screw kneader, etc. After The powder coatings are produced by grinding and, if necessary, by sifting and sieving to the desired grain size distribution set.
  • the powder coatings described are following the order baked together with the electrocoat.
  • the electrocoating and powder coating layers are baked on melting of the powder coating and thus its uniform distribution, and to harden the binders.
  • the burn-in process lasts 10 to 40 minutes, preferably 15 to 30 minutes.
  • the method according to the invention finds a preferred use the coating of radiators, car bodies and Ruto accessories, machine parts, compressors, shelves, Office furniture and comparable industrial products.
  • the subject of the invention also includes a multi-layer coating Substrate which is characterized in that it is manufactured by first coating a layer on the substrate in an electrodeposition bath Electrocoating applied and then dried, then a layer of powder paint is applied and finally electrocoat and powder coating are baked together in one step.
  • the electrocoat layer of the multi-coated The substrate according to the invention preferably has a thickness of 5 to 35 ⁇ m, very particularly preferably 10 to 25 ⁇ m.
  • the powder coating layer has preferably a thickness of 30 to 200 microns, very particularly preferred 50 to 120 ⁇ m.
  • Figure 1 shows schematically the layer structure of the invention Substrate.
  • the layer is initially on the substrate 1 itself 2 made of electro dipping paint, which is usually 10 times thicker Layer 3 of powder coating is covered.
  • the substrate In the manufacture of the substrate according to the invention, the substrate first coated in an electro-dip bath 4. Then it will Electrodeposition bath removed and in a drying plant 5 Blow dry with air. Then e.g. creating one High voltage in a cabin 6 powder coating finely distributed on the Sprayed surface of the substrate. This powder paint is then in the furnace 7 together with the electrocoat layer at temperatures baked from approx. 150 to 220 ° C.
  • reaction mixture is then left on Cool to 90 ° C and add 183 g of butyl glycol and for further dilution 293 g of isobutanol.
  • temperature has dropped to 70 ° C, there is 41 g of N, N, -dimethylaminopropylamine are added, this temperature is kept for 3 h and carries out.
  • the resin has a solids content of 70.2% and a base content of 0.97 milliequivalents / gram.
  • 1120 g of the resin solution prepared according to point 1 are mixed with 420 g of the blocked solution prepared according to point 2 Polyisocyanate mixed at room temperature with stirring.
  • 2.2 g of a 50th % By weight solution of a commercially available defoaming agent (Surfynol; commercial product of Air Chemicals) in Ethylene glycol monobutyl ether and 18 g of glacial acetic acid are stirred in. After that 678 g of deionized water are added over 4 portions. It is then mixed with a further 1154 g of deionized water in small amounts Portions diluted.
  • the resulting aqueous dispersion is in a Vacuum distillation freed from low-boiling solvents and then with deionized water to a solids content of 33 Diluted wt%.
  • 2200 parts by weight of the dispersion prepared according to point 3 are made with 810 parts by weight of those according to item 5 Pigment paste added and with deionized water to 5000 Parts by weight filled up.
  • Parameters voltage between 100 and 400 V, preferably 150 to 300 V Temperature 24 to 35 ° C, preferably 28 to 32 ° C Time 120 to 300s, preferably 150 to 240s.
  • the radiator is rinsed and air so far blown off so that no more liquid drips off.
  • the resulting powder coating film does not show any malfunctions, as few fission products and Escape solvent from the KTL.
  • the Branding losses of KTL at most 15%, preferably at most 13% be.

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Claims (10)

  1. Procédé en vue du revêtement multicouches de substrats à l'aide d'un vernis pour trempage électrophorétique et d'un vernis en poudre, lors duquel
    a) au moins une couche (2) provenant d'un vernis fluide, de préférence, d'un vernis pour trempage électrophorétique, est appliquée sur un substrat (1), de préférence, en métal, en particulier, en fer ou en zinc,
    b) le substrat (1) est séché après l'immersion complètement ou partiellement,
    c) au moins une couche de vernis en poudre (3) est appliquée, et
    d) le vernis pour trempage électrophorétique et le vernis en poudre sont durcis par cuisson simultanément,
    caractérisé en ce que le séchage se fait à des températures ≤ 100°C, de préférence, ≤ 40°C, et en ce que, de ce fait, la teneur en solvants est réduite à un point tel que la perte de substances, lors du durcissement par cuisson de la couche de vernis pour trempage électrophorétique, par dégazage des solvants et des produits de clivage volatils est de moins de 20%, de préférence, de 13%.
  2. Procédé selon la revendication 1, caractérisé en ce que le séchage préalable de la couche de vernis pour trempage électrophorétique se fait par soufflage à l'aide d'air et/ou à températures élevées, de préférence, allant jusqu'à 40°C.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le séchage dure ≤ 60 minutes, de préférence, ≤ 30 minutes.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la cuisson conjointe du vernis pour trempage électrophorétique et du vernis en poudre se fait à des températures de 150 à 220°C, de préférence, de 160 à 200°C.
  5. Procédé selon la revendication 4, caractérisé en ce que la cuisson conjointe se fait pour une durée de 10 à 40 minutes, de préférence, de 15 à 30 minutes.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'application du vernis en poudre se fait par adhérence électrostatique, de préférence, par une tension élevée ou par un chargement par friction.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que, dans l'étape a) l'on utilise un vernis pour trempage électrophorétique, qui se réticule à une température de moins de 170°C, de préférence, à une température de 140°C à 160°C.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'on utilise un vernis en poudre, dont la température de réticulation se situe à une valeur de 10 à 60°C, de préférence, de 10 à 40°C au-dessus de la température de réticulation du vernis pour trempage électrophorétique.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'on utilise un vernis en poudre qui contient des agents de dégazage dans une concentration allant jusqu'à 2% en poids, tout particulièrement, de préférence, de 0,4% en poids.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le vernis en poudre contient, en tant qu'agent de dégazage, des composés de la formule
    Figure 00290001
    R étant un alcanol ayant 1 - 6 atomes de C et R1 ainsi que R2 étant des groupements benzoyle ou phényle et R1 et R2 pouvant être identiques ou différents.
EP97903348A 1996-02-23 1997-02-21 Procede permettant de recouvrir des substrats de plusieurs couches de substance de trempage electro-phoretique et de poudre pour revetement electrostatique Revoked EP0881955B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19606706 1996-02-23
DE19606706A DE19606706A1 (de) 1996-02-23 1996-02-23 Verfahren zur mehrlagigen Beschichtung von Substraten mit Elektrotauchlack und Pulverlack
PCT/EP1997/000831 WO1997030796A1 (fr) 1996-02-23 1997-02-21 Procede permettant de recouvrir des substrats de plusieurs couches de substance de trempage electro-phoretique et de poudre pour revetement electrostatique

Publications (2)

Publication Number Publication Date
EP0881955A1 EP0881955A1 (fr) 1998-12-09
EP0881955B1 true EP0881955B1 (fr) 2004-04-21

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EP97903348A Revoked EP0881955B1 (fr) 1996-02-23 1997-02-21 Procede permettant de recouvrir des substrats de plusieurs couches de substance de trempage electro-phoretique et de poudre pour revetement electrostatique

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US (2) US6254751B1 (fr)
EP (1) EP0881955B1 (fr)
JP (1) JP2000505718A (fr)
AT (1) ATE264720T1 (fr)
DE (2) DE19606706A1 (fr)
WO (1) WO1997030796A1 (fr)

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DE59711545D1 (de) 2004-05-27
EP0881955A1 (fr) 1998-12-09
JP2000505718A (ja) 2000-05-16
ATE264720T1 (de) 2004-05-15
US6254751B1 (en) 2001-07-03
DE19606706A1 (de) 1997-08-28
WO1997030796A1 (fr) 1997-08-28
US20010011639A1 (en) 2001-08-09

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