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EP1039974A2 - Composite caoutchouc-metal - Google Patents

Composite caoutchouc-metal

Info

Publication number
EP1039974A2
EP1039974A2 EP98965765A EP98965765A EP1039974A2 EP 1039974 A2 EP1039974 A2 EP 1039974A2 EP 98965765 A EP98965765 A EP 98965765A EP 98965765 A EP98965765 A EP 98965765A EP 1039974 A2 EP1039974 A2 EP 1039974A2
Authority
EP
European Patent Office
Prior art keywords
rubber
self
metal
resin
binder
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Withdrawn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
EP98965765A
Other languages
German (de)
English (en)
Inventor
Ralf Schelbach
Ilona Lange
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 EP1039974A2 publication Critical patent/EP1039974A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • 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
    • B05D2530/00—Rubber or the like
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

  • the invention relates to a method for producing a rubber-metal composite, the innovation of which is that a layer of a self-depositing resin is applied to the metal before the rubber is vulcanized in a later step. Furthermore, the invention relates to a composite component made of metal and rubber, which contains a hardened layer of a self-separating resin between the metal surface and the rubber. Composite components of this type can be used in many technical fields. Examples include vehicle and mechanical engineering.
  • the natural requirement for rubber-metal composite components is that the rubber adheres sufficiently firmly to the metal. Sufficiently firm adhesion is given if, in adhesion tests in which the rubber and metal bond is torn apart, the fracture occurs within the rubber compound and not between rubber and metal.
  • the corrosion resistance of the rubber-metal composites is a serious problem in many applications.
  • the composites can come into contact with corrosive media such as salt water and must have sufficient corrosion resistance for this.
  • the entire rubber-metal composite could be painted over after its manufacture.
  • lacquers that have to be baked at a temperature at which the rubber is damaged cannot be used for this.
  • paints that cannot be burned in do not provide adequate corrosion protection.
  • DE-A-27 48 686 describes a method for increasing the corrosion resistance of a rubber-metal structure, in which an epoxy resin-based powder coating is applied to the metal surface before being connected to the rubber.
  • This coating has the disadvantage that it softens at the temperatures of the rubber vulcanization. Since vulcanization is usually carried out under pressure, there is a risk that the rubber will shift on the softened surface. The same danger exists with a later load at a temperature that occurs above the softening point of the powder coating (from about 50 ° C). Such temperatures can easily be reached, for example, in a motor vehicle parked in the sun.
  • EP-A-54 861 proposes to coat the metal with a cataphoretic dip coating before the rubber is applied.
  • this is complex in terms of plant technology, since chemical pretreatment of the metal surface, such as phosphating, including rinsing, has to be carried out before the cataphoretic dip coating. There are therefore several upstream process steps and thus several treatment baths required.
  • the cataphoretic dip painting requires a lot of energy and therefore has economic disadvantages.
  • the object of the invention is to provide a new method for producing a rubber-metal composite.
  • the metal should be coated with a protective coating known to have good anti-corrosion properties before the rubber is applied.
  • This protective coating should be able to be applied in a technically simple and thus economical manner and should not soften under the conditions of the vulcanization of the rubber.
  • the invention accordingly relates to a method for producing a rubber-metal composite on a metal, characterized in that a) a self-depositing resin is deposited and cured on the metal, b) if desired, a primer is applied to the resin, c ) a binder is applied to the primer or to the self-separating resin, d) a natural or synthetic rubber is applied to the binder and e) the rubber is vulcanized at a temperature in the range from 90 to 220 ° C.
  • Metals whose ions lead to the coagulation and deposition of the self-depositing resin are suitable as the metal substrate.
  • Cast iron, steel or other iron-containing substrates are currently considered for this. Accordingly, the method is preferably carried out using iron-containing substrates. However, it can also be carried out on zinc or galvanized steel if suitable baths of self-separating resins are selected and / or suitable pre-rinses are used. Other metal substrates are also suitable, provided that self-depositing resins are available for this.
  • the self-separating resins which can be used for the purposes of this invention are also referred to in the art as autophoresis resins or autophoresis lacquers or autophoretic lacquers.
  • autophoretic R Coating Chemicals is used in Anglo-Saxon language.
  • ACC * is often used for this in this language area.
  • the principle of autophoretic paint deposition is that an acidic aqueous emulsion of an organic polymer is provided. If a metal surface is brought into contact with such an emulsion, metal ions are released from the surface by the action of the acid. These combine with the polymer particles and lead to their coagulation.
  • the coagulated polymer separates as a coating on the metal surface. If the metal surface is completely covered with polymer, the process comes to a standstill.
  • the layer thicknesses obtained are generally in the range from about 15 to about 30 ⁇ m.
  • the metal parts are removed from the treatment bath and excess treatment emulsion is rinsed off with water. Reactive rinsing is often carried out, which improves the adhesion of the autophoretic paint to the metal and improves corrosion protection.
  • solutions of chromic acid and / or chromates are suitable.
  • the resin is then cured by heating to a temperature in the range from 140 to 250 ° C., preferably 150 to 180 ° C.
  • the self-depositing resins which can be used in the process according to the invention are known as such in the prior art for coating metal parts. Their corrosion protection effect has been sufficiently tested.
  • Examples of self-separating resins, such as can be used in the process according to the invention are listed in WO 93/15154. Examples include urethane resins, epoxy resins, polyester resins and resins based on different acrylates.
  • acrylate resins are those that contain one or more of the following monomers: methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-
  • Glycidyl methacrylate acrylamide, methacrylamide, acrylic acid and methacrylic acid, as well as acrylic alkyd resins.
  • These acrylates can exist as copolymers with ethylene, styrene, vinyl chloride, vinylidene chloride and vinyl acetate.
  • Epoxy-based resins which can also be used in the process according to the invention, are described, for example, in WO 97/07163. In addition to pure epoxy resins, epoxy-acrylate-based resins are also suitable. In addition to the self-depositing resin and acid, the emulsions often contain oxidizing agents and / or fluoride ions. This improves the deposition process. Examples of such process variants which can be used in the course of the process sequence according to the invention are: EP-A-32 297, EP-A-374 772, WO 93/15154 and WO 93/16813.
  • the self-separating resin is cured at a temperature in the range from 140 to 250, in particular from 150 to 180 ° C.
  • a so-called primer can now be applied to the self-separating resin.
  • Primers are usually dispersions of organic polymers in organic solvents.
  • phenolic resins, chlorinated rubber and epoxy resins can be used, which can also be used in combination with one another. Phenolic resins are preferably combined either with chlorinated rubber or with epoxy resins.
  • the primers can contain metal oxides and / or fillers as additives. After application, the primers are dried at a temperature in the range between about 20 and about 100 ° C. The dry layer layer is usually about 7 to about 10 microns.
  • aqueous primer dispersions can also be used.
  • a binder is applied to the primer layer or, if the primer has been dispensed with, to the hardened self-depositing resin.
  • binders are known in the prior art for the production of rubber-metal composites.
  • the basis of the technically customary binders is generally a mixture of halogenated polymers such as chlorinated rubber and crosslinkers. Fillers may also be present.
  • the bond between the rubber and the binder is improved if the binder additionally contains nitroso-substituted aromatics. A technically common example of this is p-dinitrosobenzene.
  • the binders are usually in the form of dispersions containing solvents. They are dried at 20 to 100 ° C, with a layer of about 10 to about 15 microns is set. Water-based binders are also available and can be used in the sequence of processes according to the invention.
  • a natural or synthetic rubber is applied to the binder.
  • This can be selected, for example, from natural rubber, styrene-butadiene rubber, ethylene, propylene, diene rubber and nitrile-butadiene rubber. All types of rubber that can be cross-linked by hot vulcanization are suitable. Examples are the rubbers NR; IR, IIR, NBR, HNBR, CR, ACM, CSM, AEM, SBR and EPDM. Preferred rubbers are: NR, TR and NBR.
  • the rubber is vulcanized at a temperature in the range of 90 to 220 ° C, preferably in the range of 120 to 190 ° C.
  • the rubber mass is preferably pressed against the substrate during the vulcanization step.
  • pressures in the range from about 50 to about 200 bar are exerted.
  • the vulcanization time depends on the type of rubber used and the size of the components. It can therefore fluctuate within wide limits and can range, for example, from about 5 to about 120 minutes.
  • vulcanization can take place at a temperature in the range between 150 and 180 ° C Duration of 10 minutes at a pressure of about 100 bar.
  • the preliminary vulcanization can be carried out for a period of time in the range from approximately 5 to approximately 15 minutes at a temperature between approximately 90 and approximately 120 ° C., and the vulcanization for a period of time in the range of approximately 10 to approximately 20 minutes at a temperature in the range between approximately 160 and about 190 ° C.
  • the invention in a second aspect, relates to a composite component made of metal and rubber, which contains a hardened layer of a self-separating resin between the metal surface and the rubber.
  • a composite component made of metal and rubber which contains a hardened layer of a self-separating resin between the metal surface and the rubber.
  • the composite components according to the invention and obtainable by the method according to the invention have the advantage that the good corrosion-protecting layer of the self-separating resin lies between metal and rubber.
  • the composite components are often designed in such a way that the entire metal surface is not covered with rubber.
  • the metal surface, which is not covered with rubber, lies however under the continuous layer of the self-separating resin and is thereby protected against corrosion.
  • the layer of self-depositing resin covers the entire metal surface regardless of whether the rubber follows or not. This avoids a point of corrosion attack where the rubber coating begins.
  • the sequence of processes according to the invention can, for example, be embedded in the following treatment sequence:
  • the dry adhesion of the rubber-metal composite was checked using a peel test in accordance with DIN 53531, Part 1. Unblasted ASTM-B bodies, ST 37, were used as test specimens.
  • the organic-based binder Chemosil R 411 was applied by dipping or the water-based binder XW 7484 by brushing in a first test series without reactive rinsing of the self-depositing resin and without using a primer.
  • the natural rubber NR 11426 and the synthetic nitrile butadiene rubber NBR 60041 were used as rubber.
  • the rubber was cured at 160 ° C under a pressure of 100 bar for 10 to 30 minutes.
  • the adhesive values were determined in daN / mm using a tear machine and the tear pattern was then assessed.
  • Table 2 shows adhesion values and crack patterns when using the autophoretic 703 acrylate-based self-separating resin, Henkel Surface Technologies. After the self-separating resin had been separated, a reactive rinse was used
  • Binders and primers are commercial products from Henkel KGaA in Düsseldorf. Test methods, comparative tests, rubber types used and vulcanization conditions as above.
  • Table 2 Rubber-metal composites on acrylate-based self-separating resin (mean values from 3 measurements each); Products and evaluation: cf. Table 1; Comparative examples: blasted sheet

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un procédé de production d'un composite caoutchouc-métal à partir d'un métal, caractérisé en ce qu'on procède aux étapes suivantes: a) on fait déposer sur le métal une résine autodéposante que l'on fait durcir; b) si désiré, on applique un primaire sur la résine; c) on applique sur ledit primaire ou sur la résine autodéposante un liant; d) on dépose sur le liant un caoutchouc naturel ou synthétique; et e) on vulcanise le caoutchouc à une température comprise dans la plage 90-220 DEG C. L'invention concerne également un composant composite pouvant être obtenu selon ledit procédé.
EP98965765A 1997-12-13 1998-12-04 Composite caoutchouc-metal Withdrawn EP1039974A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19755421A DE19755421A1 (de) 1997-12-13 1997-12-13 Gummi-Metall-Verbund
DE19755421 1997-12-13
PCT/EP1998/007904 WO1999030841A2 (fr) 1997-12-13 1998-12-04 Composite caoutchouc-metal

Publications (1)

Publication Number Publication Date
EP1039974A2 true EP1039974A2 (fr) 2000-10-04

Family

ID=7851778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98965765A Withdrawn EP1039974A2 (fr) 1997-12-13 1998-12-04 Composite caoutchouc-metal

Country Status (15)

Country Link
US (1) US6379752B1 (fr)
EP (1) EP1039974A2 (fr)
JP (1) JP4054177B2 (fr)
CN (1) CN1281403A (fr)
AU (1) AU2158499A (fr)
BR (1) BR9813518A (fr)
CA (1) CA2299195A1 (fr)
CZ (1) CZ20002183A3 (fr)
DE (1) DE19755421A1 (fr)
HR (1) HRP20000357A2 (fr)
ID (1) ID25470A (fr)
PL (1) PL341709A1 (fr)
TR (1) TR200001674T2 (fr)
WO (1) WO1999030841A2 (fr)
ZA (1) ZA9811396B (fr)

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EP1049742B1 (fr) 1998-01-27 2008-03-26 Lord Corporation Couche primaire ou revetêment aqueux
AU2339699A (en) 1998-01-27 1999-08-09 Lord Corporation Aqueous metal treatment composition
ES2226789T3 (es) 1999-01-22 2005-04-01 Lord Corporation Adhesivo autodepositable.
WO2000071337A1 (fr) * 1999-05-26 2000-11-30 Henkel Corporation Revetements appliques par depot sans courant
CA2400603A1 (fr) * 2000-02-18 2001-08-23 Henkel Kommanditgesellschaft Auf Aktien Composites en caoutchouc-metal
AU2001243166A1 (en) * 2000-02-18 2001-08-27 Penguinradio, Inc. Internet wired audio device
US6645633B2 (en) 2001-09-25 2003-11-11 Henkel Corporation Autodeposition compositions
CN101633771B (zh) 2002-07-15 2012-05-30 亨克尔两合股份公司 基于烯属不饱和单体改性的环氧乳液的耐腐蚀性膜
US7388044B2 (en) 2002-07-15 2008-06-17 Henkel Kommanditgesellschaft Auf Aktien Coatings with enhanced water-barrier and anti-corrosive properties
US20060172076A1 (en) 2002-08-30 2006-08-03 Lord Corporation Autodeposition metal dip coating process
CZ301051B6 (cs) * 2004-12-22 2009-10-21 Atotech Cz, A.S. Roztok pro úpravu kovu pred vulkanizací gumy
US20080202623A1 (en) * 2007-02-22 2008-08-28 Deangelis Alfred R Electrocoated conductive fabric
CN101420826B (zh) * 2007-10-25 2012-10-10 鸿富锦精密工业（深圳）有限公司 壳体及表面处理方法
RU2400512C1 (ru) * 2009-03-16 2010-09-27 Федеральное государственное унитарное предприятие "Научно-производственное предприятие "Прогресс" (ФГУП "НПП "Прогресс") Способ склеивания резины с металлом
CN102582160A (zh) * 2011-12-30 2012-07-18 南昌大学 发泡橡胶-金属复合密封材料及其制备方法
CN104718259B (zh) * 2012-07-25 2017-08-04 洛德公司 改良的硫化后粘结
CN102873816B (zh) * 2012-10-11 2015-02-18 金发科技股份有限公司 一体化注塑成型胶水筛选方法
PL444087A1 (pl) * 2023-03-15 2024-09-16 Firma Handlowo Usługowo Produkcyjna Blachodach Janusz I Bartosz Bochnak Spółka Jawna Pokrycie dachowe

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DE3067649D1 (en) 1979-12-12 1984-05-30 Amchem Prod An autodepositing coating composition, a process for autodepositing an organic coating on a metal surface and a metal surface when so-coated
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Also Published As

Publication number Publication date
PL341709A1 (en) 2001-04-23
ZA9811396B (en) 1999-06-14
ID25470A (id) 2000-10-05
HRP20000357A2 (en) 2001-02-28
US6379752B1 (en) 2002-04-30
WO1999030841A3 (fr) 1999-08-19
WO1999030841A2 (fr) 1999-06-24
BR9813518A (pt) 2000-10-03
JP2002512136A (ja) 2002-04-23
CA2299195A1 (fr) 1999-06-24
AU2158499A (en) 1999-07-05
TR200001674T2 (tr) 2000-12-21
DE19755421A1 (de) 1999-06-17
CZ20002183A3 (cs) 2002-01-16
JP4054177B2 (ja) 2008-02-27
CN1281403A (zh) 2001-01-24

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