EP2513243A2 - Collage de repli de bordage - Google Patents

Collage de repli de bordage

Info

Publication number
EP2513243A2
EP2513243A2 EP10795366A EP10795366A EP2513243A2 EP 2513243 A2 EP2513243 A2 EP 2513243A2 EP 10795366 A EP10795366 A EP 10795366A EP 10795366 A EP10795366 A EP 10795366A EP 2513243 A2 EP2513243 A2 EP 2513243A2
Authority
EP
European Patent Office
Prior art keywords
group
metallic particles
adhesive
composition
thermosetting epoxy
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Withdrawn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
EP10795366A
Other languages
German (de)
English (en)
Inventor
Michael Gutgsell
Jan Olaf Schulenburg
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
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 Sika Technology AG filed Critical Sika Technology AG
Priority to EP10795366A priority Critical patent/EP2513243A2/fr
Publication of EP2513243A2 publication Critical patent/EP2513243A2/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Withdrawn legal-status Critical Current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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D27/00—Connections between superstructure or understructure sub-units
    • B62D27/02—Connections between superstructure or understructure sub-units rigid
    • B62D27/026—Connections by glue bonding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/14—Sealings between relatively-stationary surfaces by means of granular or plastic material, or fluid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin

Definitions

  • the invention relates to the field of Bördelfalzverklebache.
  • Edge banding bonds have long been used in industrial production. It is known means of transport, such as doors,
  • Trunk bonnets, rear panel flaps produce engine compartment hoods and the like from an outer panel and an inner panel by means of hinge connection.
  • an adhesive is used, which connects the inner panel with the outer panel.
  • adhesives for edgebanding bonds must have the shortest possible crosslinking times. For example, as an adhesive
  • thermosetting adhesives use, wherein the heat input in industrial manufacturing typically indirectly via the heating of the
  • Object of the present invention is therefore, adhesives for
  • thermosetting epoxy composition containing an average of metallic particles
  • At least one hardener B for epoxy resins which increased by
  • Temperature is activated; such as
  • thermosetting epoxy composition contains at least one
  • Epoxy resin A with an average of more than one epoxide group per molecule.
  • the epoxide group is preferably present as a glycidyl ether group.
  • Epoxy resin A having on average more than one epoxide group per molecule is preferably an epoxy liquid resin or a solid epoxy resin.
  • the term "solid epoxy resin” is well known to the person skilled in the art and is used in contrast to "liquid epoxy resins”. The glass transition temperature of solid resins is above room temperature, i. they join
  • Preferred solid epoxy resins have the formula (X)
  • substituents R 'and R "independently of one another are either H or CH 3 .
  • the index s stands for a value of> 1 .5, in particular from 2 to 12.
  • Such solid epoxy resins are commercially available, for example, from Dow or Huntsman or Hexion.
  • epoxy resins in the narrower sense, i. where the index s has a value of> 1 .5.
  • Preferred liquid epoxy resins have the formula (XI)
  • the substituents R '"and R""independently of one another are either H or CH 3.
  • the index r stands for a value from 0 to 1.
  • r stands for a value of less than 0.2.
  • DGEBA diglycidyl ethers of bisphenol A
  • bisphenol F bisphenol F
  • bisphenol A F bisphenol A F
  • 'A / F' refers to a mixture of acetone with formaldehyde, which is used as starting material in its preparation becomes
  • liquid resins Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER TM 331 or DER TM 330 (Dow) or Epikote 828 (Hexion).
  • the epoxy resin A is an epoxy liquid resin of formula (XI).
  • the thermosetting epoxy composition contains both at least one epoxy liquid resin of formula (XI) and at least one solid epoxy resin of formula (X).
  • the proportion of epoxy resin A is preferably 5 to 85% by weight, in particular 10 to 70% by weight, preferably 10 to 60% by weight, based on the weight of the thermosetting epoxy composition.
  • thermosetting epoxy composition further contains at least one curing agent B for epoxy resins, which is activated by elevated temperature. It is preferably a curing agent which is selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and derivatives thereof.
  • substituted ureas such as, for example, 3-chloro-4-methylphenylurea (chlorotoluron), or phenyldimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1 , 1-dimethylurea (fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron) or non-aromatic-substituted ureas.
  • substituted ureas such as, for example, 3-chloro-4-methylphenylurea (chlorotoluron), or phenyldimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1 , 1-dimethylurea (fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron) or
  • Hardener B is preferably a hardener which is selected from the group consisting of dicyandiamide, guanamine, guanidines, aminoguanidines, substituted ureas, imidazoles and amine complexes, and derivatives thereof.
  • hardener B in conjunction with
  • the total amount of hardener B is 0.5 to 12% by weight.
  • thermosetting epoxy composition thermosetting epoxy composition.
  • thermosetting epoxy composition further contains metallic particles having an average particle size of 50 - 3000 ⁇ .
  • metal particles in the present document means particles containing metal or metal alloys.
  • the metallic particles have an average particle size of 100 to 1000 ⁇ , in particular from 200 to 400 ⁇ on.
  • the metallic particles have such properties
  • Distribution of the particle size to that more than 70, preferably more than 80% of the metallic particles not more than 50%, preferably not more than 30% differ from the average particle size.
  • a typical measurement method for determining the particle size is a determination based on a sieve analysis according to DIN 66165.
  • composition of the metallic particles has a hardness measured according to the hardness test method Vickers DIN ISO 6507: 2005 of less than 120 HV 1, preferably less than 50 HV 1, particularly preferably less than 30 HV 1.
  • Typical values for the hardness HV 1 for metals are, for example: aluminum 17 HV 1, copper 37 HV 1, tin 6 HV 1, zinc 40 HV 1, chrome 100 HV 1, iron 60 HV 1, nickel 64 HV 1, and lead 5 HV 1.
  • Epoxy composition as an adhesive for Bördelfalzverklebitch advantageous. Since adhesives are pressed in crimp seam bonds, the metallic particles are due to a previously mentioned hardness with the applied pressing force to the intended layer thickness for the adhesive layer brought. As the metallic particles are preferably larger
  • Diameter than the adhesive layer thickness leads to a hardness mentioned that the metallic particles are on both sides in contact with the outer sheet, respectively the inner sheet after pressing.
  • the metallic particles are pressed under the applied pressure, respectively, are pressed to the intended adhesive layer thickness, so the metallic particles do not withstand the pressure during compression and plastically deform.
  • a significant proportion of the surface of the metallic particles in the pressed state with the outer panel, resp. the inner panel, in contact is to be understood as meaning more than 15%, preferably 25-80%, in particular 50-75%, of the surface of the metallic particles.
  • the skilled person is clear that between metallic particles in the pressed state and inner plate and / or outer plate may be a very thin layer of
  • Adhesive binder can be located.
  • the composition of the metallic particles preferably has a thermal conductivity of greater than 10 W / (m-K), preferably greater than 50 W / (m-K), particularly preferably greater than 100 W / (m-K).
  • Typical thermal conductivities for metals are, for example: aluminum 200 W / (mK), copper 380 W / (mK), tin 65 W / (mK), zinc 1 10 W / (mK), chromium 95 W / (mK), iron 80 W / (mK), nickel 85 W / (mK), and lead 35 W / (mK).
  • thermal conductivity is understood to mean the thermal conductivity at 23 ° C.
  • the composition of the metallic particles contains a metal selected from the list consisting of aluminum, copper, tin, zinc, chromium, iron, nickel and lead.
  • the composition of the metallic particles consists of a metal selected from the list mentioned above or consists of a metal Alloy comprising one of the metals selected from the list mentioned above.
  • the metal particles in the case of induction heating, can continue to have a positive effect on the curing behavior due to electrical or induction-related effects.
  • the metallic particles can be designed differently.
  • the metallic particles may, for example, be platy, ribbon-like,
  • thermosetting epoxy composition has spacers in a particularly preferred embodiment. As a spacer, in the present document a body is understood which holds two bodies at a distance from each other when the spacer is located between these two bodies.
  • the spacer can be designed differently. Very different materials and shapes of spacers can be used. Particularly preferred are such spacers which have the most uniform expansion thicknesses possible. Furthermore, preference is given to spacers of this type which have no tips which are perpendicular to the inner panel and / or outer panel, because the sheet could deform due to the small contact surface of the outer panel and / or the inner panel at the high compression pressure, so that the position the spacer on can sign off the outer panel, which is optically often unacceptable. Particularly preferred are balls and cubes as spacers.
  • the spacers have in particular a spherical shape, preferably a spherical shape. Most preferred are spherical spacers.
  • the spacers can be hollow or filled. Hollow spacers are often preferred for weight reasons.
  • the wall thickness of such hollow spacers depends on the mechanical properties of the wall material, in particular its compressive strength. Examples of such hollow spacers are hollow glass spheres and ceramic hollow spheres.
  • the spacers can be made of different materials. In particular, it is of great advantage for the present method if the spacer is pressure-stable and as hard as possible.
  • composition of the spacer advantageously has a hardness measured by hardness test method Vickers DIN ISO 6507: 2005 of greater than 200 HV 1, preferably greater than 400 HV 1, in particular greater than 600 HV 1 on.
  • the spacer resists the pressure during the pressing.
  • the spacer is therefore in particular made of glass, ceramic, aluminum oxide, silicon dioxide, zirconium oxide, nitride, in particular boron nitride, or carbide, in particular silicon carbide.
  • Size distribution in particular via a monomodal size distribution, i. that all spacers are approximately the same size.
  • the spacer is made of glass or ceramic.
  • the proportion of the spacer is preferably selected such that the volume fraction of the spacer is not more than 10% by volume, in particular between 0.1 and 4% by volume, preferably between 0.5 and 3% by volume, based on the total volume of the thermosetting epoxy composition.
  • the spacers advantageously have a particle size of less than 1 mm. It is particularly advantageous if the metallic particles have an average particle size which is 10 -500%, preferably 150-400%, of the average particle size of the spacers.
  • the thermosetting epoxy resin composition further contains at least one toughener D.
  • Supplements of 0.1-50 wt .-%, in particular from 0.5 to 40 wt .-%, causes a significant increase in toughness and thus is able to absorb higher bending, tensile, impact or impact stress before the matrix enters or breaks.
  • the toughener D can be a solid or a liquid
  • Toughener especially a liquid toughener.
  • the toughener D is a
  • Such liquid rubbers are, for example, under the name Hypro®, formerly Hycar®, CTBN and CTBNX and ETBN of
  • Nanoresins AG Germany commercially available.
  • epoxy-containing elastomer-modified polymers such as those under the product line Polydis®, preferably from the product line Polydis® 36, the company Struktol® (Schill + Seilacher Group, Germany) or under the product line Albipox (Nanoresins, Germany) are commercially available, suitable.
  • this toughener D is a polyacrylate liquid rubber which is completely miscible with liquid epoxy resins and does not adhere until the epoxy resin matrix cures
  • this toughener D is a polyether amide terminated with carboxyl groups or epoxide groups.
  • Such polyamides are in particular produced from the reaction of amino-terminated polyethylene ethers or polypropylene ethers, as described in US Pat
  • Example be marketed under the name Jeffamine® by Huntsman, with dicarboxylic anhydride subsequent reaction with epoxy resins, as described in Example 15 in conjunction with Example 13 of DE 2123033. Hydroxybenzoic acid or hydroxybenzoates may be used instead of dicarboxylic acid anhydride.
  • Toughener D is a terminally blocked polyurethane prepolymer of formula (I).
  • R 1 is a p-valent radical of an isocyanate-terminated linear or branched polyurethane prepolymer PU1 after removal of the terminal isocyanate groups and p is from 2 to 8.
  • R 2 is independently a substituent which is selected from the group consisting of
  • R 5 , R 6 , R 7 and R 8 are each independently an alkyl or cycloalkyl or aralkyl or arylalkyl group, or R 5 forms together with R 6 , or R 7 together with R 8 , a part of a 4- to 7-membered ring, which is possibly substituted.
  • R 9 and R 10 are each independently an alkyl or aralkyl or arylalkyl group or an alkyloxy or aryloxy or aralkyloxy group and R 11 is an alkyl group.
  • R 12 , R 13 and R 14 each independently represent a
  • R 15 , R 16 and R 17 are each independently H or an alkyl group, or an aryl group or an aralkyl group, and R 18 is an aralkyl group or a mono- or polynuclear substituted or unsubstituted aromatic group which optionally has aromatic hydroxyl groups having.
  • R 4 is a radical of a primary or secondary hydroxyl-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxide and
  • Epoxide groups and m for a value of 1, 2 or 3.
  • the terminally blocked polyurethane prepolymer of the formula (I) has 8 radicals R 2 which are different from one another.
  • R 18 are in particular on the one hand phenols or polyphenols, especially bisphenols, to consider after removal of a hydroxyl group.
  • Preferred examples of such phenols and bisphenols are, in particular, phenol, cresol, resorcinol, pyrocatechol, cardanol (3-penta-decenylphenol (from cashew nut shell oil)), nonylphenol, phenols reacted with styrene or dicyclopentadiene, bisphenol A, bis Phenol-F and 2,2'-diallyl-bisphenol-A.
  • R 18 in particular, hydroxybenzyl alcohol and benzyl alcohol are considered after removal of a hydroxyl group.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 9 ' , R 10 , R 11 , R 15 , R 16 or R 17 is an alkyl group, this is in particular a linear or branched d- C2o-alkyl group.
  • Aralkyl group this group is in particular an aromatic group bound via methylene, in particular a benzyl group.
  • R 5, R 6, R 7, R 8, R 9, R 9 'or R 10 is an alkylaryl group, this is particularly a group bonded through phenylene d- to C2o-alkyl group, such as a tolyl or xylyl group ,
  • radicals R 2 are preferably the substituents of the formulas
  • Preferred substituents of the formula are monophenols or polyphenols, in particular bisphenols, after removal of a phenolic hydrogen atom.
  • Particularly preferred examples of such radicals R 2 are radicals which are selected from the group consisting of
  • the radical Y in this case represents a saturated or olefinically unsaturated hydrocarbon radical having 1 to 20 C atoms, in particular having 1 to 15 C atoms.
  • Y in particular allyl, methyl, nonyl, dodecyl or an unsaturated Ci 5 alkyl radical having 1 to 3 double bonds are preferred.
  • R 2 is , which is from the
  • reaction can be carried out sequentially or with a mixture of these compounds.
  • the monohydroxyl epoxy compound of the formula (V) has 1, 2 or 3
  • the hydroxyl group of this monohydroxyl epoxy compound (V) may be a primary or a secondary hydroxyl group.
  • Such monohydroxyl epoxy compounds can be produced, for example, by reacting polyols with epichlorohydrin. Depending on
  • hydroxyl-containing epoxides examples include butanediol monoglycidyl ethers (contained in butanediol diglycidyl ether), hexanediol monoglycidyl ether (contained in hexanediol diglycidyl ether), cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl ether (contained in trimethylolpropane triglycidyl ether mixture), glycerol diglycidyl ether (contained as a mixture in US Pat
  • Glycerol triglycidyl ether pentaerythritol triglycidyl ether (as a mixture contained in pentaerythritol tetraglycidyl ether).
  • pentaerythritol triglycidyl ether as a mixture contained in pentaerythritol tetraglycidyl ether.
  • trimethylolpropane diglycidyl ether which occurs in a relatively high proportion in commonly prepared Trimethylolpropantriglycidylether used.
  • hydroxyl-containing epoxides in particular glycidol, 3-glycidyloxybenzyl alcohol or hydroxymethylcyclohexene oxide.
  • distillation residues which are obtained in the production of high purity, distilled epoxy liquid resins. Such distillation residues have an up to three times higher concentration of hydroxyl-containing epoxides than commercially available undistilled epoxide
  • Liquid resins a wide variety of epoxides with a ß-hydroxy ether group, prepared by the reaction of (poly) epoxides with a deficit of monovalent nucleophiles such as carboxylic acids, phenols, thiols or sec-amines, can be used.
  • monovalent nucleophiles such as carboxylic acids, phenols, thiols or sec-amines
  • the radical R 4 is in particular vorzu t a trivalent radical of the formula
  • R is methyl or H.
  • the free primary or secondary OH functionality of the monohydroxyl epoxy compound of the formula (V) permits efficient reaction terminal isocyanate groups of prepolymers, without having to use disproportionate excesses of the epoxy component.
  • terminally blocked polyurethane prepolymer of the formula (I) is advantageously between 1 and 50% by weight, in particular between 3 and 40% by weight, based on the total weight of the thermosetting
  • the thermosetting epoxy composition is preferably highly viscous, that is, it has a viscosity of more than 900 Pas, in particular more than 1000 Pas, at 25 ° C.
  • the viscosity at 25 ° C has a value between 1000 Pas and 4000 Pas.
  • the viscosity is measured by oscillography using a rheometer with heatable plate (MCR 201, Anton Paar company) (gap 1000 ⁇ , measuring plate diameter: 25 mm (plate / plate), deformation 0.01 at 5 Hz, temperature: 25 ° C), certainly.
  • thermosetting one-part epoxy resin adhesives as described in U.S. Pat
  • SikaPower® product line are commercially available from Sika Automotive GmbH.
  • Another aspect of the invention relates to a method for producing a Bördelfalzverklebung. This includes at least the steps
  • thermosetting epoxy composition as mentioned above, on an inner panel or on a thermosetting epoxy composition
  • thermosetting epoxy composition b) contacting the thermosetting epoxy composition with the outer panel or the inner panel; c) flanging the outer sheet around the inner sheet, so that in the interior of the crimp fold heat-curing epoxy composition is present;
  • thermosetting epoxy composition e
  • thermosetting epoxy composition is applied in a first step (a) of the inventive method to an inner panel or an outer panel. This is done advantageously at a
  • thermosetting epoxy composition of 23 ° C to 80 ° C, in particular from 23 ° C and 60 ° C, preferably from 50 to 60 ° C.
  • thermosetting epoxy composition The order of the thermosetting epoxy composition, im
  • adhesive typically takes place in the edge area of the outer panel.
  • the amount and exact application point of the adhesive is such that after the compression of the crimp fold described below, it is filled as completely as possible with adhesive.
  • the order is preferably carried out automatically and preferably in the form of an adhesive caterpillar.
  • the adhesive is then contacted with the outer panel or the inner panel.
  • the inner plate and the outer plate are in contact with the adhesive.
  • a third step (c) of the method according to the invention the outer panel is crimped around the inner panel, so that adhesive is present in the interior of the fold thus formed.
  • a fourth step (d) of the method according to the invention the crimp fold is then pressed.
  • the thickness of the spacer is influenced in particular above all by the thickness of the flanging fold to be achieved, and thus in particular by the thickness of the outer panel, also referred to in this document as "d z .”
  • the ratio of the thickness (d y ) of the spacer to The thickness (d z ) of the outer sheet has a value of 0.05-0.70
  • spacers of the thickness of in particular 0.08 to 0.4 mm are used 0.2 mm and outer plates of thickness 0.5 to 1.2 mm
  • the thickness of the inner plates is preferably selected in the same thickness range as the outer plate.
  • the inner plate and outer plate in principle, all the plates known by the expert are suitable.
  • these are those sheet materials which are already used for edge banding in transport construction or in the production of white goods.
  • Preferred sheets are steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel, Bonazink-coated steel, and subsequently phosphated steel, as well as aluminum in particular in the variants typically occurring in the car industry.
  • the crimping and pressing takes place with tools known to the person skilled in the art.
  • thermal energy is introduced into the adhesive.
  • the feeding of the thermal energy causes the crosslinking of the adhesive in thermosetting adhesives, or accelerates the crosslinking of the adhesive, so that a sufficiently high strength of Bördelfalzverklebung is achieved as quickly as possible.
  • a step f) of crosslinking of the adhesive follows.
  • the thermal energy is in particular about heating in one
  • Furnace via infrared radiation or induction heating, preferably via induction heating, introduced into the adhesive.
  • the adhesive is heated to a temperature of 100-220 ° C., preferably 120-200 ° C.
  • the final cross-linking can also take place in the cathodic rotary kiln.
  • Another aspect of the invention relates to a Bördelfalzverklebung, which is prepared by the method described above.
  • the invention relates to the use of the method described above for the production of Bordelfalzverklebitch in the production of means of transport, especially of automobiles, buses, trucks, rail vehicles, ships or aircraft, or white goods, especially washing machines, tumblers or dishwashers.
  • Such articles or hem flange adhesive-bonded bodies are in particular means of transport, in particular an automobile, bus, truck, rail vehicle. vehicle, a ship or an aircraft, or a white goods, in particular a washing machine, tumbler or dishwasher.
  • Fig. 1 a-e is a schematic cross-sectional view of the production of a
  • Fig. 1 a application of an adhesive on the outer panel
  • Fig. 1 e Beading of the outer panel and pressing the Bördelfalzes Fig. 1 e introducing thermal energy and crosslinking of the adhesive Fig. 2a cross-section through an inventive adhesive
  • FIGS. 1 a to 1 e show diagrammatically different intermediate stages in a possible method for producing a
  • the non-inventive adhesive 4 '(without metallic particles) can be used without spacers 6, as shown in FIG. 1 a, or with spacers, as shown in FIGS. 1 b to 1 e.
  • the outer panel 2 already has a deformation of the in this illustration
  • the spacers 5 are in the figures 1 b to 1 e balls.
  • Figure 1 c shows schematically how the non-inventive adhesive 4 'is contacted with the inner panel 3. In this presentation, the
  • Inner sheet 3 from above on the non-inventive adhesive 4 'occupied outer sheet 2 moves out and it is under slight pressure contact between inner sheet 3 and non-inventive adhesive 4'.
  • FIG. 1d shows the result of crimping the outer sheet 2 about the inner sheet 3 with subsequent pressing of the crimp fold 1 to an adhesive layer thickness d x , which corresponds to the thickness d y of the spacer 6.
  • FIG. 1d shows the intermediate stage after these two process steps.
  • Figure 1 e shows the step of introducing thermal energy ( ⁇ ) in the non-inventive adhesive 4 '. This is done by
  • the thermal energy can be done for example by an IR emitter, oven or H alone Kunststoffflash.
  • Outer sheet 2 transfers the heat to the non-inventive adhesive 4 ', which then crosslinked under heat.
  • an all-round effect of heat around the hem flange to achieve a rapid uniform hardening of the adhesive 4 ' would be achieved.
  • FIG. 2a shows a cross-section through an adhesive 4 according to the invention, which is a thermosetting epoxy composition as described in the section "Methods of Carrying Out the Invention". described is.
  • the term "adhesive according to the invention” is therefore to be understood as meaning a use according to the invention.
  • FIG. 2b shows the introduction of thermal energy and crosslinking of an adhesive according to the invention, wherein FIG
  • the adhesive layer thickness d x is less than the diameter of the metallic particles 5 prior to compression, the compression process leads to a contact on both sides of the metallic particles with the outer panel, respectively the inner panel, with deformation of the metallic particle 5. Due to the higher thermal conductivity of the metallic particles the corresponding adhesive without metallic particles is a faster heat input compared to a non-inventive adhesive that has no metallic particles or only metallic particles whose diameter is smaller than the adhesive layer thickness d x .
  • Figures 3a, 3b and 3c show the same facts as Figures 2a to 2c, wherein the adhesive composition additionally
  • Spacer having the thickness d y .
  • This is advantageous in that thereby the adhesive layer thickness d x can be adjusted over the thickness of the spacer 6 d y , whereby the additional heat input of the metallic particles can be controlled better over a controlled adhesive layer thickness d x .
  • SikaPower®-492 is a thermosetting epoxy resin adhesive commercially available from Sika Automotive GmbH containing one
  • Toughening agent of the formula (I) This has at 25 ° C a viscosity of about 2700 Pas and at 50 ° C of about 1000 Pas.
  • Glass beads (Sigmund Lindner GmbH, Germany) of diameter 0.1-0.11 mm, 0.25-0.3 mm, or 1 .2 mm were also added to the adhesive with stirring. The added amount of glass beads was 2% by volume based on the
  • This comparative adhesive was designated VK1.
  • An adhesive K1 according to the invention was also prepared by adding to SikaPower®-492 aluminum particles (Ecka Aluminum AS 91) with a diameter smaller than 0.315 mm and glass beads (Sigmund Lindner GmbH, Germany) of diameter 0.1-0.1 1 mm, 0.25-0.3 mm , or 1 .2 mm was added with stirring. The amount added
  • Glass beads was 2% by volume, the added amount of aluminum particles was 9% by weight based on the final composition.
  • the substrate used on the one hand was electrolytically galvanized sheet steel (DC-04) with a thickness of 0.8 mm (also referred to below as sheet for short), which was previously cleaned using heptane.
  • DC-04 electrolytically galvanized sheet steel
  • 0.8 mm also referred to below as sheet for short
  • a plastic test piece made of glass fiber reinforced plastic having a thickness of 2.4 mm (hereinafter also referred to simply as GFR) was used, which was used without prior purification.
  • the respective adhesive was at 50 ° C on an adhesive surface of 25 x 10 mm on an electrolytically galvanized steel sheet, respectively.
  • the tensile shear strength (ZSF) of the specimens was according to DIN EN
  • the adhesive K1 according to the invention contains, in the composition with glass spheres of 0.1 mm diameter, metallic particles which have a larger particle diameter, in this case up to 300% larger particle diameter, than the glass spheres used as spacers.
  • the metallic aluminum particles are therefore due to the pressing on both sides with a significant proportion of the surface in contact with the sheet and thereby lead to an additional

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Transportation (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne l'utilisation d'une composition époxy thermodurcissable contenant : au moins une résine époxy A comprenant en moyenne plus d'un groupe époxyde par molécule; au moins un agent durcissant B pour résines époxy, qui est activé sous l'effet des hautes températures; et des particules métalliques ayant une granulométrie moyenne de 50 - 3000 μm, ladite composition étant employée en tant qu'adhésif dans des collages de replis de bordage. L'invention se caractérise par une pénétration efficace de la chaleur dans l'adhésif du collage de repli de bordage.
EP10795366A 2009-12-18 2010-12-17 Collage de repli de bordage Withdrawn EP2513243A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10795366A EP2513243A2 (fr) 2009-12-18 2010-12-17 Collage de repli de bordage

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09179931A EP2336262A1 (fr) 2009-12-18 2009-12-18 Adhesion par sertissage au pli
PCT/EP2010/070147 WO2011073422A2 (fr) 2009-12-18 2010-12-17 Collage de repli de bordage
EP10795366A EP2513243A2 (fr) 2009-12-18 2010-12-17 Collage de repli de bordage

Publications (1)

Publication Number Publication Date
EP2513243A2 true EP2513243A2 (fr) 2012-10-24

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ID=42286654

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Application Number Title Priority Date Filing Date
EP09179931A Withdrawn EP2336262A1 (fr) 2009-12-18 2009-12-18 Adhesion par sertissage au pli
EP10795366A Withdrawn EP2513243A2 (fr) 2009-12-18 2010-12-17 Collage de repli de bordage

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Application Number Title Priority Date Filing Date
EP09179931A Withdrawn EP2336262A1 (fr) 2009-12-18 2009-12-18 Adhesion par sertissage au pli

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EP (2) EP2336262A1 (fr)
WO (1) WO2011073422A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013108517A1 (de) * 2013-08-07 2015-02-12 Thyssenkrupp Steel Europe Ag Verfahren zum Verbinden zweier Bleche für ein Fahrzeug
DE102013019050B4 (de) * 2013-11-15 2021-06-02 Adient Luxembourg Holding S.À R.L. Fügeverfahren und Bauteilanordnung
DE102015219234A1 (de) * 2015-10-06 2017-04-06 Continental Automotive Gmbh Dichtmasse und Verwendung einer solchen, Gehäuse und Verfahren zur Herstellung eines solchen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2123033A1 (de) 1971-02-11 1972-08-24 Du Pont Epoxy haltige Polymermasse
US4749833A (en) * 1987-08-07 1988-06-07 Tocco, Inc. Induction heating for adhesive bonding
DE700337T1 (de) * 1993-05-25 1996-10-10 Lord Corp., Erie, Pa. Methode zum erreichen einer mechanischen verbindung zwischen oberflächen
WO2001023466A1 (fr) * 1999-09-27 2001-04-05 Georgia Tech Research Corp. Adhesif electroconducteur contenant du polyurethanne modifie en epoxy
EP1935955A1 (fr) 2006-12-21 2008-06-25 Sika Technology AG Méthode pour coller la feuillure de bord ouverte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011073422A2 *

Also Published As

Publication number Publication date
EP2336262A1 (fr) 2011-06-22
WO2011073422A2 (fr) 2011-06-23
WO2011073422A3 (fr) 2011-08-11

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