EP0822868A1 - Pieces metalliques munies d'une couche anticorrosion - Google Patents

Pieces metalliques munies d'une couche anticorrosion

Info

Publication number
EP0822868A1
EP0822868A1 EP96914939A EP96914939A EP0822868A1 EP 0822868 A1 EP0822868 A1 EP 0822868A1 EP 96914939 A EP96914939 A EP 96914939A EP 96914939 A EP96914939 A EP 96914939A EP 0822868 A1 EP0822868 A1 EP 0822868A1
Authority
EP
European Patent Office
Prior art keywords
corrosion
metal
rubber
corrosion protection
metal parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96914939A
Other languages
German (de)
English (en)
Inventor
Klaus Marten
Malte Reppenhagen
Rainer Wefringhaus
Heinz-Werner Alberts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0822868A1 publication Critical patent/EP0822868A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings

Definitions

  • the invention relates to metal parts with a corrosion protection layer on the basis of a PU, epoxy or phenol resin and its production and use for the production of rubber / metal composite parts.
  • JA 78/288671-A recommends protecting steel against corrosion with a 10 to 100 ⁇ m thick epoxy resin coating, the resin containing 1 to 70% by weight of ferric oxide.
  • DE 3504228-C describes the use of a PU coating as corrosion protection for metals.
  • the polyurethane is said to be produced from castor oil polyol with a functionality of at least 2 and a polyisocyanate.
  • Common coating additives can be added to the coating composition, for example iron oxide as a filler. It is also known to vulcanize rubbers coated in this way with the aid of adhesives.
  • DE 17 19 158-C describes a solvent-based adhesive for bonding metals and elastomers, the rubber / metal composite parts obtained being said to be particularly resistant to environmental influences, for example salt water. According to Example 4, the adhesive contains triglycidyl isocyanurate, dinitrosonaphthalene and chlorinated
  • Ethylene / propylene / diene terpoly erisat, channel black and Fe2Ü3 (27 wt .-%, based on the solids) as well as methyl ethyl ketone and xylene.
  • the adhesive can be sprayed onto the cleaned metal surfaces pretreated with sandblasters. Drying and curing take place at temperatures and at times that are normally required for the vulcanization of compounded elastomers.
  • the metals mentioned are: cold-rolled steel, stainless steel, aluminum alloys, copper, brass and bronze.
  • the following types of rubber are examined: nitrile, natural, SBR, butyl, poly (chlorobutadiene), EPDM, silicone and polyacrylate rubber.
  • iron is bonded to rubber by first producing a 0.05 to 0.3 ⁇ m thick layer of magnetic iron oxide (Fe3Ü4) on the iron surface, followed by the primer Che lok 205 and then the adhesive Che lok 220 sprayed on and then, after drying, rubber is vulcanized under pressure. None is said about the corrosion behavior. If the rubber / metal composite part is coated with a layer of lacquer, there are problems with the adhesion of the lacquer to the rubber and with corrosion in the metal / rubber boundary area.
  • Fe3Ü4 magnetic iron oxide
  • DE 27 48686-A proposes that the metal on the entire area at risk of corrosion First coat with an epoxy resin and then glue the rubber to this layer. For example, one should first clean and pretreat the iron surface (for example with sandblasting) and then coat it with a powdered resin (diglycidyl ether of bisphenol A epoxy resin) and with a hardener (trimellitic anhydride). After curing at 232 ° C, an adhesive filler based on phenolic resin and an adhesive coating of a halogenated polyolefin and an aromatic nitroso compound are applied. After this adhesive system had dried, rubber was finally vulcanized under high pressure at 149 ° C. in the course of 15 minutes.
  • a powdered resin diglycidyl ether of bisphenol A epoxy resin
  • a hardener titanium anhydride
  • the powdered coating composition generally contains, in addition to the resin and the hardener, a dye, a filler, an additive which controls the flowability and an anti-corrosion agent.
  • a disadvantage of this process is that a uniform coating of paint cannot be achieved by spraying on the paint system. This applies in particular to hard-to-reach areas of a metal part, such as occur with complicated Gu ⁇ mn ' / Meta11 composite parts.
  • the lacquer coating is to be applied by cataphoretic dip coating.
  • the layer thickness should be different.
  • the paint layer should be significantly thicker than 20 ⁇ m.
  • the layer thickness should be less than 20 ⁇ m if possible.
  • Another disadvantage of this method is that special devices are necessary for this.
  • the solution according to the invention can be found in the patent claims. It essentially consists in the fact that the corrosion protection layer based on PU, epoxy or phenolic resins contains 10 to 80% by weight of corrosion protection pigments, based on the solids content.
  • the anti-corrosion pigments are known substances for this purpose, namely lead-containing pigments (e.g. lead mines, lead silicon chromate and calcium plumbate), chromate pigments (zinc calcium chromate, zinc tetraoxide chromate, strontium chromate and barium chromate), phosphate pigments (e.g. zinc phosphate and chromium phosphate), metal pigments (zinc dust and lead dust) and in particular metal oxides (for example lead dioxide and zinc oxide).
  • lead-containing pigments e.g. lead mines, lead silicon chromate and calcium plumbate
  • chromate pigments zinc calcium chromate, zinc tetraoxide chromate, strontium chromate and barium chromate
  • phosphate pigments e.g. zinc phosphate and chromium phosphate
  • metal pigments e dust and lead dust
  • metal oxides for example lead dioxide and zinc oxide.
  • Iron oxides are of particular importance in the case of metal oxides
  • the anti-corrosion pigments should have an average diameter of 0.1 to 2 ⁇ m, in particular 0.3 to 0.7 ⁇ m.
  • the concentration of the anti-corrosion pigments - based on the solids content - is preferably 20 to 70% by weight, in particular 30 to 50% by weight.
  • the corrosion protection layer is based on reactive resins, namely on a polyurethane resin and above all on a phenolic and Epoxy resin.
  • Polyols based on fat derivatives for example unsaturated fats, which were first epoxidized and then reacted with alcohols or carboxylic acids, are particularly suitable for building up the polyurethane and epoxy coating.
  • the phenolic resins the novolak and resole resins are of particular importance.
  • the organic coatings can also contain the usual additives, in particular anti-aging agents, elasticizing agents (e.g. nitrile rubber), flow agents (e.g. preparation from an alkyd resin / lecithin mixture).
  • anti-aging agents e.g. nitrile rubber
  • flow agents e.g. preparation from an alkyd resin / lecithin mixture.
  • the solvent or dispersant used is of particular importance.
  • the solvent system used can be any one in which the film former is dissolved, dispersed or softened and which can be easily evaporated.
  • xylene or other aromatic hydrocarbon solvents are also preferably used, although ketone solvents such as methyl ethyl ketone etc. can also be used advantageously.
  • the choice of solvent depends primarily on the binder used. Solvents or plasticizers for the various binders are known to the person skilled in the art.
  • the amount of solvent can vary over a fairly wide range.
  • the coating composition can have a solids content of from 1 to about 55%, in particular from 15 to 25%.
  • the upper limit of the solids content is determined by the processability of the mass.
  • a Solids content of about 30 to 40% is used and the optimum is a content of 35%.
  • the solvent content of the coating composition can be regulated in a known manner.
  • the viscosity naturally depends to a large extent on the binder used as well as on the particle size of the solid constituents. All of these factors must be weighed against one another in order to obtain a coating composition which does not separate or forms a non-redispersible sediment during storage.
  • the aqueous or organic solution or dispersion is applied to the metal surface.
  • the metal can be, for example: steel, aluminum, copper, brass or the like. Extensive preparation of the metal surface is not necessary; degreasing the metal surface is sufficient to obtain excellent bonds. Of course, they are improved by mechanical or chemical pretreatment.
  • mechanical metal pretreatment for example, alloyed steels are first degreased in stabilized liquid or vaporous perchlorethylene, then with a hard, sharp-edged blasting material with a grain size of 0.5-2 mm (preferably chilled cast iron 0.8-1.2 mm) blasted. The average roughness should be max. 20 ⁇ m (preferably 10 +/- 5 ⁇ m).
  • the active surface created in this way must be free of grease and oil.
  • Aluminum, brass, other non-ferrous metals or stainless steel are pretreated as previously described; however, electrical corundum is used here instead of chilled cast iron. Alloyed steels can also be provided with a microcrystalline ZnCa phosphate layer or with a Zn phosphate layer. In order to achieve optimal adhesion, the layer weight should not exceed 2 g / qm.
  • Aluminum and its alloys are preferably provided with a Cr-VI layer. The iron alloy can also be galvanized. Matt, thin zinc layers, which are additionally passivated by means of Cr-VI layers, zirconium salts or iron phosphate, enable reliable adhesion.
  • the corrosion protection agent is applied to the entire surface of the pretreated metal surface, in a conventional manner, e.g. by casting, rolling, brushing, dipping, knife coating and in particular by spraying, especially with compressed air. Other application methods known in coating technology can also be used, apart from the use of electrophoresis.
  • the quantity applied depends on whether the surfaces are additionally protected by rubber or not. In the event that it is protected with rubber, a layer thickness in the dry state of 5-30, in particular 7 to 17 ⁇ m, is sufficient. In the event that the metal is not protected by rubber, the layer thickness should be 10 to 100, in particular 20 to 50 ⁇ m.
  • the anti-corrosion agent applied to the metal surface is then hardened to the extent necessary for the subsequent processing. If no further binding with a rubber is to take place, hardening takes place.
  • the usual times and temperatures known in paint technology are to be used for this.
  • the applied anticorrosive agent is only solidified to such an extent that good handling until vulcanization is possible without the anticorrosive layer being damaged. A simple drying (ventilation) at ambient temperature or at air temperatures up to 50 ° C may be sufficient.
  • the drying depends on the specific conditions of the respective situation. Their optimal design can easily be found out with a few trials. For example, it is advisable to dry films with a thickness of 10 ⁇ m dry layer thickness for 20 minutes at room temperature or 1 minute with circulating air at 120 ° C. With a dry layer thickness of 20 ⁇ m, drying for 45 minutes at room temperature or 2 minutes with circulating air at 120 ° C is advisable. This drying time at 120 ° C can be reduced to 30 seconds if parts preheated to 60 ° C are sprayed. However, the object temperature of the preheated parts should allow sufficient wetting of the surface and should therefore be in a certain temperature range, depending on the chosen dilution. Which is limited by the boiling point of the solvent.
  • coated metal parts with a dry film thickness of more than 20 ⁇ m come into direct contact with the vulcanizing mold, it is advisable to harden the film more intensively (e.g. 2 minutes with circulating air at 200 ° C) in order to avoid contamination of the molds. Hardening in IR, UHF or induction current systems is also possible. With the latter method there is a risk of overcrosslinking of the primer if work is carried out with settings that are too energetic.
  • Suitable binders are based on mixtures of halogenated polymers and crosslinking systems and, if appropriate, additives (for example fillers, film formers or Halogen catcher).
  • Commercial binders of this type are: Chemosil 411, Chemosil 220, Chemosil 222, Chemosil 231 G and Chemosil X 9500 as well as aqueous binders such as XW 7484.
  • Chemosil 411, Chemosil 220, Chemosil 222, Chemosil 231 G and Chemosil X 9500 as well as aqueous binders such as XW 7484.
  • Megum, Thixon, Parlock, Cilbond, Chemolok, Unilok or Armlok The names given above are trademarks.
  • the binders are applied in a known manner.
  • the manufacturer's technical information sheets must be observed in detail.
  • the metal parts coated with the anticorrosive agent and with the binder are connected in a vulcanization tool to the rubber mixture to be vulcanized.
  • All types of rubber that can be crosslinked during hot vulcanization are suitable: e.g. NR, IR, IIR, NBR, HNBR, CR, ACM, CSM, AEM, SBR and EPDM.
  • Preferred rubbers are: NR, TR and NBR.
  • the vulcanization temperature is between 90 and 220 ° C, preferably between 150 and 180 ° C.
  • the vulcanization time depends on the vulcanization speed, the rubber mixture and the size of the parts.
  • the anti-corrosion agent and the binder can be used on existing systems such as the chain spraying machines are processed.
  • the primer is an anti-corrosion agent, there is no need to apply an anti-corrosion agent after vulcanization.
  • the primer can be free of halogens.
  • the invention is illustrated by the following examples.
  • Example 1 Metal test specimen with corrosion protection
  • PU (1) resin from 100 parts of diphenylmethane diisocyanate (homologs and isomers) and 54 parts of an aliphatic polyetherester diol with an OHN of 200 to 230.
  • Both systems still contained 5 parts of zeolite paste.
  • Metallon E 2203 100: 40 / resin: hardener
  • Edenol 3454 (16 parts on resin) was used as a plasticizer additive.
  • a resin mixture consisting of a resin from Süd-West-Chemie and one from Hooker was used here.
  • the temperature was raised from 35 ° C to 55 ° C.
  • the salt concentration was increased from 5% to 20%.
  • the pH was adjusted to pH 1 with acetic acid.
  • the spray quantity was doubled.
  • Example 2 Rubber / metal test specimen according to DIN 53531
  • Metal ST 37 steel
  • Pretreatment The metal parts are degreased in 1,1,1-trichloroethane vapor until no more condensate runs off (approx. 10 min). After cooling, the steel parts are blasted with cast steel gravel until they have a uniform matt gray surface. After blasting, the parts are freed again from the blasting dust with CHC steam, as described above.
  • Corrosion protection agent HT 8710 (consisting essentially of phenolic resin, dissolved in ethanol with 25% by weight iron oxide, ⁇ -Fe2 ⁇ 3) "black"
  • Binder Chemosil 220 (consisting essentially of halogenated polymers and crosslinkers)
  • test specimens After vulcanization, the test specimens are conditioned according to DIN 53500.
  • test specimens are subjected to a peeling test in accordance with DIN 53531 Part 1 in a tearing machine.
  • the adhesion values found are averaged arithmetically.
  • the tear pattern is assessed and evaluated in% R (rubber break).
  • the adhesive value is in the usual range of 35 - 45 daN / inch.
  • the rubber break is also in the usual range of at least 98% rubber break.
  • test specimens are loaded in a suitable apparatus with a load of 2 kg on the rubber strap perpendicular to the binding surface and left in boiling water for 8 hours. After this time, the water is drained off and the samples are left to cool in the unloaded state. After peeling off the rubber layer, the damage to the bond is assessed and evaluated.
  • the rubber break is in the usual range of at least 90% rubber break.
  • a 250-hour SST is carried out with the test specimens produced in accordance with DIN 53531.
  • the weld line is loaded with 2 kp / inch.
  • no initial background corrosion can be found when using the new primer / anti-corrosion agent.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne des pièces métalliques munies d'une couche anticorrosion à base d'une résine PU, époxy ou phénol contenant entre 10 et 80 % en poids de pigments anticorrosion par rapport à la teneur en solides. L'oxyde ferrique α (noir) constitue le pigment anticorrosion préféré. La couche anticorrosion sert avantageusement de couche de fond pour une liaison ultérieure avec du caoutchouc dans les conditions de la vulcanisation à chaud. La couche de fond, comme les liants, sont appliqués de préférence par pulvérisation sous air comprimé. Ce procédé permet de parvenir à une bonne résistance à la corrosion du composite caoutchouc/métal, à l'aide de moyens simples.
EP96914939A 1995-04-28 1996-04-18 Pieces metalliques munies d'une couche anticorrosion Withdrawn EP0822868A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19515234 1995-04-28
DE1995115234 DE19515234A1 (de) 1995-04-28 1995-04-28 Metallteile mit einer Korrosionsschutz-Schicht
PCT/EP1996/001617 WO1996033816A1 (fr) 1995-04-28 1996-04-18 Pieces metalliques munies d'une couche anticorrosion

Publications (1)

Publication Number Publication Date
EP0822868A1 true EP0822868A1 (fr) 1998-02-11

Family

ID=7760348

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96914939A Withdrawn EP0822868A1 (fr) 1995-04-28 1996-04-18 Pieces metalliques munies d'une couche anticorrosion

Country Status (3)

Country Link
EP (1) EP0822868A1 (fr)
DE (1) DE19515234A1 (fr)
WO (1) WO1996033816A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19634329A1 (de) * 1996-08-24 1998-02-26 Henkel Kgaa Zweikomponenten-Epoxy-System zur Beschichtung von Metallen
DE19708880A1 (de) * 1997-03-05 1998-09-10 Widia Gmbh Schneideinsatz zum Zerspanen
DE19737685C2 (de) * 1997-08-29 1999-08-12 Sonderhoff Ernst Fa Abschirmdichtung
DE19755421A1 (de) * 1997-12-13 1999-06-17 Henkel Kgaa Gummi-Metall-Verbund
DE10046809C2 (de) * 2000-09-21 2002-11-07 Alfons Knoche Korrosionsfester Niet und Verfahren zu seiner Herstellung
US7348370B2 (en) 2005-04-27 2008-03-25 United Technologies Corporation Metal oxides and hydroxides as corrosion inhibitor pigments for a chromate-free corrosion resistant epoxy primer
EP2591029A1 (fr) 2010-07-08 2013-05-15 Huntsman International LLC {0>revêtement anticorrosion à base de polyisocyanate<}0{><0}

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Publication number Priority date Publication date Assignee Title
CA890370A (en) * 1972-01-11 Chrysler Corporation Bonding ferrous surface by magnetic iron oxide
US2078917A (en) * 1934-08-24 1937-04-27 Us Rubber Co Method of attaching rubber to metal and articles produced thereby
GB487096A (en) * 1937-05-27 1938-06-15 Bristol Aeroplane Co Ltd Improvements in the protection of metals against erosion
GB821956A (en) * 1956-08-07 1959-10-14 Rohm & Haas Process for coating metals and product thereof
FR1230493A (fr) * 1959-02-10 1960-09-16 Parker Ste Continentale Procédé pour faire adhérer du caoutchouc sur des alliages à base de fer et en particulier sur les aciers inoxydables et les aciers fortement alliés, et produit obtenu à l'aide de ce procédé
IL24408A (en) * 1965-10-04 1969-06-25 Wassermann A Anti-corrosive paint compositions
DE1719158C3 (de) * 1966-08-29 1980-11-06 Henkel Kgaa, 4000 Duesseldorf Klebstoffe auf Basis von Triglycidylisocyanurat
US4079168A (en) * 1976-11-01 1978-03-14 Lord Corporation Rubber-metal composite structures having improved resistance to corrosion
GB2028827B (en) * 1978-08-31 1983-06-15 Ford Motor Co Anticorrosive primer composition
DE3047992A1 (de) * 1980-12-19 1982-07-15 Metzeler Kautschuk GmbH, 8000 München Verfahren zur herstellung eines lackueberzuges auf dem metallteil eines gummi/metall-verbundteils
US4417008A (en) * 1981-06-30 1983-11-22 Elkem Metals Company Improved color pigment for solvent-base paint formulations
JPS60166353A (ja) * 1984-02-09 1985-08-29 Dai Ichi Kogyo Seiyaku Co Ltd ポリウレタン金属防食塗料組成物
JPS61192372A (ja) * 1985-02-21 1986-08-26 Nippon Steel Corp 鋼構造物の水中塗装方法
JPS6234966A (ja) * 1985-08-08 1987-02-14 Chugoku Toryo Kk 防錆塗料組成物
US5510191A (en) * 1993-04-02 1996-04-23 Nok Corporation NBR based rubber laminated metal plate gasket material

Non-Patent Citations (1)

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Title
See references of WO9633816A1 *

Also Published As

Publication number Publication date
DE19515234A1 (de) 1996-10-31
WO1996033816A1 (fr) 1996-10-31

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