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
  • B05D7/24—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 for applying particular liquids or other fluent materials
• • 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
  • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
• • 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
  • B05D7/14—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 to metal, e.g. car bodies
• • 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
  • B05D7/53—Base coat plus clear coat type
  • B05D7/534—Base coat plus clear coat type the first layer being 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
  • B05D7/52—Two layers
  • B05D7/54—No clear coat specified
  • B05D7/542—No clear coat specified the two layers being cured or baked together
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
• • 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
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
  • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
  • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
  • C23F11/173—Macromolecular compounds
• • 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
  • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
  • B05D2401/20—Aqueous dispersion or solution
• • 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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment

Definitions

• the invention relates to a method for the coating of surfaces, a corresponding coating and the use of coated articles by this method.
• the following techniques are preferably used for the production of, in particular, anticorrosive coatings mainly consisting of an organic matrix and organic and / or inorganic additional components.
• the classical methods are based on the use of the Theological properties of the formulations used to achieve a complete coating of a joined workpiece. Although, by continuously rotating the subject workpiece after the dipping operation, accumulation of coating material at critical locations can be reduced, it is not possible with this method to achieve a completely homogeneous coating. In addition, at locations with higher coating levels during the drying and / or crosslinking process, voids such as blistering and cookers can occur which affect the quality of the overall coating.
• the electrophoretic methods avoid this problem by using electric current to deposit a uniform coating in the dipping. With this method, it is possible to produce largely homogeneous coatings on metallic workpieces.
• the deposited coatings show a very good adhesion in the wet state to the metallic substrate, whereby the workpiece can be treated in a subsequent rinsing step without detachment of the coating. As a result, the previously inaccessible areas on the workpiece are freed from excess coating solution and thus no defects can occur during the drying process.
• this technique has the following disadvantages in an electric immersion coating (ETL), such as in cathodic dip painting (KTL):
• ETL electric immersion coating
• KTL cathodic dip painting
• a corresponding immersion bath together with all electrical and mechanical equipment from the temperature control, power supply and electrical insulation, circulation device and feed device to the Disposal of the anolyte acid, which is formed in the electrolytic coating, and constructed very expensive with an ultrafiltration for Lackrezyklitation and control devices.
• ETL electric immersion coating
• KTL cathodic dip painting
• the known autophoretic methods are based on an electroless concept consisting of a pickling attack on the substrate surface used in which metal ions are dissolved out of the surface and an emulsion coagulates due to the concentration of metallic ions at the resulting interface.
• these methods do not have the above-mentioned limitation of the electrolytic processes with respect to the Faraday cage effect, the coatings produced during the process must be fixed after the first activation step in a complex multistage dipping process.
• the pickling attack leads to unavoidable contamination of the active zone by metal ions which must be removed from the zones.
• the method relies on a chemical deposition process that is not is self-regulating and can not be stopped if necessary, such. B. by switching off the electric current in the electrolytic process.
• the formation of too high a layer thickness is unavoidable.
• Document DE 102014213873 A1 discloses a process for coating substrates and articles coated by this process, in which cleaned surfaces of substrates are contacted and coated with an aqueous composition in the form of dispersion and / or suspension, and after drying of the organic coating Coating with a similar or further coating composition may be done before drying and / or baking.
• the essential feature of this process is that, prior to coating with an aqueous composition in the form of a dispersion and / or suspension, the substrate is coated with a polyvalent metal cations incorporating colloidal siliceous sol or a silane or silicate modified polymer.
• the invention relates to a process for coating metallic surfaces of substrates with aqueous compositions, also referred to below as coating compositions, in the form of a dispersion and / or suspension containing at least one stabilized binder and a gelling agent and with those in a pretreatment stage and / or during
• aqueous compositions also referred to below as coating compositions
• coating compositions in the form of a dispersion and / or suspension containing at least one stabilized binder and a gelling agent and with those in a pretreatment stage and / or during
• the contacting of cations dissolved from the metallic surface forms a coating based on an ionic gel, in which the coating is carried out by:
• a purified substrate is immersed in the mixture according to b) for at least 1 minute at room temperature and
• a test without gelling agent is carried out by preparing a mixture of demineralized water and 5 to 20% by weight of the dispersion to be tested;
• the mixture prepared under e) is also adjusted to a pH of 1 to 7 and
• the substrates with metallic surfaces when treated with the aqueous composition of a stabilized binder and gelling agent selected according to the invention, form a coating based on an ionic gel with the cations liberated from the metallic surface during the contacting and that the deposited on the substrate ionic gel layer allows the diffusing out further cations dissolved out of the metallic surface, so that the coating can be carried out with further coating compositions according to the invention in further coating baths / stages.
• stabilized binders are selected which fulfill the condition that
• the mixture prepared under e) is also adjusted by means of mineral acid to a pH of 1, 5 to 5 and
• the stabilized binders are particularly preferably selected from the group consisting of: nonionically stabilized polyepoxy dispersions, nonionically stabilized polyurethane dispersions and ionically stabilized polyacrylate dispersions.
• the aqueous compositions contain stabilized dispersions having a solids content of from 20 to 90% by weight, a viscosity of from 100 to 5000 mPas, a density of from 1.0 to 1.2 g / cm 3, and a pH in the range of zero From 5 to 10 in an amount of 0.01 to 80.0 wt .-% based on the total mass of the resulting mixture and at least one gelling agent in an amount of 0.001 to 20.0 wt .-% based on the total mass of resulting mixture.
• the aqueous compositions further contain one or more members selected from the following groups:
• a crosslinker selected from the group consisting of silanes, siloxanes, types of phenolic resins or amines in an amount of 0.01 g / L to 50 g / L,
• At least one additive selected from the group consisting of pigments, biocides, dispersing agents, film-forming aids, adjuncts for adjusting the pH, thickener and leveling agent.
• the gelling agent contains or consists of: a) at least one polysaccharide based on glycogens, amyloses, amylopectins, calloses, agar, algins, alginates, pectins, carrageenans, celluloses, chitins, chitosans, curdlanes, dextrans, fructans, collagens, gellan Gum, gum arabic, starches, xanthans, tragacanth, karayans, tara gums and glucomannans; b) at least one anionic polyelectrolyte of natural origin based on polyamino acids, collagens, polypeptides, lignins or c) at least one synthetic anionic polyelectrolyte based on polyamino acids, polyacrylic acids, polyacrylic acid copolymers, acrylamide copolymers, lignins, polyvinylsulfonic acid, polycarboxylic acids, polyphospho
• the aqueous compositions and organic coatings prepared therefrom contain at least one anionic polysaccharide selected from those having a degree of esterification of the carboxy function in the range of 5 to 75% based on the total number of alcohol and carboxy groups.
• the aqueous compositions and organic coatings produced contain at least one anionic polysaccharide or at least one anionic polyelectrolyte selected from those having a molecular weight in the range of 500th to 1000000 g / mol "1
• the aqueous compositions and the organic coatings produced contain at least one anionic polysaccharide or at least one anionic polyelectrolyte selected from those having a degree of amidation of the carboxy functions in the range of 1 to 50% or a degree of epoxidation of the carboxy functions of up to 80%.
• the anionic polyelectrolytes are modified with adhesion groups selected from the group consisting of chemical groups of multifunctional epoxides, isocyanates, primary amines, secondary amines, tertiary amines, quaternary amines, amides, imides, imidazoles, formamides, Michael reaction products, carbodiimides, carbenes, cyclic carbenes, cyclocarbonates, multifunctional carboxylic acids, amino acids, nucleic acids, methacrylamides, polyacrylic acids, polyacrylic acid derivatives, polyvinyl alcohols, polyphenols, polyols having at least one alkyl and / or aryl radical, caprolactam, phosphoric acids, phosphoric esters, epoxide esters, sulfonic acids, sulfonic esters, vinylsulfonic acids, vinylphosphonic acids, catechol, silanes and the silanols and / or siloxanes, triazines
• the aqueous compositions and the organic coatings produced therefrom have a content of at least one complexing agent for metal cations or a polymer which has been complexing-modified metal cations.
• the aqueous compositions and the organic coatings produced therefrom have a content of at least one complexing agent selected from those based on maleic acid, alendronic acid, itaconic acid, citraconic acid or mesaconic acid or the anhydrides or half esters of these carboxylic acids.
• the aqueous compositions and organic coatings prepared therefrom contain at least one type of cation selected from cationic salts selected from the group consisting of melamine salts, nitrososalts, oxonium salts, ammonium salts, quaternary nitrogen salts, salts of ammonium derivatives and metal salts of Ag, Al, Ba, Ca, Co, Cu, Fe, In, Mg, Mn, Mo, Ni, Pb, Sn, Ta, Ti, V, W, Zn and / or Zr.
• cationic salts selected from the group consisting of melamine salts, nitrososalts, oxonium salts, ammonium salts, quaternary nitrogen salts, salts of ammonium derivatives and metal salts of Ag, Al, Ba, Ca, Co, Cu, Fe, In, Mg, Mn, Mo, Ni, Pb, Sn, Ta, Ti, V, W, Zn and / or Zr.
• the aqueous compositions contain a crosslinker selected from the group consisting of: silanes, siloxanes, types of phenolic resins or amines in an amount of 0.01 g / L to 50 g / L.
• a crosslinker selected from the group consisting of: silanes, siloxanes, types of phenolic resins or amines in an amount of 0.01 g / L to 50 g / L.
• the aqueous compositions contain complex titanium and / or zirconium fluorides in an amount of from 0.01 g / L to 50 g / L.
• the aqueous compositions contain complex titanium and / or zirconium fluorides in an amount of from 0.1 g / L to 30 g / L.
• the aqueous compositions have a content of at least one defoamer.
• the aqueous compositions may further contain at least one additive selected from the group consisting of: pigments, biocides, dispersing aids, film-forming aids, pH adjusters, thickeners and leveling agents.
• the metallic surfaces are cleaned, pickled or pretreated.
• each of the aqueous compositions forms a coating based on an ionic gel, the layer thickness of all deposited coatings after drying and crosslinking of all applied layers being in the range from 3 to 500 ⁇ m, preferably from 5 to 300 ⁇ m, and particularly preferably 8 to 100 ⁇ and 2 to 10, preferably 3 to 5 layers are deposited.
• the individual organic coatings are formed in 0.05 to 20 minutes in an immersion bath and after drying each have a dry film thickness in the range of 1 to 100 ⁇ , preferably from 3 to 60 ⁇ and particularly preferably 5 to 30 ⁇ on.
• the invention also relates to aqueous compositions for use in the process according to the invention each consisting of a mixture of at least one stabilized dispersion having a solids content of 30 to 90% by weight, a viscosity of 100 to 5000 mPas and a density of 1, 0 to 1, 2 g / cm 3 in an amount of 0.01 to 80.0 wt .-% based on the total mass of the resulting mixture with a gelling agent in an amount of 0.001 to 20.0 wt .-% based on the total mass of resulting mixture, wherein the aqueous compositions have a pH in the range of 1 to 7.
• the aqueous compositions further contain one or more members selected from the following groups:
• a crosslinker selected from the group consisting of silanes, siloxanes, types of phenolic resins or amines in an amount of 0.01 g / L to 50 g / L,
• the coating of the invention can be preferably used for coated substrates as wire, wire mesh, tape, sheet metal, profile, trim, part of a vehicle or missile, element for a household appliance, element in construction, frame, guard rail, radiator or fence element, molding more complicated Geometry or small parts such as screw, nut, flange or spring. It is particularly preferably used in the automotive industry, in construction, for the appliance industry, for household appliances or in heating. The use of the method according to the invention is particularly preferred for coating substrates which cause problems in the coating with an electrodeposition paint. The invention will be described in more detail below with reference to examples, without thereby limiting the general teaching according to claim 1 of the invention. Examples
• Preceding is a general description of the materials used and the implementation of the method.
• Nonionically stabilized polyepoxy dispersion having a solids content of 45-49%, a pH of 5.0-6.0, a viscosity of 1000-2000 mPas, an epoxy equivalent of 2300-2800 and a density of 1.1 g / cm 3 .
• Nonionically stabilized polyurethane dispersion having a solids content of 30%, a pH of 3.0-6.0, a viscosity of 300-2000 mPas and a density of 1.1 g / cm 3 .
• Dispersion C Ionically stabilized polyacrylate dispersion having a solids content of 50%, a pH of 7.5-8.5, a viscosity of 200 mPas, a density of 1.05 g / cm 3 .
• gel formers used
• a 2% aqueous solution of the polysaccharide was used.
• a polysaccharide having a molecular weight of about 70 ⁇ 00 g / mol, a degree of amidation of 0%, a degree of esterification of 15%, an epoxidation degree of 0%, a galacturonic acid content of 85% was used.
• a 2% aqueous solution of the polysaccharide was used.
• the tables refer to the amount of solution per liter of formulation.
• Additives were preferably used when the formulations needed to be pH adjusted or foam formed.
• Table 1 Formulation examples for the coating and coating sequence according to the invention E: rinsing the organic coating:
• Rinsing after the organic coating serves to remove non-adherent components of the formulation and clusters of the formulation and to make the process as close to reality as usual for industrial applications.
• Drying or drying under film formation filming in the sense of the present invention also being understood to mean baking or crosslinking of the coating, in particular of the organic polymeric constituents:
• a five-layer coating optically clearly distinguishable by the pigment additives is obtained using the three binders used by way of example in the different layers.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Chemical Treatment Of Metals (AREA)

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• 2015
  • 2015-02-27 AU AU2015222090A patent/AU2015222090B2/en not_active Ceased
  • 2015-02-27 SG SG11201607140XA patent/SG11201607140XA/en unknown
  • 2015-02-27 ES ES15706813T patent/ES2753527T3/es active Active
  • 2015-02-27 BR BR112016019705-4A patent/BR112016019705B1/pt active IP Right Grant
  • 2015-02-27 EP EP15706813.1A patent/EP3110566B1/de active Active
  • 2015-02-27 US US15/121,998 patent/US11389823B2/en active Active
  • 2015-02-27 WO PCT/EP2015/054105 patent/WO2015128449A1/de not_active Ceased
  • 2015-02-27 CA CA2939783A patent/CA2939783A1/en not_active Abandoned
  • 2015-02-27 JP JP2016554433A patent/JP6645976B2/ja active Active
  • 2015-02-27 RU RU2016138171A patent/RU2701019C2/ru active
  • 2015-02-27 CN CN201580020675.5A patent/CN106413920B/zh active Active
  • 2015-02-27 KR KR1020167026611A patent/KR102399225B1/ko active Active
  • 2015-02-27 DE DE102015203507.7A patent/DE102015203507A1/de not_active Withdrawn
  • 2015-02-27 MX MX2016011120A patent/MX391294B/es unknown
• 2016
  • 2016-09-27 ZA ZA2016/06675A patent/ZA201606675B/en unknown

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