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WO2008020036A1 - Procédé de fixation d'un composant sur un partenaire d'assemblage à laquer - Google Patents

Procédé de fixation d'un composant sur un partenaire d'assemblage à laquer Download PDF

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Publication number
WO2008020036A1
WO2008020036A1 PCT/EP2007/058449 EP2007058449W WO2008020036A1 WO 2008020036 A1 WO2008020036 A1 WO 2008020036A1 EP 2007058449 W EP2007058449 W EP 2007058449W WO 2008020036 A1 WO2008020036 A1 WO 2008020036A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive film
component
joining partner
adhesive
heat
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.)
Ceased
Application number
PCT/EP2007/058449
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German (de)
English (en)
Inventor
Klaus KEITE-TELGENBÜSCHER
Hans Karl Engeldinger
Anja Staiger
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.)
Tesa SE
Original Assignee
Tesa SE
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 Tesa SE filed Critical Tesa SE
Priority to DE112007001739T priority Critical patent/DE112007001739A5/de
Publication of WO2008020036A1 publication Critical patent/WO2008020036A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B11/00—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding
    • F16B11/006—Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding by gluing
    • 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
    • F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B37/00—Nuts or like thread-engaging members
    • F16B37/04—Devices for fastening nuts to surfaces, e.g. sheets, plates
    • F16B37/048—Non-releasable devices

Definitions

  • the invention relates to a method for fixing a component on a joining partner to be painted.
  • Adhesive surface is first covered by a thin film and only after removing the
  • thermosetting adhesive has the property of softening at the temperature at which the final coating of the paint applied to the body is cured, and it solidifies when the applied paint coat cools.
  • the fasteners must be kept as long on the body panel during the adhesive until the cooled adhesive has entered a strong adhesive bond. Since the curing of the adhesive in a r baking temperature of 180 0 C usually takes about 30 minutes, the holding means must remain in operation during this time.
  • EP 0 741 842 B1 fastening elements which are equipped with a layer of a hardenable reactive hot-melt adhesive by means of injection molding. Similar fasteners having a component-sintered reactive polyurethane adhesive layer are sold under the Techbond brand by Raybond (Saint-Louis, France). The adhesive application is very high here with about 900 microns thick, resulting in the squeezing of the adhesive from the adhesive joint under the pressure of the binding process. Moreover, disadvantageous in both of the aforementioned fasteners of the great effort for injection molding or sintering (in particular the equipment and tool costs), which must be driven to produce the adhesive layers. The alternatively proposed in EP 0 741 842 B1 immersion of the fasteners to be coated in a bath of molten adhesive leads to less accurate application rates and due to the adhesive flow uneven adhesive surfaces.
  • the problem with fixing with an adhesive is that the bodies are painted.
  • the bolts for example, can therefore no longer be glued to the paint after the painting because it does not provide a good primer.
  • On the other Side would be a corresponding treatment of the body after painting, for example, a partial removal of the paint, too expensive.
  • the bonding process must therefore be done before the painting process. This poses the problem that the adhesive used on the one hand survives the processes taking place during the painting and on the other hand during the
  • the adhesive must not give any components in the respective baths, because this entails contamination of the paint baths, which in turn led to a very undesirable premature replacement of the same for obvious reasons.
  • the adhesive has a sufficient initial tack, so that the desired component is immediately fixed to the substrate at least so far that the bond withstands mechanical stress until, if necessary, the adhesive reaches its final bond strength in subsequent process steps.
  • a disadvantage of the aforementioned solutions of the prior art is that the adhesive must first have largely reached its final bond strength in order to withstand the painting process. For crosslinking systems this means waiting for longer curing times before painting can begin.
  • Figure 1 provides a visual overview. After assembly, the body is cleaned of adhering contaminants such as fats, oils and dirt particles in a multi-stage degreasing and rinsing zone. During degreasing alkaline cleaners and possibly additional surfactants are usually used. The subsequent rinsing takes place with water.
  • the phosphating takes place, nowadays usually a zinc phosphating.
  • Phosphating is understood to mean the production of a sparingly soluble metal phosphate layer on the metallic base body, the substrate. Although the result is corrosion protection, this process is always associated with corrosion. By chemical processes, the acid phosphating solution becomes a necessary pickling reaction is triggered, which not only dissolves the top (almost not measurably small) metal layers, but also at the same time breaks off the last impurities.
  • the steel component is either immersed in a metal phosphate bath or sprayed in a chamber with metal phosphate solution. This forms on the surface of about 1 to 30 microns thin, firmly bonded to the base metal metal phosphate layer. These may be iron, manganese or zinc phosphate layers.
  • the metal phosphate layer serves as a primer for a paint coating and prevents sub-rusting of the paint layer. Further fields of application are phosphating for the cold forming of steel in combination with lubricants, corrosion protection in combination with corrosion inhibitors such as oils and the reduction of manganese phosphating.
  • the body In order to produce as many small crystals as possible during the formation of the layer, the body is pre-rinsed in an activating solution.
  • the polymeric titanium phosphates contained therein act as nucleation nuclei for the subsequent zinc phosphating. Since the highest demands are placed on corrosion resistance, zinc phosphating is preferred over iron phosphating.
  • the zinc phosphating baths are acidified (pH 3) and usually contain manganese, nickel and zinc phosphates as layer-forming substances as well as various additives for better process control and suppression of gas bubble formation in the pickling reaction.
  • the reaction of the phosphating solution with the base material forms a firmly adhering fine-crystalline zinc phosphate layer. The resulting sludge from reaction products must be removed from the process.
  • a multiple rinse with demineralized water and a post-passivation in which the interstices are sealed within the phosphate layer.
  • Post-passivation baths based on organic polymers or zirconium salts are available here. The only a few thousandths of a millimeter thick phosphate layer forms an ideal primer for the paint.
  • the electrophoretic painting is a dipping process in which the coating is effected by the action of an electric field (50 to 400 V).
  • the body to be painted, the electric current conducting body is introduced as an anode or cathode in the dye bath, in practice, the pool wall acts as a second Electrode.
  • the deposited amount of paint is directly proportional to the amount of electricity supplied.
  • the electrophoretic coating is used especially for priming. There are no spray losses, and the resulting coatings are very even in hard to reach places.
  • non-conductive substrates such as plastics, glass, ceramics, etc., it is used to coat the electrostatic charge of the paint particles (so-called electrostatic coating).
  • All electrodeposition paints are water-soluble (suspensions of binders and pigments in demineralised water) with only low concentrations of organic solvents (about 3%). Thus, neither fire protection nor special occupational safety measures are necessary when operating KTL systems
  • the KTL bath consists of about 80% water, 19% are binders and pigments, only about 1 to 2% are organic solvents.
  • the pH is slightly acidic and is about 6 to 6.5.
  • the deposition mechanism is divided into several stages: The water-insoluble synthetic resin becomes dispersible in water only in combination with an organic acid.
  • an alkaline boundary layer formation (pH 11 to 13) occurs due to the evolution of hydrogen. Due to the increased OH concentration on the workpiece surface, the paint dissolved in the water coagulates and deposits on the component in the form of a fine lacquer layer.
  • the bath in the tank at an average flow rate of about 0.2 m / s is moved, based on the tank contents, the bath is circulated 4 to 6 times per hour.
  • a constant control of the bath composition is required.
  • the organic acids released at the anode are separated by a dialysis system and thus the pH of the bath is kept stable. This is followed by a multi-stage rinsing zone with ultrafiltrate from the paint recovery or demineralized water.
  • the paint is baked at about 180 0 C, the layer thickness is 20 to 30 microns.
  • an additional second lacquer layer is applied as a filling layer. Only now does the actual painting with the coloring topcoat, as well as the clearcoat. When the following is the solvent-free paint, this means aqueous paints, powder coatings or powder slurries.
  • Powder coating is a coating process in which a usually electrically conductive material is coated with powder coatings.
  • the powder is sprayed electrostatically or tribostatically on the substrate to be coated and then baked. In advance, the workpiece is to be degreased well and, if necessary, treated with corrosion protection.
  • the baking temperatures depending on the application, vary widely. Typical baking conditions are between 140 and 200 ° C.
  • Various binders are used today, but typical are powder coatings based on, for example, polyurethane, epoxy or polyester resins.
  • the powder may also be applied by vortex sintering.
  • a heated workpiece is immersed briefly in a fluidized by means of compressed air powder made of plastic.
  • the surface-adherent powder melts due to the heat of the workpiece and coats the surface with a continuous plastic layer.
  • Powder clearcoats are known, for example, from DE 42 22 194 A.
  • Powder slurry coatings are powder coatings in the form of aqueous dispersions. Such slurries are described for example in US 4,268,542 A, DE 195 18 392 A, DE 196 13 547 A and DE 198 14 471 A.
  • the invention relates to a method for fixing a component on a joining partner to be painted, wherein a portion of a heat-activatable adhesive film is heated so that the adhesive film reaches a not fully crosslinked state,
  • the component is fixed to the joining partner with the section of the incompletely crosslinked heat-activatable adhesive film,
  • the first fixation of the component with the film section on the joining partner develops at least such a high holding force that the component is held with its own weight in the appropriate position.
  • This initial, incompletely crosslinked adhesive bond withstands a painting process, such as a CDP process, and does not appreciably affect the painting process or the media used therein.
  • a painting process such as a CDP process
  • the useful life of a phosphating or KLT bath is not significantly reduced.
  • the joining partner is according to a preferred embodiment of metal, more preferably it is a body of a vehicle such as watercraft, land vehicles (trucks, automobiles, etc.), aircraft, spacecraft or combinations thereof, for example, amphibious vehicles.
  • a vehicle such as watercraft, land vehicles (trucks, automobiles, etc.), aircraft, spacecraft or combinations thereof, for example, amphibious vehicles.
  • a further development of the method is in which the adhesive film is heated after fixing on the joining partner, so that it reaches a not fully crosslinked state and fixes the component on the Fügeteil, ie a method for fixing a component on a to be painted Joining partner, where
  • the component is fixed on the joining partner with a section of a heat-activatable adhesive film, At least the adhesive film is heated so that it reaches an incompletely crosslinked state and fixes the component on the adherend,
  • the joining partner is painted together with the component fixed thereon,
  • the painted joining partner is dried together with the component fixed thereto in a thermal drying, wherein the thermal energy leads to a complete crosslinking of the heat-activated adhesive film, so that the component is permanently fixed on the joining partner.
  • the adhesive film may have a thickness of up to 500 ⁇ m. According to an advantageous embodiment of the invention, this is 10 to 250 microns, especially 50 to 200 microns,
  • the heat-activatable adhesive film contains at least the following constituents: i) one or more vinylaromatic block copolymers, the total content of
  • Vinylaromatic block copolymers on the adhesive is 20% by weight to 75% by weight, preferably 30% by weight to 70% by weight, particularly preferably 40% by weight to 60%
  • one or more adhesive resins having a softening point measured by the ring and ball method (the usual standard method for determining softening methods (according to the test standard ASTM E 28)) of over 120 0 C in a proportion of 25 wt % to 70% by weight.
  • the vinylaromatic block copolymers are styrenic block copolymers, which in turn, in a particularly advantageous embodiment of the invention, are styrene-butadiene or styrene-isoprene block copolymers.
  • Thermoplastic elastomers especially those based on block copolymers are known as elastomeric component for adhesives. Especially in the production of pressure-sensitive adhesives they are used.
  • Vinylaromatic block copolymers preferably styrene block copolymers, have a very high cohesion due to their block structure and the phase separation of the soft and hard phases implied thereby. Besides They also have a high ductility, as they are used in applications
  • Styrene block copolymers alone are not tacky and can also be cured by thermal
  • Tackiness comes about only through the addition of different low molecular weight resins. It is between two types of
  • Soft block are compatible with the Styrolendblöcken, and those that are better or exclusively compatible with the Endblocks.
  • the bond strength is significantly increased by the use of high-melting resins with softening points above 120 0 C. Be only high melting
  • Adhesive resins used are often no longer tacky at room temperature.
  • the bond strengths can be achieved by skillful selection of resins that of the thermoplastic systems.
  • An advantage of the simultaneous use of vinylaromatic block copolymers is the ease of processing both from solution and from the melt.
  • Preferred adhesives are those based on block copolymers comprising polymer blocks formed by vinylaromatics (A blocks), preferably styrene, and those formed by polymerization of 1,3-dienes (B blocks), preferably butadiene and isoprene, use. Both homo- and copolymer blocks can be used according to the invention. Resulting block copolymers may contain the same or different B blocks, which may be partially, selectively or fully hydrogenated. Block copolymers may have linear A-B-A structure. It is also possible to use block copolymers of radial form as well as star-shaped and linear multiblock copolymers. As further components, A-B diblock copolymers may be present. Block copolymers of vinylaromatics and isobutylene can likewise be used according to the invention. All of the aforementioned polymers may be used alone or in admixture with each other.
  • Block copolymers having a block polystyrene content of 20 to 30% by weight have proven particularly advantageous.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • block copolymers and their hydrogenation products which utilize further polydiene-containing elastomer blocks can also be used according to the invention.
  • polystyrene resin those based on pure hydrocarbons, for example unsaturated polydienes such as natural or synthetically produced polyisoprene or
  • Polybutadiene chemically substantially saturated elastomers such as saturated ethylene-propylene copolymers, ⁇ -olefin copolymers, polyisobutylene, butyl rubber, ethylene-propylene rubber, and chemically functionalized hydrocarbons such as halogen-containing, acrylate-containing or vinyl ether-containing polyolefins are used which up to a share of up to 100 phr in relation to the
  • Vinyl aromatic block copolymer may be present.
  • tackifiers use pressure-sensitive adhesives according to the invention as the main component in particular medium-block compatible resins having a softening point above 120 0 C, measured by the ring and ball method.
  • hydrogenated and nonhydrogenated derivatives of rosin, polyterpene resins preferably based on alpha-pinene, terpene-phenolic resins, non-crosslinking phenolic resins, novolaks, hydrogenated and non-hydrogenated polymers of dicyclopentadiene, hydrogenated and non-hydrogenated polymers of preferably C 8 - and are particularly suitable Cg aromatics, hydrogenated C 5 / C 9 polymers and aromatically modified, selectively hydrogenated dicyclopentadiene derivatives.
  • the aforementioned adhesive resins can be used both alone and in admixture.
  • Tackifier resins having a softening point below 120 0 C can be used in formulations of the invention in a weight ratio of 50 wt .-%, based on the total content of midblock compatible resins may be present.
  • resins that are compatible with the vinyl aromatic blocks of the vinyl aromatic block copolymers can also be used.
  • resins based on pure aromatics such as, for example, alpha-methylstyrene, vinyltoluene or styrene or resins of mixtures of different aromatic monomers.
  • coumarone-indene resins which are obtained from the coal tar.
  • Another class of useful resins are low molecular weight polyphenylene oxides, which are particularly compatible with Styrolendblöcken in styrene block copolymers. Endblock-compatible resins can be present up to a weight fraction of 25% by weight, based on the total adhesive composition.
  • additives which may be used are typically primary antioxidants, such as sterically hindered phenols, secondary antioxidants, such as phosphites or thioethers, process stabilizers, such as C radical scavengers, light stabilizers, such as UV absorbers or hindered amines, antiozonants , Metal deactivators and processing aids, to name but a few.
  • primary antioxidants such as sterically hindered phenols
  • secondary antioxidants such as phosphites or thioethers
  • process stabilizers such as C radical scavengers
  • light stabilizers such as UV absorbers or hindered amines, antiozonants , Metal deactivators and processing aids, to name but a few.
  • Plasticizers such as plasticizer oils or low molecular weight liquid polymers, such as low molecular weight polyisobutylenes having molecular weights ⁇ 1500 g / mol (number average), or liquid EPDM types are typically used in small amounts of ⁇ 10 wt .-%. Fillers such as silica, glass (ground or in the form of spheres), aluminas, zinc oxides, calcium carbonates, calcium sulfates, titanium dioxides, carbon blacks and colored pigments, to name a few, may also be used.
  • the adhesive film can in particular be added to spheres with a metallic, ie conductive coating (for example gold or silver) or metal-containing particles.
  • the particles may be made of pure metal (gold, silver), but may also be made of an alloy which should then contain the metal to a considerable extent to ensure conductivity. If, in the following, the metallized spheres (preferably of glass) are mentioned, the person skilled in the art knows that these mentioned particles must always be read.
  • the SpacerpAME are of particular spherical geometry and consist of a hard material that does not melt at the increased bonding temperature and is difficult or not deformable.
  • the Spacerpgreg can also be conductive, but they should be harder than the metallized particles. Furthermore, they should have a smaller diameter than the conductive particles.
  • the thickness of the Spacerp corresponds approximately to the desired thickness of the adhesive layer after the pressing or bonding. They thus have a diameter which is slightly smaller than the thickness of the adhesive film. They allow a precise adjustment of this thickness by the bonding process under temperature, pressure and the plane parallelism of the plunger, even if these bonding parameters vary.
  • the spacers mentioned are preferably spherical hard particles such as glass beads. A metal layer on these spheres is possible, but not necessary, because the optionally additionally present soft metallized particles cause sufficient conductivity and thus already a conductive system is present.
  • the heat-activatable adhesive film contains at least the following constituents: i) one or more vinylaromatic block copolymers, wherein the total proportion of vinylaromatic block copolymers in the adhesive is from 20% by weight to 75% by weight, preferably from 30% by weight to 70% by weight, particularly preferably from 40% by weight to 60 Wt .-%, and ii) one or more endblock compatible resins in a proportion of 25 wt .-% to 70 wt .-%.
  • the midblock compatible resins While in tack adhesion the midblock compatible resins provide tackiness and the endblock compatible resins are used primarily to enhance cohesion and improved thermal stability, in heat activated systems the endblock compatible resins provide tackiness at elevated temperatures resulting in very high bonding performance.
  • the bond strengths can be achieved by skillful selection of resins that of the thermoplastic systems. Advantageous is the ease of processing both from solution and from the melt.
  • the heat-activatable adhesive film contains at least the following constituents: i) one or more vinylaromatic block copolymers and ii) at least one reactive resin.
  • the reactive resins used are mainly phenolic resins and alkylphenol resins.
  • the use concentration is in an advantageous embodiment at least 5 wt .-% based on the total adhesive. These resins are preferably used in a concentration of 10 to 25 wt .-%.
  • oxides or salts of polyvalent metals are used, preferably magnesium or zinc compounds, used as oxides or salts of long-chain organic acids, for example as stearates. Other salts can be used.
  • co-catalysts such as bromobutyl rubber or chlorosulfone rubber may be used, to name but a few.
  • the adhesives used may also contain the adhesive resins customary for the compounding of vinylaromatic block copolymers.
  • suitable resins for example, certain rosin, hydrocarbon and coumarone resins have been found
  • the heat-activatable adhesive film contains at least the following constituents: a.) A thermoplastic polymer in an amount of at least 30% by weight, b.) One or more tackifying resins in an amount of from 5 to 50% by weight and / or c.) epoxy resins with hardeners, optionally also accelerators, in a proportion of 5 to 40 wt .-%, d.) optionally metallized particles with a proportion of 0.1 to 40 wt .-%, particularly preferably 10 wt %, e.) optionally only difficult or non-deformable spacer particles with a proportion of 1 to 10% by weight, which do not melt at the bonding temperature of the adhesive film.
  • the elastomer preferably comes from the group of polyolefins, polyesters, polyurethanes or polyamides or may be a modified rubber such as nitrile rubber or polyvinyl butyral, polyvinyl formal, polyvinyl acetate, carboxylated or epoxylated SEBS polymer.
  • the chemical crosslinking reaction (based on epoxides or phenolic resin condensation) of the resins at elevated temperature achieves high strengths between the adhesive film and the surface to be bonded and achieves high internal strength of the product.
  • the addition of the reactive resin / hardener systems also leads to a lowering of the softening temperature of the above-mentioned polymers, which is their Processing temperature and speed advantageously lowers.
  • the suitable product is a self-adhesive product at room or slightly elevated temperatures. When the product is heated, it also reduces the viscosity in the short term, allowing the product to wet even rough surfaces.
  • the heat-activatable adhesive film contains at least the following constituents: a) an acid or acid anhydride-modified acrylonitrile-butadiene copolymer and b) an epoxy resin and / or a reactive resin, as already described above, wherein the weight ratio of the two components a / b is greater than 1.5, and wherein no additional non-polymeric hardener is used.
  • the heat-activatable adhesive film contains at least the following constituents: a) an acrylonitrile-butadiene copolymer having a weight fraction from 40 to 80% by weight, b) a polyvinyl acetal having a weight fraction from 2 to 30% by weight, c) an epoxy resin with a weight fraction of 10 to 50 wt .-% and d) a curing agent, wherein the epoxy groups are chemically crosslinked at high temperatures with the curing agent.
  • nitrile rubbers in particular all acrylonitrile-butadiene copolymers can be used with an acrylonitrile content of 15 to 50 wt .-%.
  • copolymers of acrylonitrile, butadiene and isoprene can be used.
  • the proportion of 1, 2-linked butadiene is variable.
  • the aforementioned polymers can be hydrogenated to a different degree and fully hydrogenated polymers having a double bond content of less than 1% can be used.
  • All of these nitrile rubbers are carboxylated to a certain extent; the proportion of the acid groups is preferably from 2 to 15% by weight.
  • Commercially, such systems are available, for example, under the name Nipol 1072 or Nipol NX 775 from Zeon.
  • Hydrogenated carboxylated nitrile rubbers are commercially available under the name Therban XT VP KA 8889 from Lanxess.
  • polyvinyl acetals all acetals are meant as polyvinyl derivatives, including polyvinylformal or polyvinyl butyral, with different contents of polyvinyl alcohol, and preferably polyvinyl butyrals obtained from polyvinyl alcohol.
  • polyvinyl alcohol can vary between 5 and 40 wt .-%.
  • Polyvinyl butyrals are preferred because they are much easier to get in solution. Both the nitrile rubbers and the polyvinyl butyrals can be dissolved in short-chain alcohols and ketones, such as ethanol or butanone. Butanone is preferred because the remaining components, especially the epoxy resins can be better dissolved in butanone.
  • Epoxy resins are usually understood as meaning both monomeric and oligomeric compounds having more than one epoxide group per molecule. These may be reaction products of glycidic esters or epichlorohydrin with bisphenol A or bisphenol F or mixtures of these two. It is also possible to use epoxy novolak resins obtained by reaction of epichlorohydrin with the reaction product of phenols and formaldehyde. Also, monomeric compounds having multiple epoxide end groups used as thinners for epoxy resins are useful. Also elastically modified epoxy resins can be used.
  • epoxy resins examples include Araldite TM 6010, CY-281 TM, ECN TM 1273, ECN TM 1280, MY 720, RD-2 from Ciba Geigy, DER TM 331, 732, 736, DEN TM 432 from Dow Chemicals, Epon TM 812, 825, 826, 828, 830 etc. from Shell Chemicals, HPT TM 1071, 1079 also from Shell Chemicals, Bakelite TM EPR 161, 166, 172, 191, 194 etc. from Bakelite AG.
  • aliphatic epoxy resins are, for example, vinylcyclohexane dioxides such as ERL-4206, 4221, 4201, 4289 or 0400 from Union Carbide Corp.
  • Elastified epoxy resins are available from Noveon under the name Hycar.
  • Epoxy diluents, monomeric compounds having a plurality of epoxide groups are, for example, Bakelite TM EPD KR, EPD Z8, EPD HD, EPD WF, etc. of Bakelite AG or Polypox TM R 9, R 12, R 15, R 19, R 20 etc. from UCCP ,
  • the adhesive film contains more than one epoxy resin.
  • other elastomers can also be used.
  • unmodified elastomers for example polyvinyl alcohol, polyvinyl acetate, styrene block copolymers, polyvinyl formal, polyvinyl butyral or soluble polyesters.
  • copolymers with maleic anhydride for example a copolymer of polyvinyl methyl ether and maleic anhydride, for example available under the name Gantrez TM, marketed by ISP.
  • non-hydrogenated, partially or fully hydrogenated resins based on rosin and rosin derivatives hydrogenated polymers of dicyclopentadiene, non-hydrogenated, partially, selectively or completely hydrogenated hydrocarbon resins based on C 5 -, C 5 / Cg or Cg monomer streams, polyterpene resins based on ⁇ -pinene and / or ⁇ -pinene and / or ⁇ -limonene, hydrogenated polymers of preferably pure Cs and Cg aromatics are used.
  • the aforementioned adhesive resins can be used both alone and in admixture.
  • additives can typically be used:
  • Fillers such as silica, glass (milled or in the form of spheres), aluminas, zinc oxides, calcium carbonates, titanium dioxides, carbon blacks, metal powders, etc.
  • plasticizers for example low molecular weight polyisoprenes, polybutadienes, polyisobutylenes or polyethylene glycols and polypropylene glycols can be used.
  • the adhesive does not generally escape from the adhesive joint during bonding and hot pressing. During this process, the epoxy resins crosslink with the elastomers, resulting in a three-dimensional network.
  • Accelerators can be for example: 1. Mono- and Diurons
  • Tertiary amines such as benzyldimethylamine, dimethylaminomethylphenol, tris (dimethylaminomethyl) phenol
  • the term "not completely crosslinked” means that the chemical crosslinking potential is not fully utilized during the process of heat curing, so that the adhesive film remains even softer and more elastic than a completely cured film. in which several chemical reactions are possible and of which in the state of "incomplete crosslinking" at least one is not or has not completely expired.
  • the degree of curing can be determined by a so-called DSC analysis, a differential scanning calorimetry abbreviation
  • the DSC analysis method is codified as "ISO 11 357, parts 1 to 5 of 1999".
  • the heat-activatable adhesive film used is resistant to the customary cleaning and pretreatment processes, media and conditions used in body construction, in particular to degreasing, activation, phosphating and passivation.
  • the crosslinkable adhesive film preferably has a characteristic activation temperature of at least 40 ° C., more preferably of at least 80 ° C. This prevents possible reactions already during storage or during transport.
  • Adhesive films are preferred which already at an activation temperature of not more than 130 0 C, more preferably of not more than 1 10 0 C, an initial strength of more than 1 MPa according to DIN EN 1465 (substrate: aluminum plates 100x20x1.6 mm 3 , etched, bond area 20 mm 2 , test speed 10 mm / min).
  • the activation time to achieve the initial strength is preferably less than 1 minute, more preferably less than 30 seconds, most preferably less than 10 seconds.
  • the films are not or only slightly tacky at temperatures below 60 0 C, so that the film can be easily positioned.
  • the bond strength at room temperature according to ASTM D 3330-04 is preferably less than 3 N / cm, more preferably less than 1 N / cm.
  • Strengths of more than 8 MPa are particularly advantageously achieved in the tensile shear test according to DIN EN 1465 (substrate: aluminum plates 100 ⁇ 20 ⁇ 1, 6 mm 3 , etched, bond area 20 mm 2 , test speed 10 mm / min) after curing.
  • the adhesion is in an advantageous embodiment of the adhesive film on oiled sheets. Further preferably, the adhesive sheet reaches a strength of more than 4 MPa in the tensile shear test according to DIN EN 1465 (bond area 20 mm 2 , test speed 10 mm / min) on said oiled body panels.
  • the heating of the adhesive film at the point of adhesion is carried out by any known to the expert form of heat generation and supply, in particular by heat conduction.
  • the bolt and / or the body panel are heated before and / or during the bolt with the intervening film and the
  • Body panel is pressed.
  • the required heat can also be achieved, for example
  • a post-curing of the adhesive bond by the thermal drying is advantageously carried out together with the curing of the body paint in the painting oven.
  • the cycle time during application of the fastening element (bolt) can be shortened, since it is not necessary to wait until the required final strength is reached. It is also particularly advantageous to supply the heat to the fastening element (bolt) and / or the joining partner and / or the adhesive film already during the approach of the bolt and / or the adhesive film to the bonding site in order to further shorten the cycle times.
  • the fastening element and / or the body panel is heated by induction and thus heat is conducted into the adhesive film.
  • Particularly preferred frequencies of 10 to 2000 kHz are used.
  • Corresponding devices are described in DE 196 38 521 A1 and DE 10 2004 012 786 A1.
  • the adhesive film is adapted in its geometry exactly the bonding surface by punching or otherwise shaping.
  • the adhesive film is applied to the
  • fasteners prelaminated, wherein the lamination temperature is below the crosslinking temperature. This facilitates the placement of the bolt and the adhesive film on the body.
  • the so equipped fasteners offer the great advantage that they are adhesive-free until the use of fasteners and that only by the activation of the prelaminated adhesive film at the place of use, the inherent adhesive force is released, which practically leads to a permanent connection.
  • a heat-activatable adhesive film of the following composition was produced:
  • the talc-powdered rubber granules were homogenized in a kneader together with 100 parts by weight of a mixture of equal parts of methyl ethyl ketone and toluene for 10 hours. Subsequently, the resins and the HMTA were added andußknetet.
  • the preparation of the electrodeposition paint used for test purposes can be taken, for example, from the disclosure of US Pat. No. 4,920,162 A.
  • a process according to the invention was carried out using the heat-activatable adhesive film from Example 1 in the following steps:
  • step 4 8. cooling the adhesive bond After step 4, the initial strength of the adhesive bond was tested according to DIN EN 1465 (test speed 10 mm / min). It resulted in a value of 2.3 MPa.
  • step 5 the strength of the adhesive bond according to DIN EN 1465 (test speed 10 mm / min) was also tested. It resulted in a value of 2.6 MPa.
  • step 8 the strength of the adhesive bond according to DIN EN 1465 (test speed 10 mm / min) was also tested. It gave a value of 16.2 MPa.
  • a process according to the invention was carried out using the heat-activatable adhesive film from Example 1 in the following steps:
  • Steps 2 to 4 were carried out according to Example 1. 5.
  • the test specimens were then subjected to an automotive finishing process according to Figure 1 including the pretreatment steps of degreasing, activating, phosphating, passivating and cathodic painting and curing (180 ° C., 20 minutes) by attaching them to a body shell which went through this process ,
  • step 4 the initial strength of the adhesive bond was tested according to DIN EN 1465 (test speed 10 mm / min). It gave a value of 1, 9 MPa.
  • step 5 the strength of the adhesive bond according to DIN EN 1465 (test speed 10 mm / min) was tested. It resulted in a value of 13.6 MPa.
  • steps 1 to 3 are already carried out by the manufacturer of the fastening elements and the element with the adhesive film is then cooled. The user of the fasteners then performs only the steps 4 to 10.
  • FIG. 2 shows, by way of example, four different embodiments of adhesive components.
  • FIG. 3 shows a fastening element (2) which is adhesively bonded to a joining partner (3) by means of a heat-activatable adhesive film (1).

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un procédé de fixation d'un composant sur un partenaire d'assemblage (3) à laquer, une section d'une feuille adhésive (1) activable par la chaleur étant chauffée de sorte que la feuille adhésive atteint un état non entièrement réticulé, le composant (2) étant fixé avec la section de la feuille adhésive activable par la chaleur, non entièrement réticulée, sur le partenaire d'assemblage, le partenaire d'assemblage conjointement avec le composant fixé sur celui-ci étant laqué, le partenaire d'assemblage laqué étant séché conjointement avec le composant fixé sur celui-ci lors d'un séchage thermique, l'énergie thermique entraînant une réticulation complète de la feuille adhésive activable par la chaleur, de sorte que le composant est fixé durablement sur le partenaire d'assemblage.
PCT/EP2007/058449 2006-08-17 2007-08-15 Procédé de fixation d'un composant sur un partenaire d'assemblage à laquer Ceased WO2008020036A1 (fr)

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DE112007001739T DE112007001739A5 (de) 2006-08-17 2007-08-15 Verfahren zur Fixierung eines Bauteils auf einem zu lackierenden Fügepartner

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DE200610038624 DE102006038624A1 (de) 2006-08-17 2006-08-17 Verfahren zur Fixierung eines Bauteils auf einem zu lackierenden Fügepartner
DE102006038624.8 2006-08-17

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WO2009123777A1 (fr) * 2008-03-31 2009-10-08 Illinois Tool Works Inc. Ensemble d’écrou-cage
WO2011036008A3 (fr) * 2009-09-23 2011-05-26 Newfrey Llc Procédé de réunion, accessoire de réunion et élément de fixation
WO2011134618A1 (fr) * 2010-04-30 2011-11-03 Volkswagen Aktiengesellschaft Structure de carrosserie d'un véhicule automobile présentant un profil de support en forme de t, procédé de fabrication de la structure de carrosserie et carrosserie ou élément de carrosserie
DE102012213511A1 (de) * 2012-07-31 2014-02-06 Aktiebolaget Skf Verfahren zum Montieren eines ersten Maschinenteils in ein zweites Maschinenteil
CN101965231B (zh) * 2008-02-29 2014-05-14 艾格斯特韦斯蒂格钢铁厂有限公司 制备刮水器的弹簧条的方法
WO2016096177A1 (fr) * 2014-12-18 2016-06-23 Newfrey Llc Composant de jonction et son procédé de production
DE102015010577A1 (de) * 2015-08-12 2017-02-16 GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) Verfahren zur Herstellung eines Karosserie-Rohbaues
DE102016102232A1 (de) 2016-02-10 2017-08-10 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Vorrichtung und Verfahren zum Befestigen eines Funktionselements
EP3330334A1 (fr) * 2016-11-30 2018-06-06 Newfrey LLC Procédé d'assemblage et élément de fixation
WO2025132879A1 (fr) 2023-12-22 2025-06-26 Tesa Se Procédé de fermeture permanente de trous avec protection contre des surpressions et élément adhésif pour le procédé

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DE102008061812A1 (de) * 2008-12-11 2010-06-24 Twb Presswerk Gmbh & Co. Kg Verfahren zum Herstellen eines Blechstrukturteiles
AT512705A1 (de) 2012-03-21 2013-10-15 Mark Metallwarenfabrik Gmbh Halteelement

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FR2542829A1 (fr) 1983-03-15 1984-09-21 Itw De France Attache pour la fixation de pieces sur un support
DE8712151U1 (de) 1987-09-08 1987-10-29 Chemo Fotochemische Druck Gmbh, 5600 Wuppertal Halterung für Karosserieverkleidungsteile
US5277737A (en) * 1990-12-24 1994-01-11 Ford Motor Company Dielectric curing of adhesives
DE4222194A1 (de) 1992-07-07 1994-01-13 Basf Lacke & Farben Verfahren zur Herstellung einer zweischichtigen Lackierung und für dieses Verfahren geeignete Pulverlacke
EP0741842A1 (fr) 1994-01-28 1996-11-13 A. Raymond & Cie Element de fixation collable pour maintenir des elements structuraux ou fonctionnels sur des supports
DE19613547A1 (de) 1995-04-10 1996-11-07 Basf Lacke & Farben Wäßrige Pulverklarlack-Dispersion
DE19638521A1 (de) 1996-09-20 1998-03-26 Raymond A & Cie Vorrichtung zum automatisierten Setzen von Haltebolzen auf Trägerflächen
DE10017783A1 (de) * 2000-04-10 2001-10-11 Henkel Kgaa Schlagfeste Epoxidharz-Zusammensetzungen
DE102004016712A1 (de) * 2003-04-07 2004-11-18 General Motors Corp. (N.D.Ges.D. Staates Delaware), Detroit Mit Klebstoff verkapseltes Blindnietsystem
US20040112531A1 (en) * 2003-05-14 2004-06-17 L&L Products, Inc. Method of adhering members and an assembly formed thereby
EP1541610A1 (fr) * 2003-12-09 2005-06-15 Henkel Kommanditgesellschaft auf Aktien Adhésif à deux composants pour son utilisation dans la construction de vehicules
EP1568749A1 (fr) * 2004-02-25 2005-08-31 Sika Technology AG Adhesif a deux composants pour la production de materiaux semi-finis et de composites sandwich
DE102004012786A1 (de) 2004-03-15 2005-09-29 Newfrey Llc, Newark Fügevorrichtung zum Befestigen von kleinteiligen Bauelementen an einer Trägerfläche durch Kleben
EP1772635A2 (fr) * 2005-10-04 2007-04-11 Böllhoff Verbindungstechnik GmbH Raccord et procédure de sa fixation sur une surface

Cited By (19)

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Publication number Priority date Publication date Assignee Title
CN101965231B (zh) * 2008-02-29 2014-05-14 艾格斯特韦斯蒂格钢铁厂有限公司 制备刮水器的弹簧条的方法
WO2009123777A1 (fr) * 2008-03-31 2009-10-08 Illinois Tool Works Inc. Ensemble d’écrou-cage
US8029221B2 (en) 2008-03-31 2011-10-04 Illinois Tool Works, Inc. Cage nut assembly
US8741081B2 (en) 2009-09-23 2014-06-03 Newfrey Llc Joining method, joining appliance and fastening element
CN102666761B (zh) * 2009-09-23 2015-06-03 纽弗雷公司 连接方法、连接器具和固定元件
JP2013505343A (ja) * 2009-09-23 2013-02-14 ニューフレイ リミテッド ライアビリティ カンパニー 接合方法、接合器具及び締結要素
KR101741861B1 (ko) * 2009-09-23 2017-05-30 뉴프리 엘엘씨 접합 방법, 접합 기구 및 체결 요소
CN102666761A (zh) * 2009-09-23 2012-09-12 纽弗雷公司 连接方法、连接器具和固定元件
WO2011036008A3 (fr) * 2009-09-23 2011-05-26 Newfrey Llc Procédé de réunion, accessoire de réunion et élément de fixation
WO2011134618A1 (fr) * 2010-04-30 2011-11-03 Volkswagen Aktiengesellschaft Structure de carrosserie d'un véhicule automobile présentant un profil de support en forme de t, procédé de fabrication de la structure de carrosserie et carrosserie ou élément de carrosserie
DE102012213511B4 (de) 2012-07-31 2017-02-23 Aktiebolaget Skf Verfahren zum Montieren eines ersten Maschinenteils in ein zweites Maschinenteil
DE102012213511A1 (de) * 2012-07-31 2014-02-06 Aktiebolaget Skf Verfahren zum Montieren eines ersten Maschinenteils in ein zweites Maschinenteil
US9925610B2 (en) 2012-07-31 2018-03-27 Aktiebolaget Skf Method for installing a first machine part into a second machine part
WO2016096177A1 (fr) * 2014-12-18 2016-06-23 Newfrey Llc Composant de jonction et son procédé de production
JP2018507357A (ja) * 2014-12-18 2018-03-15 ニューフレイ リミテッド ライアビリティ カンパニー 接合構成要素及びその製造方法
DE102015010577A1 (de) * 2015-08-12 2017-02-16 GM Global Technology Operations LLC (n. d. Ges. d. Staates Delaware) Verfahren zur Herstellung eines Karosserie-Rohbaues
DE102016102232A1 (de) 2016-02-10 2017-08-10 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Vorrichtung und Verfahren zum Befestigen eines Funktionselements
EP3330334A1 (fr) * 2016-11-30 2018-06-06 Newfrey LLC Procédé d'assemblage et élément de fixation
WO2025132879A1 (fr) 2023-12-22 2025-06-26 Tesa Se Procédé de fermeture permanente de trous avec protection contre des surpressions et élément adhésif pour le procédé

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