EP1088598B1 - Procédé pour fabriquer un film polymérique sur un substrat, concentré et liquide de traitement pour se faire - Google Patents

Procédé pour fabriquer un film polymérique sur un substrat, concentré et liquide de traitement pour se faire Download PDF

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Publication number
EP1088598B1
EP1088598B1 EP00120052A EP00120052A EP1088598B1 EP 1088598 B1 EP1088598 B1 EP 1088598B1 EP 00120052 A EP00120052 A EP 00120052A EP 00120052 A EP00120052 A EP 00120052A EP 1088598 B1 EP1088598 B1 EP 1088598B1
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EP
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Prior art keywords
treatment liquid
film
temperature
water
substrate
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EP00120052A
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German (de)
English (en)
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EP1088598A2 (fr
EP1088598A3 (fr
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Heribert Domes
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Chemetall GmbH
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Chemetall 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
    • B05D7/14—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

Definitions

  • the invention relates to a method for producing a film of plastic or a plastic-containing material on a metal surface and a concentrate for producing a treatment liquid and a treatment liquid for the production of the polymeric film.
  • Polymeric films on metal surfaces are used in a variety of ways. There are also a variety of large-scale processes for coatings of metal workpieces or workpieces with a metallic surface with a polymeric film. Depending on the nature of the metal surface or the workpieces, the application of a polymeric film can be carried out without difficulty or be provided with considerable disadvantages. By suitable chemical and physical adjustment of the applied polymeric solution or dispersion can be produced in several processes in one operation, a polymeric layer of the desired thickness. For example, in a roller coating method such as roll coating, it is of particular importance to match the concentration of the plastic-containing treatment solution and the roller pressure of the application device, the roller speed and the direction of travel of the rollers to the substrate. Comparatively simple, the treatment of small or relatively large, rounded workpieces, which are usually coated in the electro-dip or spray process.
  • Dipping method at room temperature without electrical deposition are associated with the disadvantage that due to the geometry of the parts different layer thicknesses are produced and that remain at the drain points drops of the plastic-containing solution or dispersion, which are visible after the subsequent drying as thickening. Even after a subsequent spray painting these thickenings are clearly visible. In addition to the less attractive appearance, the treated parts - depending on the purpose - u. U. also useless because of lack of fitting accuracy.
  • DE-A-197 25 780 describes a method for applying plastic or plastic-containing layers to metallic items at about room temperature and its use as a pretreatment of the items for the subsequent powder coating.
  • a solution or dispersion having a content of 5 to 50 wt .-% of an organic polymer is brought into contact with the metallic component, dried the applied solution or dispersion, the coated item then with a substantially identical, but very dilute solution or Dispersion brought into contact and finally dried. Due to the double immersion treatment, drop-like unevenness and larger thickening are avoided. Nevertheless, the layer thickness at the outflow edge is often larger by a factor of 2 to 3 than at the other surfaces of the individual part. However, if dipping only once, the layer thickness at the run-off edge would be about 30 to 53 times thicker than at the other surfaces of the item.
  • WO 94/10244 which also discloses the features of the preamble of claim 1, describes several compositions for the pretreatment of substrates with polymeric solutions or dispersions and a process for coating substrates with such treatment liquids.
  • treatment liquids which are applied in the dipping process in which a polymeric solution or dispersion with a so-called “compatible dispersion” and mixed with water and the bath is heated to a temperature in the range of about 27 to 71 ° C and in which the parts to be coated are heated to a temperature in the range of about 104 to 927 ° C.
  • the so-called compatible dispersion contains according to the examples e.g.
  • Graphite, aluminum, titanium oxide or a black pigment the mixtures with a compatible dispersion according to the examples indicating that they are pigment dispersions for coloring protective films and for improving the lubricity of the substrate surface treated therewith (lubricating varnish).
  • the examples each describe two synthetic resins with a pigment addition, but no content of corrosion inhibitors to improve the anti-corrosive properties.
  • the synthetic resins used are acid-functional, physically drying acrylate resins which are not resistant to alkaline media (pH 6 - 14). For this reason, only a slight corrosion protection is expected.
  • the dry film resulting from this formulation is not resistant to alkaline liquids which serve to further process the coated parts, e.g. against drilling oils, against lubricants for cutting deformation or against alkaline water-based paints for recoating.
  • the object is achieved with a method for producing a plastic film or a plastic-containing film on a metal surface, wherein a treatment liquid which at the beginning of wetting with the treatment liquid 0.1 to 50 wt .-% of one or more resins containing non-volatile film-forming mixture and 99.9 to 50 wt .-% of a water-miscible or / and water-soluble solvent and / or water, on the metal surface forms a film, wherein the volatile portion at least partially escapes, wherein the treatment liquid contains synthetic resins, almost one hundred percent or with neutralizing agents are neutralized in excess, wherein the neutralization with neutralizing agents of two or three types of neutralizing agents selected from 1) long-volatile, 2.) medium volatile and 3.) short-volatile neutralizing agents, wherein the treatment liquid at the beginning of wetting mi t of the treatment liquid has a temperature in the range of 10 to 100 ° C, wherein the metal surface at the beginning of wetting with the treatment liquid has a temperature at least 20 ° C
  • the temperature difference between the metal surface and the treatment liquid at the beginning of wetting with the treatment liquid is advantageously at least 25 ° C, preferably at least 32 ° C, more preferably at least 45 ° C, most preferably at least 55 ° C.
  • the temperature of the substrate may also be advantageously at least 70 ° C, at least 100 ° C or in many cases at least 150 ° C above the temperature of the treatment liquid.
  • the selected temperature difference may depend substantially on the nature of the heating of the substrates and, if necessary. Of the involvement in a mass production, not only by the chemical and physical conditions of film formation.
  • polymeric film is intended in this application to mean a film made of plastic or of a plastic-containing material Under the treatment of the metal surface according to the invention, the application of a passivation layer to the surface of a metallic material (alloy or metal), which prevents the corrosion of metal surfaces, is understood.
  • treatment in the context of this application is intended to include the term pretreatment” - unless otherwise stated at the text in which a usually only temporarily protective layer is applied later by at least one further protective layer, in particular Lacquer layer, is superimposed. For the purposes of this application, however, this term should not include the formation of a primer layer.
  • curing in the context of this application is intended to include both chemical crosslinking and physical curing.
  • water-miscible is to be understood as a generic term for the term “water-dispersible”.
  • the metal surface is meant both the surface of a metallic workpiece (substrate) of at least one metal and / or at least one alloy in which the metal or alloy reaches to the surface, as well as a workpiece made of any material that is metallic Coating is provided and therefore has a metal surface, on which in turn a polymeric protective layer is applied.
  • a metallic workpiece substrate
  • a plastic-containing workpiece such as a fiber composite - e.g. for bumpers, panels, body parts - act. This requires comparatively low treatment temperatures.
  • the substrate may consist essentially of aluminum, iron, copper, magnesium, zinc, tin and / or at least one of their alloys and, if necessary, may additionally be coated with metal, in particular with aluminum, lead, copper, zinc, tin or their alloys.
  • the metallic coating may in particular have been applied by hot dipping, thermal spraying or by physical, chemical or electrolytic deposition.
  • the metallic substrate was produced, inter alia, by casting and / or rolling.
  • the metal surface is provided with a primer layer before wetting with the film-forming treatment liquid - either with an inorganic adhesion promoter layer, in particular with a phosphate, a silicate or zirconium or / and titanium-containing adhesion promoter layer, or / and with an organic adhesion promoter layer, in particular with a phosphonate, polyvinyl butyral crosslinked with acids (classic wash primer) and / or at least one butyl titanate or / and silane-containing adhesion promoter layer.
  • an inorganic adhesion promoter layer in particular with a phosphate, a silicate or zirconium or / and titanium-containing adhesion promoter layer, or / and with an organic adhesion promoter layer, in particular with a phosphonate, polyvinyl butyral crosslinked with acids (classic wash primer) and / or at least one butyl titanate or / and silane-containing adhesion promoter layer.
  • an inorganic primer layer is in many cases to be selected. In the case of short-term exposure to temperatures up to 250 ° C, it is often possible to work with organic primer layers.
  • a temperature of the substrate at the beginning of wetting with the treatment liquid in the range of 200 to 450 ° C for hot-dip galvanizing with zinc or a zinc alloy and in the range of 200 to 700 ° C for the hot dip in a Melt of aluminum or an aluminum alloy such as AlSi based alloy, Galvalume® (55% Al-Zn), Galfan® or Crack-Free-Steel®.
  • the temperature is at the level as they have to be coated substrates immediately or shortly after leaving a furnace. This may in particular be a furnace for hardening, annealing or annealing or a system for hot dip.
  • the temperature should advantageously be selected such that the treatment liquid at least partially dries after wetting and removal of the substrate and that the formed film at least partially cures.
  • the organic polymers in most cases synthetic resins, are common, but by no means in all cases, at molecular weights of the order of about 800 to about 2000 at room temperature in the solid state and generally well soluble. However, the solubility decreases with increasing molecular weight. Polymers with molecular weights in the range below about 1000 are often inherently liquid. Both groups of substances are sometimes water-miscible or / and water-soluble, depending on the composition or partly depending on the number of neutralisable groups. The addition of a special organic solvent to the water can significantly increase the solubility of the polymers.
  • the resin or resins may be synthetic resins, in particular acrylates, polyesters, polyurethanes, silicone polyesters, epoxides, phenols, styrenes, resins based on urea-formaldehyde, mixtures thereof or / and their copolymers, preferably hexamethoxymethylmelamine (HMMM) resins and / or their mixtures or / and copolymers of several substances of said substance groups be. But it can also be used natural resins.
  • synthetic resins in particular acrylates, polyesters, polyurethanes, silicone polyesters, epoxides, phenols, styrenes, resins based on urea-formaldehyde, mixtures thereof or / and their copolymers, preferably hexamethoxymethylmelamine (HMMM) resins and / or their mixtures or / and copolymers of several substances of said substance groups be.
  • HMMM hexamethoxy
  • the resin or resins may be present as a solution or dispersion, in particular as an emulsion or suspension; preferably, a solution is used.
  • a solution is used for the deposition of a film on a metal surface according to the invention at elevated temperature
  • synthetic resins which are present in the treatment liquid in the form of a solution e.g. neutralized acid-functional acrylate resins having an acid number of at least 50, usually in the range of 150 to 250.
  • the treatment liquid contains synthetic resins which contain a sufficient number of neutralized or neutralisable groups. Synthetic resins with almost 100 percent neutralizable or neutralized groups or better synthetic resins with an addition of neutralizing agents in excess are usually readily soluble in water. As a result, coagulation, which can easily occur above 40 ° C, can be avoided.
  • neutralizing agents can be used, for example, in a mixing ratio of 1: 1: 1. Such a mixture is matched simultaneously to optimum solubility or dispersibility of the resins in the treatment liquid and thus to optimum bath stability in the temperature range up to 100 ° C as well as optimum water resistance and weathering resistance after drying.
  • Dispersions behave differently with so-called internal emulsifiers. No foreign substances are added to these dispersions and they behave excellently since no uncontrolled hydrophilic effects can occur.
  • a glycol ether or N-methylpyrrolidone and / or water can be used, in the case of using a solvent mixture, in particular a mixture of at least one long-chain alcohol, such as Propylene glycol, a Esteralkohof, a glycol ether and / or butanediol with water, preferably only water.
  • the water used may be of the quality e.g. of city water, well water or recycled water. In many cases, however, it is advantageous or recommended for a series production to use a partially or fully demineralized water quality in order to limit the unwanted salination of the treatment liquids by the salt loads of the water used.
  • the treatment liquid may contain at least one volatile and / or nonvolatile additive for adjusting defoaming, adhesion, preservation, in particular against fungal and bacterial attack, neutralization, surface wetting, rheology and / or course.
  • volatile and / or nonvolatile additive for adjusting defoaming, adhesion, preservation, in particular against fungal and bacterial attack, neutralization, surface wetting, rheology and / or course.
  • corrosion inhibitors are added as pigments and / or in dissolved form, for example at least one phosphate, titanate or / and zirconate, in particular dicalcium phosphate, dimagnesium phosphate, iron (III) phosphate, modified alkali metal phosphate, aluminum triphosphate or at least one zirconium complex compound improved corrosion protection of the overall layer can be achieved. Also by the addition of an N-ethylmorpholine complex, the corrosion-protective effect of the resins can be significantly increased. This is particularly advantageous for the life of the components to be treated.
  • the subsequently insufficiently painted lots have high corrosion resistance due to the content of corrosion inhibitors in the film. It has surprisingly been found that it is possible with the inventive method to achieve sufficient corrosion protection even at the insufficiently covered with paint lots of galvanized steel or aluminum alloy body. Furthermore, so-called. Drying such as runners, noses, edge thickening are avoided by the drainage of treatment liquid with the method according to the invention. It has been shown that the According to the invention coated substrates have a nearly constant film thickness over the entire surface.
  • the treatment liquid may contain at least one neutralizing agent, e.g. an amine, in particular at least one alkanolamine, ammonia and / or sodium hydroxide solution.
  • at least one neutralizing agent e.g. an amine, in particular at least one alkanolamine, ammonia and / or sodium hydroxide solution.
  • the pH of the treatment liquid may advantageously be maintained in a range of 1 to 11, preferably in the range of 4 to 10, more preferably in the range of 7 to 9.5.
  • the polymeric film on the metal surface may be applied by immersing the substrate in the treating liquid and then drying, the substrate preferably having a temperature in the range of 100 to 200 ° C at the beginning of wetting with the treating liquid.
  • the polymeric film can be applied to the metal surface by flooding, that is, by pouring a surface of the substrate with the treatment liquid, followed by drying, wherein the substrate at the beginning of wetting with the treatment liquid, preferably a temperature in the range of 12 to 150 ° C, in particular at least 32 ° C, preferably at least 45 ° C, having.
  • the polymeric film can be applied to the metal surface by spraying the substrate with the treatment liquid and subsequent drying, wherein the substrate at the beginning of wetting with the treatment liquid advantageously a temperature in the range of 12 to 70 ° C, especially at least 32 ° C, preferably at least 45 ° C, has.
  • the spraying can be carried out in particular by atomization with air or airless.
  • the polymeric film may be applied to the metal surface by wetting the substrate with the treating liquid by knife coating, brushing or rolling followed by drying, the substrate preferably having a temperature in the range of 12 to 70 ° C, especially at the beginning of wetting with the treating liquid at least 32 ° C, preferably at least 45 ° C having.
  • Rinsing after the application of the polymeric film is not required and usually makes no sense, because it could be used to partially remove the deposited film.
  • the method according to the invention is particularly advantageous when the substrate is subjected to a preceding temperature treatment, such as e.g. annealing, annealing, hot dip coating (such as hot dip galvanizing) or hardening treatment to the temperature required for the coating.
  • a preceding temperature treatment such as e.g. annealing, annealing, hot dip coating (such as hot dip galvanizing) or hardening treatment to the temperature required for the coating.
  • the substrate will in most cases at the beginning of wetting with the treatment liquid have a temperature of at least 50 ° C above the temperature of the treatment liquid. It is recommended, especially in hot-dip galvanized cargo, that the substrate to be treated is more cooled by the treatment or even quenched.
  • polymeric resin particles After deposition of polymeric resin particles, they physically and / or crosslink chemically in the presence of suitable chemical reactants to form a closed, uniform film.
  • the polymeric film can also be formed by physical filming, ie, particle contraction, for example due to the van der Waals forces on the escape of water. Filming is particularly favored when synthetic resins with low glass transition temperatures are used or when appropriate film formers (For example, long-chain alcohols) are added for temporary plasticization of the polymers. It is particularly advantageous to use solutions of carboxyl-containing acrylates in combination with melamine-formaldehyde, since chemical crosslinking is then possible. The crosslinking produces a particularly high chemical resistance and a high resistance to weathering.
  • a film is formed which, after drying, has a layer thickness of from 0.01 to 50 ⁇ m, in particular from 0.1 to 20 ⁇ m, particularly preferably from 0.5 to 7.5 ⁇ m. In many cases, films in the range of 0.6 to 1.8 microns are preferred, in some other cases, films in the range of 2.0 to 18 microns.
  • the residence time of the substrate in the immersion bath is preferably selected so that the reactions in the treatment liquid are substantially or completely terminated during the wetting of the substrate with the treatment liquid.
  • a strong or certain bubbling of gas bubbles in the area of the contacted substrate can be taken as an indication of the reactions.
  • the residence time can be 1 to 120 seconds. In many cases, however, it will be only 2 to 60 seconds, advantageously only 3 to 30 seconds, often only 4 to 20 seconds. As a rule, the thinner or less hot the substrate is on first contact with the treatment liquid, the shorter the residence time can be selected.
  • Thicker films are formed in the process according to the invention without a greater increase in the concentration of non-volatile constituents in the treatment liquid, in particular on thicker-walled substrates. Due to their greater heat content thicker substrates tend to form thicker films, these layers can also cross-link or harden due to the larger heat supply.
  • the high temperature or the high heat content of the parts to be treated allow a faster escape of the volatile constituents of the applied wet film and therefore allow a faster concentration of the dry substance contained in the treatment liquid. The latter can help that films can be processed faster due to the higher degree of drying.
  • Thicker films can also be applied to thinner substrates by using a higher concentration of nonvolatiles in the treatment liquid.
  • the partially dried polymeric film may be thermally post-treated for final chemical crosslinking or physical curing.
  • temperatures in the range of 100 to 400 ° C, preferably at 120 to 200 ° C, more preferably from 140 to 180 ° C at.
  • the temperature here is based on the surface temperature of the substrate.
  • the time of the thermal aftertreatment may be 2 seconds to 2.5 hours, preferably 2 minutes to 1 hour, particularly preferably 10 to 30 minutes. The higher the temperature is selected, the shorter the thermal aftertreatment can fail and vice versa.
  • the treatment can i.a. done with IR radiation.
  • the film to be crosslinked is cured with UV radiation.
  • the treatment time is usually a fraction of a second to a few seconds.
  • this usually requires a certain composition of the treatment liquid and the previous complete or almost complete expulsion of the solvent or solvent mixture.
  • the substrate coated with the film is first lacquered and subsequently the polymeric film and the lacquer applied thereto are finally chemically crosslinked and / or physically cured during the thermal aftertreatment.
  • the method according to the invention is also particularly advantageous for workpieces made of aluminum alloys, in particular for motor vehicle bodies provided with a primer layer.
  • a temperature with a polymeric film that is process-conditioned after leaving a heat treatment facility e.g. at temperatures in the range of 260 to 130 ° C, preferably from 220 to 160 ° C, it can be usefully used in the substrates to be coated energy content, without having to heat the substrates again.
  • the method according to the invention can therefore be incorporated inexpensively into series production.
  • the inventive method can also be used for hot-dip galvanized workpieces.
  • As well as 1 part by weight of an N-ethylmorpholine complex proven excellent after the resins were neutralized with ammonia, 2-dimethylaminoethanol and 2-amino-2-methyl-1-propanol in the ratio of 1: 1: 1.
  • the method according to the invention offers the possibility that a lacquer layer, a foil, a foam or / and an adhesive is additionally applied to the substrate, the substrate optionally being bonded to a further shaped body or to a foil.
  • thicker films which may for example have a film thickness in the range of 5 to 25 microns. These films can serve as a single coat.
  • the concentration of the treatment liquid is increased in order to be able to apply thicker films, preferably to a content of 5 to 25% by weight of dry substance in the treatment liquid.
  • coloring or opaque Add components such as pigments or dissolved dyes of the treatment liquid to form a color-covered or / and colored glaze lacquer layer. To a certain extent, it is also possible to apply effect and metallic finishes.
  • the nonvolatile, film-forming mixture may comprise, in addition to resin (s), at least one inorganic additive in dissolved form or / and as finely divided powder, such as e.g. a carbonate, chromate, oxide, silicate, e.g. Phyllosilicate, sulphate.
  • This additive can be used as a transparent or opaque dye or as a transparent filler and / or to extend the diffusion path attacking media in the dry film to the substrate surface.
  • flaky particles are advantageous.
  • Such a one-step applied coating can be applied much cheaper than an at least two-stage coating method according to the prior art.
  • the drying time of the wet film is significantly reduced. It may in some cases - such as e.g. for galvanized construction parts for houses, bridges, etc. or for traffic safety devices, in particular traffic lights, lamps and guardrails - be subjected to a physical and / or chemical drying, so that no additional thermal drying step is required. Therefore, the one-step coating is also less expensive than related prior art one-step applied paint coatings.
  • Decorative films such as printed PVC films are state of the art.
  • the films can be self-adhesive or glued with a separately applied adhesive.
  • an adhesive layer it is possible to produce adhesive bonds to other components, in particular metal parts.
  • Such compounds are i.a. Can be used for vehicle bodies, trailers, campers, aircraft.
  • adhesive bonds to glass, plastic, wood or other materials are possible, e.g. for gluing glass panes.
  • the object is further achieved with a treatment liquid for producing a plastic film or plastic-containing film on a metal surface during the wetting of the metal surface with the treatment liquid, wherein the treatment liquid 0.1 to 50 wt .-% of one or more resins containing non-volatile film-forming mixture and 99 , 9 to 50 wt .-% of a water-miscible or water-soluble solvent and / or water and is maintained at a temperature of 10 to 100 ° C, wherein the treatment liquid contains synthetic resins which are almost 100% or neutralized with neutralizing agents in excess, the Neutralization with neutralizing agents from two or three types of neutralizing agents selected from 1.) long-volatile, 2.) medium volatiles and 3.) short-volatile neutralizing agents, wherein the treatment liquid is adjusted so that its constituents during the operating time, during the life and at the temperature of the film formation do not or almost not coagulate, do not or not significantly sediment and not or not significantly decomposed, wherein the molecular weight distribution and the viscosity of
  • a concentrate for producing a treatment liquid according to the invention the concentrate after dilution giving the treatment liquid, the concentrate containing 1 to 90% by weight of a non-volatile film-forming mixture containing one or more resins and 99 to 10% by weight.
  • a water-miscible or / and water-soluble solvent and / or Water the concentrate or treating liquid containing synthetic resins which are almost 100% or neutralized with neutralizing agents in excess, the neutralization with neutralizing agents being selected from two or three kinds of neutralizing agents selected from 1.) long-volatile, 2.) medium volatility and 3..
  • Concentrate or the treatment liquid are adjusted so that their constituents during the storage time, during the operating time, during the life and at the temperature of the film formation not or almost not coagulate, not or not significantly sediment and not sediment or not significantly decomposed and wherein the molecular weight distribution and the viscosity of the concentrate and the treatment liquid do not change significantly during storage time and use.
  • Operating time is understood to mean working with the treatment liquid according to the invention, in which hotter parts are brought into contact with the treatment liquid in order to form a polymeric film thereon.
  • the stability of the concentrate and the treatment liquid should be ensured to the extent that no serious disturbances of operation due to instability occur.
  • the treatment liquid contains 0.1 to 15% by weight of the nonvolatile film-forming mixture and 99.9 to 85% by weight of a water-miscible or / and water-soluble solvent or / and water.
  • the treatment liquid contains 0.1 to 5 wt .-% of the nonvolatile film-forming mixture and 99.9 to 95 wt .-% of a water-miscible and / or water-soluble solvent and / or water.
  • the preferred content of the nonvolatile film-forming mixture in the treatment liquid may also vary depending on the composition of the treatment liquid and the desired layer.
  • the content of the nonvolatile film-forming mixture in the treatment liquid will advantageously be at least 0.8% by weight or at most 3% by weight, in some cases at least 1% by weight or up to 2.5% by weight. %.
  • the content of at least one solvent in the treatment liquid is then at most 99.2 wt .-% or at least 97 wt .-% or at most 99 wt .-% or at most 97.5 wt .-%.
  • treatment liquids which have a content of the nonvolatile film-forming mixture in the range from 0.5 to 5% by weight, preferably 1 to 3% by weight, and 99.5% to 95 wt .-% of at least one solvent.
  • treatment liquids containing a content of the non-volatile film-forming mixture in the range of 0.5 to 5 wt .-%, preferably 1 to 3 wt .-%, and 99.5 to 95 wt .-% of at least one solvent.
  • treatment liquids which have a content of the nonvolatile film-forming mixture in the range from 4 to 12% by weight, preferably 6 to 10% by weight, and 96 to 88% by weight, of at least one solvent are suitable for the colored coating of substrates.
  • the concentrate contains 5 to 80% by weight of a non-volatile film-forming mixture containing one or more resins and 95 to 20% by weight of a water-miscible and / or water-soluble solvent and / or water, more preferably 10 to 70 and 90 to 30, respectively wt .-%.
  • the temperature of the treatment liquid is preferably maintained at at least 35 ° C., particularly preferably at least 40 ° C., very particularly at 50 to 70 ° C.
  • the preferred temperature ranges may vary depending on the composition of the treatment liquid and the desired layer, and may also be shifted to temperatures in the range of 75 to 95 ° C, for example.
  • Prerequisite for a successful continuous use of the treatment liquid according to the invention is its stability over at least one month, preferably over at least 6 months, more preferably over at least two years, wherein the treatment liquid is supplemented during this period and adapted to the working conditions:
  • the components of the treatment liquid should during the operating time, during the life and at the temperature of the film formation do not or almost not coagulate, do not sediment or not significantly sediment and not or not significantly decomposed, and their molecular weight distribution and viscosity should not be essential in use change.
  • the treatment liquid has a viscosity such as that of water or only a slightly increased viscosity, since it then also has difficult-to-reach areas of the parts to be treated, e.g. Drilled holes, threads and cavities achieved.
  • the treatment liquid is prepared by diluting a concentrate with water or / and a solvent mixture containing water.
  • a defoamer e.g., a leveling agent or / and a wetting agent.
  • the treatment liquid it should be noted that it is sufficiently neutralized.
  • the proportion of an organic solvent can be dispensed with if the neutralizing agents are adjusted in their volatility so that a sufficient bath stability is ensured under elevated working temperatures.
  • the crosslinked polymeric dry film according to the invention is generally water-resistant, mechanically stable, weather-resistant and more flexible than a filmed dry film, as has been produced, for example, by physical drying.
  • the crosslinked dry film of the present invention sometimes also gives a higher gloss than prior art films formed by physical drying.
  • the films according to the invention are surprisingly uniform and closed.
  • the cured polymeric film according to the invention exhibits an optimum barrier effect against the effects of weathering, for example on chemicals used in automobiles such as fuels, oils, battery acids, brake fluids, etc. This high film quality is achieved with a filmed dry film According to the prior art, which is prepared from a dispersion by physical drying, usually not reached.
  • the method according to the invention has the advantage over the methods for applying a polymeric film known in the prior art that the polymeric film can be applied from a treatment liquid in a dipping process which contains only a low concentration of the nonvolatile components and is therefore comparatively inexpensive.
  • the dipping method according to the invention has the advantage of being able to do without complex system technology, and nevertheless leads to evenly distributed dry layer thicknesses on geometrically simple or complicated parts.
  • the inventive method can be successfully used by the heat of tempering or curing is used as the starting temperature for the dipping method according to the invention.
  • temperatures at the beginning of wetting with the treatment liquid in the range of 220 to 160 ° C can be used.
  • the method according to the invention for applying the polymeric film is outstandingly suitable for permanently protecting the workpieces based on aluminum without further coating, as with an additional cathodic dip coating. An electrodeposition paint can therefore be saved.
  • the invention is basically also suitable for so-called. Endless workpieces such as wires, profiles and metal strips - narrow band, medium band and broadband.
  • the coated with a film according to the invention substrates can be used for the production of sheets, bodies, bumpers, racks, profiles, guard rail elements, shelf elements, fence elements, radiator elements, moldings of complicated geometry or small parts. They can be used in particular for preassembled bodies and their parts in the manufacture of vehicles, trailers, campers or missiles, for covers, housings, lamps, lights, traffic lights, spectacle frames, screws, nuts, springs, flanges, furniture such as garden furniture or furniture elements , In general, the invention is also particularly advantageous for parts with cavities such as parts made of or with pipes and / or profiles that are limited access to a paint, especially window and door frames, bodies, bicycle frames, pipe structures for the protection of electrical wiring or of household appliances such as pitchers and toasters.
  • the method according to the invention can advantageously be used for parts that may be formed by forming such as cold, Kaltmassiv-, hot, forming, drawing, pressing, extrusion, etc. or by casting were formed.
  • Sheets of about 100 x 100 mm in size and 2, 3 and 5 mm thick, respectively, were hot-dip galvanized from a commercial grade steel.
  • the zinc content of the zinc layer was more than 98%.
  • the zinc melt had a temperature in the range of 445 to 455 ° C when the plates were removed.
  • the plates were dipped in the treatment liquid after removal from the galvanizing bath with a time delay.
  • the treatment liquid had a temperature of about 60 ° C, since the bath was kept substantially constant at this temperature. This caused a spontaneous cooling of the hot plates.
  • the temperature of the plates e.g. when immersed in the treatment liquid was measured with a temperature sensor on the plate surface. Five plates each were coated under the same conditions. The residence time was 5 to 10 seconds and was chosen so that the reactions in the liquid were almost completed on removal.
  • the non-volatile portion in the treatment liquid was 1.2 and 2.4 wt% in Examples 1 and 2, respectively.
  • the treating liquid of Example 1 contained the air-drying, transparent formulation 1 of 30% by weight of an acid-functional acrylate resin based on pure acrylate and methacrylate and 70% by weight of an acid-functional styrene-acrylate resin.
  • This treatment liquid was intended for chromium-free preservation of piece-galvanized surfaces.
  • additives additives for the adjustment of the defoaming, the surface wetting and the course were used.
  • To neutralize the acid groups of the resins were ammonia, 2-dimethylaminoethanol and 2-amino-2-methyl-1-propanol in the ratio 1: 1: 1 and used as solvent demineralized water.
  • the resin mixture was therefore readily soluble in water in the temperature range of 15 to 100 ° C for long process times and was particularly well suited for the treatment of about 400 to 430 ° C hot parts, which were hot-dip galvanized immediately before. Despite the high temperatures of the immersed parts, the treatment liquid was stable over time.
  • the treatment liquid of Example 2 contained instead 90% by weight of a formulation 2 based on polyurethane, acrylate and polyester and 10% by weight of a melamine-formaldehyde resin. The remaining. Conditions were chosen as in Example 1. This treatment liquid was intended for the oven-drying, at elevated temperature crosslinking transparent chromium-free pretreatment or / and treatment of teilgutverzinkten surfaces or the surfaces of aluminum or aluminum alloys. The films produced with Formulation 2 still had to be treated at temperatures in the range of 140 to 200 ° C for 30 to 10 minutes to final cure the film. This treatment liquid was particularly well suited for the treatment of galvanized surfaces in the automotive industry, because it was permanently stable even at high temperatures.
  • the polymeric films were optically controlled.
  • the coating weight of the polymeric film could only be determined approximately.
  • a layer weight of 1 g / m 2 corresponds approximately to a layer thickness of 1 ⁇ m.
  • the layer coverage in the range of 0.5 to 5 ⁇ m was determined gravimetrically and averaged over 5 values.
  • the layer coverage greater than 5 microns was determined using a Permascopes Fa. Fischer and averaged over 10 values.
  • Table 1 Experiments for example 1 on hot-dip galvanized steel plates attempt Approach dip Wall thickness dive objects Temperature dip Substrate temperature before diving Substrate temperature after dipping Trokken fürdicke * 1 98.8% by weight of water 2 mm 60 ° C 400 ° C 70 ° C 0.7 ⁇ m 2 1.1% by weight of formulation.
  • Table 1 indicates a strong dependence of the film thickness as a function of the plate thickness and thus of the heat content of the substrates.
  • the films on the 5 mm thick plates were not only made thicker due to the high heat content, but also offered a much better corrosion protection than thinner films. All films on the galvanized steel plates were visually perfect: the transparent films were closed. The layer thickness distribution fluctuated on one plate only slightly. At the edges, there was no significant thickening of the protective films.
  • Table 2 Experiments to Comparative Examples 1 to 5 on hot-dip galvanized steel plates: treatment liquid and parts at room temperature (about 20 ° C) Comparative example Approach dip Wall thickness dive objects Temperature dip Substrate temperature before diving Substrate temperature after dipping Dry layer thickness * VB 1 98.8% by weight of water 2 mm 20 ° C 20 ° C 20 ° C 0.1 ⁇ m 1.1% by weight of formulation. 1 0.1% by weight of additives VB 2 92.5% by weight of water 2 mm 20 ° C 20 ° C 20 ° C 1.0 ⁇ m 6.9% by weight of formulation.
  • Comparative Examples 1 to 5 showed that the dip treatment of surfaces having a temperature of about 20 ° C in a treatment liquid of about 20 ° C about a factor of 7 thinner dry layer at the same concentration of the non-volatile film-forming Proportions in the treatment liquid are generated as if the treatment liquid is heated to 60 ° C and the substrates to be treated previously have a temperature in the range of 200 to 400 ° C.
  • concentration of the nonvolatile film-forming fraction in the treatment liquid would have to be increased by a factor of about 7 in order to achieve similar layer thicknesses at room temperature, which would have a very negative effect on the investment costs.
  • a particular disadvantage is that at room temperatures at the trailing edges and in the area of holes and threads overcoating occurs and the parts are unusable due to lack of dimensional accuracy.
  • Comparative Example 1 On selected samples outdoor weathering tests in industrial atmosphere and Schwitzbergkonstantrytests were carried out according to DIN 50 017 KK. This resulted in a thinner because of the on each a single plate strongly varying layer thickness distributions in Comparative Examples 1 and 2 coated areas insufficient corrosion protection. Comparative Example 1 showed so poor results that the corrosion protection was not better than without the alleged corrosion-protective coating, as Comparative Example 6 demonstrated.
  • edges showed much stronger coatings than the other surfaces. In some cases, layer thicknesses of more than 50 ⁇ m occurred at the edges.
  • Inventive Example 4 film formation on an aluminum alloy and subsequently applied car topcoat
  • substrates were used from a conventional aluminum alloy in the automotive industry.
  • the substrates were previously passivated Cr-free with a coating of at least one Zr / Ti compound.
  • the plates were immediately after the heat treatment during annealing - if necessary, heated with slower time for slow cooling or for the completeness of the test rich a little higher - and dipped at about the specified target temperature (Table 4).
  • the treatment liquid of Example 4 contained 95% by weight of a formulation 3 based on polyurethane and acrylate and 5% by weight of one Melamine-formaldehyde resin. It was worked with a concentration of non-volatile constituents of the treatment liquid of 2.4 wt .-%. The remaining conditions were maintained as in Example 2.
  • This treatment liquid was intended for the elevated temperature oven-drying, transparent, chromium-free treatment or / and pretreatment of the surfaces of aluminum or aluminum alloys.
  • This treatment liquid was just as well suited as the treatment liquid of Examples 2 and 3.
  • the films produced with Formulation 3 had yet to be post-treated at temperatures in the range of 140 to 200 ° C for 30 to 10 minutes for final curing.
  • the quality of the polymeric film was tested without applied car topcoat.
  • the coatings were optically perfect: the layers were closed, the layer thickness distribution was uniform and no significant thickening occurred at the edges. After application of the topcoat, all tests for determining adhesion by cross-hatching method yielded flawless results. The entire sequence of layers met the physical-technical tests of an automotive finish.
  • Inventive Example 5 Film formation on an aluminum alloy as a single-coat treatment
  • the panels of an aluminum alloy commonly used in the automotive industry have been water wetting cleaned to remove oil residue and dirt. They were not passivated.
  • the parts were heated to a temperature just above the temperature at which the parts were immersed in the treatment liquid (Table 4).
  • the residence time was 5 to 10 seconds and was chosen so that the reactions in the liquid were almost completed on removal.
  • the treatment liquid of Example 5 contained 54.7% by weight of a formulation 4 based on acrylate, methacrylate, styrene and polyester and 30% by weight of a rutile white pigment, 0.3% by weight of a carbon black pigment, 9.0% by weight of silicate and 6.0% by weight of other additives for defoaming, flow, wetting, neutralization and adjustment of the rheology.
  • Example 3 Salt spray tests to DIN 50 021 SS, alternating tests to VDA 621-415 and outdoor weathering tests to VDA 621-414 were carried out on selected samples.
  • Example 3 Run 27, Salt Spray Test and Alternate Test gave equivalent results to those of Conventional High Grade Conventional Methods (VB 7 and 8) but superior corrosion resistance over a zinc phosphate layer.
  • the coating according to the invention is far better in terms of outdoor weathering than the highest quality conventional coatings. It should be noted that only Example 3, Experiment 27, previously passivated with Ti / Zr fluorine, but not the substrates of Comparative Examples 7 to 9, since the latter are not coated according to the invention with such a passivation. The layer thickness in the region of the trailing edges was only minimally larger in example 3, experiment 27, than on the larger surfaces.

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  • Life Sciences & Earth Sciences (AREA)
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  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Claims (26)

  1. Procédé pour former un film de matière plastique ou un film contenant une matière plastique sur une surface métallique, dans lequel on forme un film sur la surface métallique en utilisant un liquide de traitement qui, au début du mouillage avec le liquide de traitement, contient 0,1 à 50 % en poids d'un mélange formateur de film, non-volatil, contenant une ou plusieurs résines, et 99,9 à 50 % en poids d'un solvant miscible à l'eau ou/et d'un solvant soluble dans l'eau ou/et d'eau, la partie volatile s'échappant alors au moins partiellement, procédé dans lequel le liquide de traitement présente, au début du mouillage avec le liquide de traitement, une température située dans le domaine allant de 10 à 100 °C, la surface métallique présente, au début du mouillage avec le liquide de traitement, une température supérieure d'au moins 20 °C à celle du liquide de traitement et située dans le domaine allant de 30 à 700 °C, et le film sert au traitement de la surface métallique, c'est-à-dire qu'il forme sur la surface métallique une couche de passivation qui empêche la corrosion de la surface métallique,
    procédé caractérisé en ce que le liquide de traitement contient des résines synthétiques qui sont neutralisées presque à 100 % ou avec des agents de neutralisation en excès, la neutralisation étant effectuée avec des agents de neutralisation de 2 ou 3 sortes, choisis parmi 1) des agents de neutralisation à volatilisation longue, 2) des agents de neutralisation à volatilisation moyenne et 3) des agents de neutralisation à volatilisation courte, et en ce que le liquide de traitement présente, au début du mouillage avec le liquide de traitement, une température de 10 à 100 °C.
  2. Procédé selon la revendication 1, caractérisé en ce que, avant le mouillage avec le liquide de traitement formateur de film, la surface métallique est pourvue d'une couche intermédiaire d'adhérence, de préférence d'une couche intermédiaire d'adhérence contenant un phosphate, un silicate ou du zirconium et/ou du titane, un phosphonate ou/et un silane.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la résine ou les résines sont des résines synthétiques, en particulier des résines acryliques, des polyesters, des polyuréthanes, des polyesters siliciés, des résines époxy, des résines phénoliques, des résines styréniques, des résines à base d'urée-formaldéhyde, des mélanges de ces résines et/ou des copolymères de ces résines.
  4. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les résines se présentent sous la forme d'une solution ou d'une dispersion, en particulier une émulsion ét/ou une suspension, de préférence sous la forme d'une solution.
  5. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le mélange non-volatil, formateur de film, contient, outre une résine ou des résines, au moins un additif minéral sous forme dissoute ou/et sous la forme d'une poudre finement divisée; comme par exemple un carbonate, un chromate, un oxyde, un silicate ou un sulfate.
  6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on emploie comme solvant pour les polymères organiques, au moins un alcool miscible à l'eau ou soluble dans l'eau, un éther de glycol, la N-méthylpyrrolidone ou/et de l'eau, et, dans le cas de l'emploi d'un mélange de solvants, en particulier un mélange d'au moins un alcool à chaîne longue, comme par exemple, le propylèneglycol, un ester-alcool, un éther de glycol ou/et du butanediol, avec de l'eau, et de préférence seulement de l'eau.
  7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le liquide de traitement contient au moins un additif volatil ou/et un additif non-volatil pour le réglage de la suppression de la mousse, de l'adhérence, de la conservation, de la neutralisation, du mouillage des surfaces, de la rhéologie ou/et de l'écoulement.
  8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le pH du liquide de traitement est maintenu à une valeur située dans le domaine allant de 1 à 11.
  9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on forme le film également par dépôt physique d'un film.
  10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le film est appliqué sur la surface métallique par immersion du support dans le liquide de traitement, puis séchage, le support présentant, au début du mouillage avec le liquide de traitement, de préférence une température située dans le domaine allant de 100 à 200 °C.
  11. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que l'on forme le film sur la surface métallique en inondant le support avec le liquide de traitement, puis en séchant, le support présentant, au début du mouillage avec le liquide de traitement, de préférence une température située dans le domaine allant de 12 à 150 °C.
  12. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le film est appliqué sur la surface métallique par pulvérisation du liquide de traitement sur le support, puis séchage, le support présentant, au début du mouillage avec le liquide de traitement, de préférence une température située dans le domaine allant de 12 à 70 °C.
  13. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le film est appliqué sur la surface métallique par mouillage du support avec le liquide de traitement par enduction à la racle, étalement ou enduction au rouleau, puis séchage, le support présentant, au début du mouillage avec le liquide de traitement, de préférence une température située dans le domaine allant de 12 à 70 °C.
  14. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le support est amené à la température nécessaire pour le revêtement lors d'un traitement thermique antérieur, comme par exemple un recuit ou un revêtement par immersion dans un bain fondu.
  15. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le support est refroidi fortement ou trempé, la température du support se trouvant alors de préférence au moins 80 °C, encore mieux au moins 100 °C au-dessus de la température du liquide de traitement.
  16. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on forme un film ayant, après séchage, une épaisseur de 0, 01 à 50 µm, en particulier de 0,1 à 20 µm et encore mieux de 0,5 à 5 µm.
  17. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le film partiellement séché est soumis à un traitement thermique ultérieur, en particulier à une température située dans le domaine allant de 100 °C à 400 °C et en particulier pendant une durée de 2 secondes à 2,5 heures, pour réaliser la réticulation chimique finale ou le durcissement physique final.
  18. Procédé selon l'une quelconque des revendications 1 à 16, caractérisé en ce que le film à réticuler est durci par irradiation avec des rayons UV.
  19. Procédé selon l'une quelconque des revendications 1 à 17, caractérisé en ce que le support est laqué seulement lorsqu'on effectue le traitement thermique ultérieur pour la réticulation chimique finale ou le durcissement physique final du film, traitement thermique qui peut servir simultanément à faire durcir la couche de laque.
  20. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on revêt d'un film des constituants en alliage d'aluminium, en particulier des constituants de carrosserie d'automobile pourvus d'une couche intermédiaire d'adhérence, en opérant à la température qui existe à la sortie d'un dispositif de traitement thermique, par exemple à des températures comprises dans le domaine allant de 260 à 130 °C, de préférence de 220 à 160 °C.
  21. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on ajoute, sous la forme de pigment et/ou sous forme dissoute, des inhibiteurs de corrosion comme par exemple au moins un phosphate, un titanate et/ou un zirconate, en particulier du phosphate dicalcique, du phosphate de dimagnésium, du phosphate de fer (III), un phosphate alcalin modifié, du triphosphate d'aluminium ou un composé complexe renfermant du zirconium.
  22. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on applique sur le support en plus une couche de laque, une feuille, de la mousse ou/et une colle, le support étant éventuellement collé à une autre pièce moulée ou à une feuille.
  23. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le support à revêtir est une tôle, une carrosserie ou une partie d'une carrosserie, une partie d'une automobile, d'une remorque, d'une caravane ou d'un engin volant, une couverture, un boîtier, une lampe, un luminaire, un élément de feux de signalisation, une pièce ou un élément de mobilier, un élément d'appareil ménager, un châssis, un profilé, une pièce moulée de géométrie compliquée, un élément de glissière de sécurité, de radiateur ou de clôture, un pare-choc, une pièce constituée de ou comportant au moins un tube et/ou un profilé, un cadre de fenêtre, de porte ou de vélo, ou une petite pièce comme par exemple une vis, un écrou, une bride, un ressort ou une monture de lunettes.
  24. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que le support a été préparé par coulée et/ou laminage et est constitué de préférence essentiellement d'aluminium, de fer, de cuivre, de magnésium, de zinc, d'étain ou de leurs alliages, et peut être revêtu en outre d'un métal, en particulier d'aluminium, de cuivre, de zinc, d'étain ou d'un alliage de ces métaux.
  25. Liquide de traitement pour la formation sur une surface métallique d'un film de matière plastique ou d'un film contenant une matière plastique, pendant le mouillage de la surface métallique avec le liquide de traitement, ledit liquide de traitement contenant 0, 1 à 50 % en poids d'un mélange non-volatil, formateur de film, contenant une ou plusieurs résines, et 99,9 à 50 % en poids d'un solvant miscible à l'eau ou soluble dans l'eau et/ou d'eau, liquide de traitement caractérisé en ce que sa température est située dans le domaine allant de 10 à 100 °C, il contient des résines synthétiques qui sont neutralisées presque à 100 % ou avec des agents de neutralisation en excès, la neutralisation étant réalisée avec des agents de neutralisation de 2 ou 3 sortes, choisis parmi 1) des agents de neutralisation à volatilisation longue, 2) des agents de neutralisation à volatilisation moyenne et 3) des agents de neutralisation à volatilisation courte, le liquide de traitement est ajusté de telle manière que ses constituants ne se coagulent pas ou pratiquement pas, ne se déposent pas ou pratiquement pas et ne sont pas ou pratiquement pas décomposés pendant la durée de service, pendant la durée de repos et à la température de formation du film, et que la répartition des masses moléculaires et la viscosité du liquide de traitement ne sont pas modifiées de manière notable lors de l'emploi.
  26. Concentré pour la préparation d'un liquide de traitement selon la revendication 25, qui fournit après dilution le liquide de traitement, caractérisé en ce que le concentré contient 1 à 90 % en poids d'un mélange formateur de film, non-volatil, contenant une ou plusieurs résines, et 99 à 10 % en poids d'un solvant miscible à l'eau ou/et d'un solvant soluble dans l'eau ou/et d'eau, en ce que le concentré ou le liquide de traitement contient des résines synthétiques qui sont neutralisées presque à 100 % ou avec des agents de neutralisation en excès, la neutralisation étant réalisée avec des agents de neutralisation de 2 ou 3 sortes, choisis parmi 1) des agents de neutralisation à volatilisation longue, 2) des agents de neutralisation à volatilisation moyenne et 3) des agents de neutralisation à volatilisation courte, en ce que le concentré ou le liquide de traitement est ajusté de telle manière que ses constituants ne se coagulent pas ou pratiquement pas, ne se déposent pas ou pratiquement pas et ne sont pas ou pratiquement pas décomposés pendant la durée de stockage, pendant la durée de service, pendant le temps de repos et à la température de formation du film, et que la répartition des masses moléculaires et la viscosité du concentré et du liquide de traitement ne sont pas modifiées de manière notable pendant la durée de stockage et lors de l'emploi.
EP00120052A 1999-09-30 2000-09-15 Procédé pour fabriquer un film polymérique sur un substrat, concentré et liquide de traitement pour se faire Expired - Lifetime EP1088598B1 (fr)

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DK2562002T3 (en) * 2007-05-27 2016-04-25 Thomas Schneider Planar member and the process for its preparation
CN101293244B (zh) * 2008-05-27 2012-05-30 王树成 钢铁表面耐酸耐碱的复合有机保护膜的制备方法
DE102008046409C5 (de) 2008-09-04 2013-08-22 Eisenmann Ag Verfahren zum Entfernen von Feststoffen aus beim Lackieren von Gegenständen entstehendem Overspray
CN101543814B (zh) * 2009-04-21 2012-03-28 黑龙江科技学院 钢铁表面的复合有机保护膜的制备方法
CN102049375A (zh) * 2010-10-26 2011-05-11 上海富臣化工有限公司 一种防止聚氨酯透明漆漆膜发白的施工方法
CN102179356B (zh) * 2011-03-31 2013-10-30 上海富臣化工有限公司 一种家具装饰方法及装饰获得的家具
AT514126A1 (de) * 2013-05-27 2014-10-15 Berndorf Band Gmbh Verfahren zum Versehen eines Metallbands mit einem Transportschutz
CN105542579B (zh) * 2016-02-26 2018-01-30 攀枝花学院 钛材表面用耐高温涂料及其应用以及钛材的生产方法
CN111229572A (zh) * 2020-01-08 2020-06-05 佛山市高明基业冷轧钢板有限公司 一种免涂油预涂钢板生产工艺

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GB8402191D0 (en) * 1984-01-27 1984-02-29 Ici Plc Coating process
FR2692912B1 (fr) * 1992-06-30 1995-06-30 Lorraine Laminage Procede de protection contre la corrosion de pieces metalliques et pieces metalliques obtenues par ce procede.
US5283280A (en) * 1992-11-05 1994-02-01 Tech One, Inc. Composition and method for coating an object of interest
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EP1088598A2 (fr) 2001-04-04
EP1088598A3 (fr) 2003-09-17

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