WO1998007896A1 - Utilisation d'acides a element halogene pour la fabrication de tuyaux metalliques revetus ou d'aciers revetus a beton arme ou d'armature - Google Patents

Utilisation d'acides a element halogene pour la fabrication de tuyaux metalliques revetus ou d'aciers revetus a beton arme ou d'armature Download PDF

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Publication number
WO1998007896A1
WO1998007896A1 PCT/EP1997/004400 EP9704400W WO9807896A1 WO 1998007896 A1 WO1998007896 A1 WO 1998007896A1 EP 9704400 W EP9704400 W EP 9704400W WO 9807896 A1 WO9807896 A1 WO 9807896A1
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Prior art keywords
acid
steels
salts
metal pipes
prestressing
Prior art date
Application number
PCT/EP1997/004400
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German (de)
English (en)
Inventor
Christopher Hilger
Dietmar Thomas
Werner BLÖMER
Rainer Schmitz
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Basf Coatings Ag
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Publication date
Application filed by Basf Coatings Ag filed Critical Basf Coatings Ag
Publication of WO1998007896A1 publication Critical patent/WO1998007896A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/10—Coatings characterised by the materials used by rubber or plastics
    • F16L58/1054—Coatings characterised by the materials used by rubber or plastics the coating being placed outside the pipe
    • 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
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06—Applying particulate 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
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B05D1/265—Extrusion coatings
    • 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
    • B05D7/146—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 to metallic pipes or tubes
    • 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
    • B05D7/148—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 using epoxy-polyolefin systems in mono- or multilayers
    • 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
    • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • 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
    • 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
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
    • E04C5/01—Reinforcing elements of metal, e.g. with non-structural coatings
    • E04C5/015—Anti-corrosion coatings or treating compositions, e.g. containing waterglass or based on another metal
    • 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
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • 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
    • B05D2254/00—Tubes
    • 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
    • B05D2350/00—Pretreatment of the substrate

Definitions

  • the present invention relates to the use of halogen element acids for the production of metal pipes, reinforcing steels or tensioning steels coated with one or more layers, a method for coating these substrates and the coated metal pipes, reinforcing steels and prestressing steels.
  • Numerous methods are known for providing steel pipes, in particular those which are laid in the ground, with a coating made of a thermoplastic material, such as polyethylene or polypropylene, for protection against corrosion.
  • the cover is usually connected to the steel tube by gluing.
  • the plastic can be applied in the form of a seamless hose by extrusion using an annular nozzle through which the pipe is passed, after the pipe surface has been coated with an adhesive. It is also known to wind the plastic helically around the tube in the form of a film strip.
  • DE-C-1965 802 discloses a method for sheathing a steel tube, in which a cleaned steel tube is inductively heated to 140-200 ° C. and coated with an epoxy resin layer as an adhesion promoter by means of spray guns. A is then applied to the curing epoxy resin layer extruded film made of an ethylene copolymer as an adhesive layer and an extruded film made of polyethylene as an outer jacket layer applied over it.
  • Such a sheathing which in principle consists of three layers, the individual layers of which can of course also be applied in each case in several partial layers, has excellent corrosion protection properties which are improved compared to the prior art at the time. In some cases, however, in particular with regard to the peel strength under the influence of moisture and elevated temperature (up to 80 ° C
  • EP-PS 0198144 a method for steel tube sheathing is also known, in which a chromate layer is applied after cleaning the steel tube surface. After drying, at least one layer of epoxy resin is applied to this layer as an adhesion promoter, and an inner layer of ethylene copolymer and an outer polyethylene layer are applied over it.
  • DE-A-43 10525 Another method of this type is known from DE-A-43 10525, in which a powder primer containing epoxidized novolak resins is used on the metal tube. phenolic crosslinking agents and fillers.
  • DE-C-36 39 417 A similar process is also evident from DE-C-36 39 417, in which an epoxy / hardener mixture is applied to the metal tube before the chromating agent has been completely converted into a thermally stable intermediate layer. This procedure is intended to improve the adhesion between the coating and the metal pipe.
  • pretreatment agents which, in addition to the most diverse organic and inorganic constituents, contain halogen element acids as an essential component.
  • WO 95/14539 shows a pretreatment agent which contains hexafluorotitanic acid, zirconic acid, hafnic acid, silicic acid, germanic acid or tin acid or tetrafluoroboric acid.
  • the pretreatment agent described in US-A-5 344504 contains tetrafluoroboric acid or hexafluorotitanic acid, zirconic acid or silicic acid.
  • hexafluorotitanic acid zirconic acid or hafnic acid are preferably used.
  • WO 85/05131 recommends the use of tetrafluoroboric acid or of hexafluorosilicic acid, titanium acid or zirconic acid. Although these pretreatment agents no longer contain hexavalent chromium, they should nevertheless be able to protect the metal as well as pretreatment agents containing chromate.
  • chromate-containing pretreatment agents Use of the chromate-containing pretreatment agents must be practiced, as long as it is not certain that the same property profile is achieved by alternative pretreatment agents as by chromate-containing agents.
  • the object of the present invention is accordingly a new pretreatment for the production of metal pipes, reinforcing steels or tensioning steels coated with one or more layers
  • chromate-containing pretreatment agents which makes it possible to dispense with chromate-containing pretreatment agents and yet, in particular with regard to the adhesion and corrosion properties, to achieve the property profile which is equivalent to that achieved with the chromating processes known from the prior art.
  • solutions are used as pretreatment agents which contain halogen element acids as an essential component.
  • the present invention relates to a new method for coating metal pipes, preferably made of steel, reinforcing steel or prestressing steel, in which a) the metal surface is cleaned, b) the pretreatment agent to be used according to the invention is applied to the metal surface, preferably by dipping,
  • the present invention relates to the coated metal pipes, reinforcing steels and prestressing steels which have been produced using the method according to the invention.
  • liquids in particular aqueous preparations, which contain halogen element acids as an essential component, are used as pretreatment agents.
  • halogen element acids examples include fluorine, chlorine, bromine and iodine. According to the invention, fluorine is used with particular preference.
  • halogen element acids examples include titanium, zirconium, hafnium vanadium, molybdenum, tungsten, silicon, germanium. Tin and boron.
  • titanium, zirconium, hafnium and silicon are preferred and titanium is particularly preferably used.
  • the halogen element acids which are advantageously used according to the invention are hexafluorotitanic acid, zirconic acid, hafnic acid, silicic acid, germanic acid or tin acid or tetrafluoroboric acid.
  • hexafluorotitanic acid, zirconic acid, hafnium acid and silica have particular advantages, which is why they are used with preference.
  • hexafluorotitanic acid is very particularly preferably used because it provides articles according to the invention with excellent adhesion between the metal surface and the plastic coating and with particularly high resistance to corrosion.
  • halogen element acids their salts can also be used, in particular the ammonium or the alkali metal salts.
  • the pretreatment agents to be used according to the invention contain further constituents such as hydrofluoric acid, hydrochloric acid, sulfuric acid or nitric acid or their salts, metal salts, metal oxides or hydroxides, silicates such as water glass or low molecular or high molecular weight organic compounds such as gluconic acid or polyacrylates.
  • suitable further constituents are known from the patents US-A-4 517028, US-A-5 344 504, WO 95/14539 or WO 85/05131.
  • the metal pipes, reinforcing steels or prestressing steels are coated in accordance with the invention in the following manner:
  • the metal surface is cleaned thoroughly. This can be achieved, for example, by blasting with steel wire.
  • the steel blasting will preferably carried out so that an average surface roughness of 40 to 100 microns.
  • the metal surface which is at room temperature or which has been preheated is then wetted with the pretreatment agents to be used according to the invention described above by pouring over. Wetting can also be done in other ways, e.g. by dipping, brushing, pouring, rolling or spraying.
  • a layer containing at least one element for example a layer containing titanium, with a basis weight of 1 to 100 mg / m 2 , preferably 3 to 30 mg / m 2 , particularly preferably 5 to 15 mg / m 2 arises.
  • a layer thickness can be influenced by the concentration of the pretreatment agent to be used according to the invention.
  • the metal surface is completely dried. This can be done in a one-step or two-step process.
  • the mixture is heated in one step to 100 to 300 ° C., preferably 180 to 250 ° C.
  • drying is carried out first at 30 to 100 ° C. and then in a second stage drying at 100 to 300 ° C., preferably 180 to 250 ° C. Drying can be done by induction heating or in a gas oven.
  • the heated and dried metal surface is then coated.
  • the metal surfaces pretreated according to the invention are suitable for coating both with one and with several layers. All known coating materials can be used, i.e. Powder coatings, powder coating dispersions or liquid coatings. Coating with powder coatings based on epoxy resin is preferred according to the invention.
  • Powder coatings which contain epoxy resins, crosslinking agents, catalysts, fillers and, if appropriate, auxiliaries and additives are suitable for coating with a layer.
  • Suitable epoxy resins are all solid epoxy resins with epoxy equivalent weights between approximately 400 and 3000. These are mainly epoxy resins based on bisphenol A and bisphenol F or epoxidized novolak resins. Mixtures of bisphenol A or bisphenol F resins and novolak resins are also suitable.
  • the epoxy resins based on bisphenol A and bisphenol F generally have a functionality ⁇ 2, the epoxidized novolak resins a functionality> 2.
  • the phenolic hydroxyl groups are etherified with alkyl, aryl or similar groups. By reacting the phenolic hydroxyl groups with epichlorohydrin, epoxy groups are incorporated into the molecule.
  • Epoxidized novolak resins are structurally related to bisphenol A resins.
  • Epoxidized novolak resins can be produced by epoxidation of novolaks, which consist, for example, of 3 to 4 phenol cores, which Methylene bridges are interconnected. Alkyl-substituted phenols which are reacted with formaldehyde can also be used as novolak resins.
  • Suitable epoxy resins are, for example, the products commercially available under the following names:
  • the Puiverlack contains crosslinking agents to harden the epoxy resins. Suitable crosslinking agents are so-called accelerated dicyandiamides, substituted dicyandiamides, amine derivatives, anhydrides, anhydride adducts and crosslinking agents containing phenolic hydroxyl groups. Accelerated dicyandiamides and crosslinking agents which have phenolic hydroxyl groups are preferred. Any phenolic resin, for example, can be used as the crosslinking agent which has phenolic hydroxyl groups, as long as it has the methylol functionality required for the reactivity.
  • Preferred phenolic resins are reaction products of phenol, substituted phenols and bisphenol A with formaldehyde, produced under alkaline conditions. Under such conditions, the methylol group is linked to the aromatic ring either ortho or para.
  • the phenolic crosslinking agents used are particularly preferably bisphenol A or bisphenol F resins containing hydroxyl groups and having a hydroxy equivalent weight in the range from 180 to 600, particularly preferably in the range from 180 to 300.
  • Such phenolic crosslinking agents are prepared by reacting bisphenol-A or bisphenol-F with components containing glycidyl groups, such as. B. the diglycidyl ether of bisphenol-A.
  • Such phenolic crosslinking agents are available, for example, under the trade names 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 used in such a ratio that the number of epoxy groups to the number of phenolic OH groups is approximately 1: 1.
  • Suitable accelerated dicyandiamide hardeners are e.g. Epikure® 143 FF (Shell-Chemie) or Grilonit® H 88071 (Ems-Chemie).
  • the powder coatings contain one or more suitable catalysts for curing epoxy resin.
  • Suitable catalysts are phosphonium salts of organic or inorganic acids, imidazole and imidazole derivatives, quaternary ammonium compounds and amines.
  • the catalysts are generally used 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.
  • Suitable phosphonium salt catalysts are ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphoniumthiocyanate, ethyltriphenylphosphonium acetate / acetic acid complex, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and tetrabutylphosphonium bromide. Acetic acid complex.
  • suitable phosphonium catalysts are described, for example, in US Pat. Nos. 3,479,990 and 3,341,580.
  • Suitable imidazole catalysts are, for example, 2-styrylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2-butylimidazole. These and other imidazole catalysts are e.g. B. described in Belgian Patent No. 756693.
  • phenolic crosslinking agents already contain catalysts for epoxy resin crosslinking.
  • the powder coatings contain fillers. These fillers are usually used in a proportion of 10 to 50% by weight, based on the total weight of the powder coating. In some cases filler contents of more than 50% by weight are also possible.
  • the powder coatings can be used as fillers e.g. Contain titanium dioxide, barium sulfate, chalk, talc, kaolin, magnesium aluminum silicate, silica modifications such as quartz, cristoblalite, tridymite, keatite, stishovite, melanophlogite, coesite or fibrous silica or mixtures of these fillers. Chemically post-treated fillers can also be used. Glycidyl group-functionalized silica modifications, such as e.g. Silbond® 6000 EST (from the company Quarzwerke) was used.
  • the powder coating materials advantageously contain 10 to 40% by weight, based on the total weight of the powder coating material, of fillers.
  • the powder coatings may also contain auxiliaries and additives. Examples of this are leveling agents, flow aids and deaerating agents, such as benzoin.
  • the powder coatings are produced by known methods (see, for example, product information from BASF Lacke + Wegner AG, "Pulverlacke", 1990) by homogenizing and dispersing, for example using an extruder, screw kneader, etc. After the powder coatings have been produced, they are adjusted to the desired particle size distribution by grinding and, if necessary, by sifting and sieving.
  • the powder coatings are applied electrostatically or triboelectrostatically or by means of a fluid bed to the previously heated metal surface.
  • further layers can be applied to the metal surfaces coated with the pretreatment agent according to the invention.
  • these consist of
  • a layer of epoxy resin primer which is preferably applied in a thickness of 20 to 600 ⁇ m, in particular 50 to 200 ⁇ m,
  • an adhesive layer preferably in a thickness of 50 to 400 ⁇ m, in particular 180 to 350 ⁇ m, and
  • Suitable epoxy resin primers are advantageously in powder form. They preferably consist of the same components as the powder coatings described in detail above.
  • the powdery epoxy resin primers are applied electrostatically or triboelectrostatically or by means of a fluid bed to the previously heated metal surface.
  • the application strength of the epoxy resin primer is usually in the range from 30 to 400 ⁇ .m.
  • Thermoplastic hard adhesives are advantageously used as the adhesive layer. They are applied to the powder primer layer either in the extrusion process as a melt or in the powder application process.
  • Suitable adhesives are copolymers, graft copolymers and ionomers which have carboxyl or anhydride groups or groups which can be hydrolyzed to carboxyl groups.
  • Suitable copolymers can be prepared by copolymerization of ethylene or propylene with cx, ⁇ -ethylenically unsaturated carboxylic acids, such as.
  • Suitable adhesives are furthermore polymers which can be prepared by grafting at least one polymer from the group of the polyolefins with up to 10% by weight, based on the total weight of the monomers, of at least one monomer from the group of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acids , their anhydrides, their esters or salts in the presence or absence of peroxides.
  • Proven thermoplastic hard adhesives for metal coating are
  • Copolymers of ethylene, (meth) acrylic acid esters and (meth) acrylic acid are commercially available under the name Lucalen® (manufacturer: BASF AG, Ludwigshafen).
  • Lucalen® manufactured by BASF AG, Ludwigshafen.
  • suitable ones Lucalen® types are Lucalen® A 291 0 M, Lucalen® A 291 0 MQ 47, Lucalen® A 31 1 0 M and Lucalen® A 31 1 0 MQ 244.
  • the application thickness of the thermoplastic hard adhesive is usually in the range from 100 to 500 ⁇ m, and the substrate temperature when applying the thermoplastic hard adhesive is in the range from 150 to about 220 ° C. It must be ensured that the epoxy resin primer is not fully cured at the time of application of the adhesion promoter in order to produce a firm bond.
  • a polyolefin coating agent is applied as the third layer to protect against mechanical action onto the melted adhesive at elevated temperature - usually in the extrusion process.
  • Suitable polyolefins are low-density, medium-density, high-density, linear low and linear very low density polyethylene, and also polypropylene, its copolymers with ethylene and other monomers, and the copolymers of ethylene and propylene with one or more comonomers from the group of the vinyl esters , Vinyl alkyl ethers and the unsaturated mono- and dicarboxylic acids and their salts, anhydrides and esters. Ethylene homopolymer is particularly preferably used as the polyolefin coating agent.
  • Suitable polyethylenes are available, for example, under the trade name Lupolen® (manufacturer: BASF AG).
  • Lupolen® types are Lupolen® 2441 D, Lupolen® 2452 D, Lupolen® 3821 D and Lupolen® 3652 D (BASF AG).
  • a fourth layer can be added to the three-layer coating described.
  • a thermally insulating material Polyurethanes or Poiypropylenes in foamed form into consideration.
  • Such a mechanically and thermally stable layer structure accordingly looks as follows:
  • the objects according to the invention are steel pipes, they can also be coated on the inside with the coating agents described in detail above.
  • the articles according to the invention produced with the aid of the method according to the invention using the pretreatment agents to be used according to the invention prove to be particularly corrosion-resistant and stable against mechanical action. They are extremely thermally strong and can therefore withstand frequent extreme temperature fluctuations without damage.
  • the described methods according to the invention are particularly suitable for the construction of protective layers of steel pipes, in particular steel pipes, such as are used for pipelines.
  • the steel pipe surface is first cleaned of rust, scale, grease, oil, dust etc. in a customary and known manner.
  • the application with the pretreatment agent to be used according to the invention is then carried out by dipping, brushing, pouring, rolling or Spraying.
  • the pretreatment agent according to Example 1.1 of WO 95/14539 is advantageously used here.
  • the coated tube is heated by means of the induction coils or by means of a gas oven.
  • thermoplastic hard adhesive is applied to the primer layer as a melt or in powder form using a conventional and known spraying device.
  • thermoplastic hard adhesive make sure that a good bond between the epoxy resin primer and the hard adhesive can only be achieved if the epoxy resin is not fully cured at the time of the hard adhesive application; preferably the degree of curing is between about 25 and 75%.
  • a ring nozzle process can also be used for smaller pipe diameters.
  • an extrusion winding process is used with a slot die.

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Architecture (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne l'utilisation d'acides à élément halogéné et/ou de leurs sels dans des produits de prétraitement sans chromate de surfaces métalliques pour la fabrication de tuyaux de métal revêtus ou d'aciers à béton armé ou d'armature, un procédé de revêtement de ces substrats, ainsi que les tuyaux métalliques revêtus et les aciers revêtus à béton armé et d'armature.
PCT/EP1997/004400 1996-08-24 1997-08-13 Utilisation d'acides a element halogene pour la fabrication de tuyaux metalliques revetus ou d'aciers revetus a beton arme ou d'armature WO1998007896A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19634222.8 1996-08-24
DE19634222A DE19634222A1 (de) 1996-08-24 1996-08-24 Beschichtete Metallrohre, beschichteter Armierungsstahl oder Spannstahl

Publications (1)

Publication Number Publication Date
WO1998007896A1 true WO1998007896A1 (fr) 1998-02-26

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PCT/EP1997/004400 WO1998007896A1 (fr) 1996-08-24 1997-08-13 Utilisation d'acides a element halogene pour la fabrication de tuyaux metalliques revetus ou d'aciers revetus a beton arme ou d'armature

Country Status (3)

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DE (1) DE19634222A1 (fr)
ID (1) ID19052A (fr)
WO (1) WO1998007896A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
US8038829B2 (en) 2006-02-22 2011-10-18 Shawcor Ltd. Coating method for pipe having weld bead

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DE10104904A1 (de) * 2001-02-03 2002-08-08 Abb Patent Gmbh Verfahren zur Ummantelung eines Körpers
DE102008007584A1 (de) * 2008-01-31 2009-08-27 Europipe Gmbh Verfahren zur Herstellung faserumwickelter Stahlleitungsrohre mit einer Korrosionsschutzumhüllung
EP3258151B1 (fr) * 2015-02-13 2020-05-27 Sanoh Industrial Co., Ltd. Tuyau métallique enrobé pour tuyauterie de véhicule et procédé de production de celui-ci

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DE1153589B (de) * 1957-03-21 1963-08-29 Jenolite Ltd Verfahren zur Behandlung der Oberflaeche von Gegenstaenden aus Eisenmetallen, die in Beton eingebettet werden
CH450105A (de) * 1964-05-19 1968-01-15 Halmstads Jarnverks Ab Verfahren zur Herstellung einer korrosionsbeständigen Oberfläche auf Armierungsmaterial aus Eisen
US4004064A (en) * 1974-01-02 1977-01-18 Joseph W. Aidlin Protective coating for articles
DE3200245A1 (de) * 1982-01-07 1983-07-14 Showa Aluminum Corp., Sakai, Osaka Verfahren zur oberflaechenbehandlung von aluminiumkoerpern
GB2173424A (en) * 1985-03-28 1986-10-15 Usui Kokusai Sangyo Kk Anticorrosive coated steel pipe
DE3639417C1 (de) * 1986-11-18 1987-11-26 Mannesmann Ag Verfahren zum Ummanteln von Gegenstaenden aus Stahl mit Kunststoff
EP0411606A2 (fr) * 1989-08-01 1991-02-06 Nippon Paint Co., Ltd. Produits chimiques et bain pour le traitement de surfaces en aluminium ou ses alliages et procédÀ© de traitement de surface
EP0608421A1 (fr) * 1991-10-15 1994-08-03 OHMI, Tadahiro Materiau metallique ayant une excellente resistance aux solutions chimiques et dispositif de traitement par solutions chimiques ou pieces d'un tel dispositif utilisant ce materiau
WO1995014539A1 (fr) * 1993-11-29 1995-06-01 Henkel Corporation Composition et procede de traitement de metaux
WO1996007772A1 (fr) * 1994-09-02 1996-03-14 Henkel Corporation Composition et procede de traitement des metaux

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8038829B2 (en) 2006-02-22 2011-10-18 Shawcor Ltd. Coating method for pipe having weld bead

Also Published As

Publication number Publication date
ID19052A (id) 1998-06-04
DE19634222A1 (de) 1998-02-26

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