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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C33/00—Moulds or cores; Details thereof or accessories therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
  • B60J1/00—Windows; Windscreens; Accessories therefor
  • B60J1/004—Mounting of windows
  • B60J1/006—Mounting of windows characterised by fixation means such as clips, adhesive, etc.
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
  • B60J10/00—Sealing arrangements
  • B60J10/70—Sealing arrangements specially adapted for windows or windscreens
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—Polyurethanes from polyesters
• • 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
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
  • C08G2170/20—Compositions for hot melt adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2250/00—Compositions for preparing crystalline polymers
• • 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
  • C09J2475/00—Presence of polyurethane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24777—Edge feature
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/2874—Adhesive compositions including aldehyde or ketone condensation polymer [e.g., urea formaldehyde polymer, melamine formaldehyde polymer, etc.]

Definitions

• the invention relates to - a heat-activatable modular component as described in claims 1 to 23; - The use of the modular component according to the invention for the direct glazing of vehicles, in particular automobiles, as described in claim 24; - A method for the direct glazing of vehicles, in particular automobiles, as described in claims 25 to 51; and an adhesive as defined in claims 52 to 54.
• EP-B1-0 345 134, EP-B1-0 312 496 and EP-B1-0 351 369 already known prefabricated vehicle windows for direct glazing by gluing into a frame, flange or the like, which have along their edge a first trough-shaped profiled adhesive strand, which is elastic, but not plastically deformable, and with one second, optionally covered and / or activated by a protective cover and / or activatable partial adhesive strand made of a material which is chemically compatible with the first partial adhesive strand.
• Such prefabricated vehicle windows can be used as a ready-to-assemble component for gluing in vehicle bodies without the use of an additional assembly adhesive.
• the preparation of the vehicle window takes place at different times and locations from the actual installation of the window.
• the pane can be prepared ready for assembly as an autonomous component in an optimized environment, with an ideal timing and under the best conditions, so that the protective cover only has to be removed and / or the second sub-strand of adhesive has to be activated immediately before assembly.
• Oxidatively curing adhesive substances These must be stored in the absence of air or oxygen and therefore require a protective film or protective cover.
• hot melts are solid at room temperature and become pasty when heated to a certain temperature, which is generally above 150 ° C. Covering with a protective film or protective cover is not absolutely necessary here, except possibly for protection against dirt or mechanical damage. In order to achieve sufficient thermal stability, such products for the automotive industry must have a softening point of more than 120 ° C. Such non-reactive adhesives are not used in structural engineering and for the bonding of safety parts.
• thermosetting adhesive substances These differ from the thermoplastic adhesive substances mentioned under (c) in that they cure irreversibly at a certain critical temperature T k . Therefore, when the second sub-strand of adhesive is applied to the first sub-strand of adhesive, they can only be heated up to a first transition temperature T l below the critical temperature T k . While such products are available, they are either sensitive to moisture and require a cover sheet, or they must be kept at the curing temperature until fully cured.
• these systems can be set to a suitable open time. Covering with a protective film or protective cover is not absolutely necessary here either. However, these systems are very slow in curing and require a long fixation after installation.
• cover sheets or protective covers are problematic in two respects. First, it is difficult to seal these covers from the trough-shaped strand, especially in the curved areas. Second, the cover material is unwanted waste that must be collected and recycled.
• Table 1 shows typical guide values for the most important properties of some of the materials mentioned in the publications mentioned.
• cycle times are required that are far below the cycle times that can be achieved with the substance groups mentioned.
• cycle times of less than 50 s are required, within which such a module is to be made adhesive and installed.
• the Mon days without the usual aids such as intermediate parts or spacers, adhesive tapes, etc., which were previously used to prevent slipping.
• the object of the invention was to create a storable, heat-activated modular component and a method for gluing a modular component to another component, in particular for direct glazing of vehicles, which meet these requirements.
• a profiled adhesive strand made of a latently reactive adhesive along its edge, which predominantly comprises: one or more polyurethanes with blocked isocyanate
• reaction can be initiated at an activation temperature of 70 to 180 ° C, and which at the same time remains sticky and non-flowing but plastically deformable for a time sufficient for assembly.
• the inventive method for direct glazing of vehicles according to the preamble of claim 24 is characterized in that: - a professional along the edge of the modular component
• Adhesive which mainly comprises:
• polyurethane precursors which consist of polyols and / or polyamines and encapsulated polyisocyanates;
• the other component brings the other component together, presses it to a predetermined joining distance, and if necessary, quickly fixes the part of the adhesive that is not yet activated to initiate the reaction to the activation temperature of 70 to 180 ° C and the composite at least until the adhesive solidifies and then allows it to fully react without further action ; with the proviso that the difference between the application temperature and the activation temperature of the adhesive is at least 20 ° C.
• the adhesive can be reacted along its contact surface with the modular component already after the application of the adhesive bead by the action of heat.
• the latently reactive adhesives to be used according to the invention contain one or more polyurethane prepolymers with blocked isocyanate groups or free-radically polymerizable groups or polyols, polyamines and encapsulated polyisocyanates, in which at least one of the components of the adhesive is crystallizing and the mixture predominantly between 25 and 80 ° C, preferably between 35 and 60 ° C, melts.
• a mixture of non-crystallizing polyurethane prepolymers and crystallizing polyurethane prepolymers or a mixture of non-crystallizing and crystallizing polymeric polyols is used in combination with polyamines and encapsulated isocyanates.
• the two types of polyurethane prepolymers can also be combined in a copolymer with crystallizing and non-crystallizing molecular parts.
• the crystallizing components that can be used are, for example, the reaction products of diisocyanates with crystallizing polyether polyols, such as polytetrahydrofuran, polyethylene glycol, with crystallizing polycarbonate polyols, such as those obtainable by reacting 1,4-butanediol with diaryl carbonates, for example diphenyl carbonate or phosgene.
• crystallizing components are the polyester polyols, e.g. Polycaprolactone or butanediol adipic acid hexanediol polycondensates or polyester amide polyols, e.g. are obtainable by reaction of a carbonyl-terminated polyamide oligomer with hydroxyl-terminated polyethylene terephthalate oligimers, or the reaction products of the polyols mentioned with diisocyanates.
• polyester polyols e.g. Polycaprolactone or butanediol adipic acid hexanediol polycondensates
• polyester amide polyols e.g. are obtainable by reaction of a carbonyl-terminated polyamide oligomer with hydroxyl-terminated polyethylene terephthalate oligimers, or the reaction products of the polyols mentioned with diisocyanates.
• non-reactive substances such as solid plasticizers, for example stearates or hydrogenated castor oil or its derivatives, can also be used as crystallizing components. be used.
• thermoplastics are ethylene-acrylate copolymers, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers and thermoplastic polyurethanes.
• reaction products of diisocyanates with short-chain diols are to be mentioned, which form hard segments.
• H-active compounds can be used as protective groups for blocking the isocyanate groups of the prepolymers which are below the decomposition temperature of the
• Oximes, phenols and lactams are particularly suitable.
• Organometallic catalysts such as dibutyltin dilaurate (DBTL), metal salts and organic acids or tertiary amines such as triethylenediamine are suitable.
• DBTL dibutyltin dilaurate
• metal salts organic acids
• tertiary amines such as triethylenediamine
• amine catalysts in the form of their salts with organic acids.
• the adhesives according to the invention can additionally contain low molecular weight polyfunctional compounds, such as polyols, for example trimethylolpropane or polyamines, for example diethyltoluenediamine, for partial pre-crosslinking of the hot adhesives during the
• latent amine hardeners such as dicyandiamide
• Phthalic anhydride-amine adducts methylene dianiline salt complexes or other latent hardeners, as are known to the person skilled in the art, can be used.
• polyurethane precursors whose polyisocyanates are low-molecular-weight solid compounds which are protected by a shell of urea and cannot react with the H-active compounds at room temperature.
• Macromolecular polyols and / or polyamines and optionally additionally low molecular weight diols and / or aromatic diamines are preferably used as chain extenders as H-active compounds.
• Amine end groups can be used in combination with the protected polyisocyanates.
• the isocyanates are preferably protected with aliphatic primary or secondary amines, such as e.g. the
• Suitable solid polyisocyanates are, for example, dimeric 4,4'-diisocyanato-diphenylmethane, 3,3'-diisocyanato-4,4'-dimethyl-N, N'-diphenylurea, trimeric isophorone diisocyanate or 1,4-phenylene diisocyanate.
• H-active compounds are used, so it's through
• latently reactive adhesives is based on polyurethanes, the chain ends of which have radical-polymerizable groups.
• groups are preferably acrylate or methacrylate groups, such as, for example, by reacting isocyanate-functional prepolymers with OH-functional acrylates or methacrylates, for example 2-hydroxyethyl acrylate or 3-hydroxypropyl acrylate, or by converting OH or NH-functional prepolymers can be obtained with isocyanato acrylates or methacrylates.
• the adhesives are reacted along the contact surface with the carrier module when the adhesive bead is applied or before the module is joined by the action of heat.
• the duration and intensity of the heat is chosen so that the thickness of the cured layer is less than the intended minimum thickness of the adhesive joint to be formed after joining.
• the cured layer formed in this way is preferably not significantly thinner, since the remaining part of the adhesive which is still to be cured after joining is thus minimal. In this case, curing after the installation is possible by conducting heat from the hot joining partner, even with thick adhesive joints.
• the materials mentioned are soft and sticky even at temperatures above 35 ° C. and are therefore suitable for joining. At the same time, they are essentially solid at room temperature and do not deform when touched.
• Preferred materials are already pumpable at a temperature T p of 50 to 60 ° C and have a first transition temperature T l of 40 to 50 ° C.
• their activation and the initiation of crosslinking take place at a temperature T k of 80 ° C., so that a quick and unproblematic activation is possible.
• the materials mentioned can be pumped from the storage container to the application device, for example a nozzle or a doctor blade, without the activation starting and without them noticeably aging.
• the materials mentioned return quickly after application to a state in which they are dry and touchable. This enables rapid clocked production of pre-coated modules.
• the materials mentioned can be heated up to the activation temperature without losing their shape.
• the activation and, if necessary, partial crosslinking can be initiated within 2 minutes, preferably within 1 minute, in a particularly preferred embodiment even within 30 seconds, and curing continues beyond assembly. Such short activation and reaction times are particularly given when polyurethane precursors are used in connection with encapsulated solid polyisocyanates.
• the adhesive is brought into a plastic form. During the installation and the subsequent fixation, the adhesive solidifies again so that the pane sits firmly without installation aids, without slipping or springing back.
• the materials mentioned can be activated by supplying electrical, electromagnetic or magnetic energy while softening at the same time without causing local overheating.
• - In a preferred embodiment using blocked isocyanate prepolymers or encapsulated
• Isocyanates have enough of the materials mentioned active isocyanate groups in order to anchor themselves on the substrates to be bonded, in particular on a painted substrate, and to establish an aging-stable connection.
• the adhesive is activated only along its contact surface with its carrier.
• any form of heat can be used to activate the glass module according to the invention.
• Heating in conventional convection ovens is not suitable to achieve rapid integral heating of the latent reactive adhesive.
• the glass itself and any edge edging are also heated to the same extent, which, in the event that immediate adhesion after assembly is achieved by cooling and crystallization of the adhesive, prevents rapid adhesion after assembly without additional fastening.
• air with a temperature below the activation temperature is suitable for melting the remaining adhesive.
• infrared radiation is very suitable for activating the base of the adhesive along its surface to the carrier.
• the modular component is irradiated from the back. This is particularly advantageous in the case of glass modules, where the heat radiation penetrates the glass practically unhindered and heats the adhesive from its contact or interface with the glass. Even if between
• a modification of this method is to use a beam-expanded, relatively long-wave laser, e.g. To use Nd-YAG laser, which moves the contact surface to the glass from the back of the glass.
• Heating with infrared radiation, especially with bright radiation, is also only suitable for activating the adhesive after the installation or joining of the modular component according to the invention, even if it has not yet hardened on its contact surface with the carrier. This is particularly the case if it is a glass module, and the method is particularly effective if the joining partner consists of a poorly heat-conducting material, in particular plastic.
• magnetic induction offers itself as a heating source.
• This energy source is already used in the automotive industry for the direct heating of double-shell steel parts, such as doors or bonnets, when gluing reinforcing parts to the outer shell.
• the adhesive is only indirectly heated by heat conduction over the steel parts. If the adhesive itself is to be heated, it must contain magnetizable and / or electrically conductive fillers which give off their heat to the matrix. A good
• Preferred fillers are magnetizable iron oxides, e.g. Ferrites, magnetites, gamma-iron oxides, which are available on the market in very fine grain sizes. Even with relatively small proportions by weight of less than 15 percent by weight, these allow heating to 150 ° C. in less than 30 s. In principle, however, it is also possible to use only electrically conductive fillers, such as iron powder or steel fibers.
• radio frequency (HF) or radio frequency (RF) field in the range from 1 to 300 MHz, one is limited to the internationally specified frequencies for industrial applications (see Table 2).
• HF radio frequency
• RF radio frequency
• special shielding of the radiation area from the surroundings may be necessary.
• the dipoles of the adhesive molecules are directly excited to rotate, and the corresponding dielectric losses heat the matrix.
• the adhesive is brought into the interior of the alternating electromagnetic field, which is built up between two electrodes adapted to the shape of the adhesive strand. With this method it is also possible to heat the adhesive bead up to 150 ° C in less than 30 seconds.
• the permissible wavebands are listed in Table 2.
• the energy is fed from a transmitter via a waveguide into a resonance resonant circuit spanned across the cross section of the adhesive strand.
• the resonant circuit must match the mass of the
• Adhesive strands are coordinated so that there are no standing waves to ensure uniform heating of the bead over the entire module surface.
• the microwave energy in the electromagnetic range from 0.3 to 5 GHz also acts directly on the macromolecules of the adhesive through dipole excitation and dielectric losses. It is also possible to accelerate the heating by conductive fillers such as carbon black or polar fillers. With this technology, a temperature of over 150 ° C can be reached in 30 seconds. This technique requires careful ab shield the work area from the outside, since microwave radiation is dangerous for the human organism. In order to better control the heating in the microwave field, it can be helpful to introduce the energy in a pulsating manner.
• Another suitable form of energy for rapid, mass-effective heating to activate the hot melt adhesive is to connect the conductive bead of adhesive to one
• Conductive fillers are known to increase the conductivity of organic materials by several orders of magnitude. Conductive fillers such as carbon black, graphite, metal flakes etc. are often used for this. Particularly suitable for the present
• Invention are fibrous conductive fillers, such as steel fibers, which can increase the conductivity by up to a factor of 10 5 . This makes it possible, by admixing such fillers, to produce products in the range from 5 to 10 percent by weight, which heat up to 150 ° C. in less than 30 seconds when the module is connected to a mains voltage power source.
• the coating which is normally applied directly to the glass via the edge zone and is used for optical masking or to protect the bead of adhesive, contains pigments which also release heat, such as metal oxides, under the influence of the heating methods mentioned above .
• a primer containing such pigments, for example soot can also be used.
• conductive covers can also protect against undesired heating.
• the adhesive strand is not activated in its entirety before assembly, but only along its contact surface with the glass, up to a layer thickness which is less than the desired or minimum layer thickness of the adhesive after the joining.
• the part of the adhesive that is not yet activated, which is in contact with the joining partner is activated after the joining.
• This can be done in that the named inactive part of the adhesive is heated above the activation temperature by direct heat, for example by hot air.
• this method is less suitable if the joining partner is highly thermally conductive and has a large mass. In this case it can be very difficult to activate the interface to the joining partner and to achieve a permanent adhesive bond with it.
• a preferred method is to heat the joining partner at its contact point with the adhesive, so that the adhesive is heated and activated by heat conduction from the joining partner. If the joining partner as a whole or over the area of its joining zone has sufficient heat capacity to heat the remaining, still inactive adhesive mass above the activation temperature, it is possible to heat the joining partner to a sufficient temperature above the activation temperature before joining. In this case, however, care must be taken to remain sufficiently below the decomposition temperature of the adhesive.
• inductive heating via a magnetic induction field in the range of 1 to 1000 kHz is an extremely fast heating method. This method is particularly well suited for the installation of components, in particular of permanently glazed windows in vehicle bodies.
• the flange is heated through the glass shortly before assembly or immediately after installation of the pane using an inductor loop running parallel to the flange.
• the Energy supply regulated via a closed control loop so that the temperature remains sufficiently below the decomposition temperature of the adhesive or the lacquer.
• Metallic joining partners can also be heated using electrical resistance heating, radiant heat or heat conduction.
• Non-metallic joining partners e.g. Plastics can be heated well using infrared radiation, hot air or heat conduction. In this case, however, it is also possible to directly heat the adhesive and, if appropriate, the joining partner by applying a high-frequency field over the area of the entire adhesive joint. Alternatively, it is also possible to work with a high-frequency magnetic field, the adhesive having to contain electrically conductive or magnetizable fillers.
• the method according to the invention is particularly advantageous for use in vehicle assembly, since it allows components which are transportable and ready to be glued to be manufactured under optimum production conditions and which only require heat activation in order to enable quick assembly and a practically immediately loadable adhesive bond.
• Table 3 lists possible and particularly preferred process variants, as made possible by the present invention. Based on the direct glazing of a car with glass modules according to the invention, table 4 shows two embodiments with typical cycle times.
• Example 6 In a 2 liter glass reactor, 2000.0 grams of the isocyanate prepolymer from Example 1 were heated to 70 to 80 ° C. while stirring in a stream of nitrogen. Thereafter, 82.1 grams of the blocking agent p-hydroxybenzoate were added to the prepolymer in countercurrent nitrogen. The reaction mixture was then heated at this temperature for 5 hours until the NCO absorption band in the infrared spectrum (2250 cm -1 ) had completely disappeared. After the mixture cooled to room temperature, the product was kept in a closed container. Example 6
• Example 8 In a 2 liter glass reactor, 2000.0 grams of the isocyanate prepolymer from Example 1 were heated to 70 ° C. with stirring and under a stream of nitrogen. Then 70.3 grams of the blocking agent epsilon-caprolactam were added. The reaction was then heated at 80 ° C. for 3 hours until the NCO absorption band had completely disappeared in the IR spectrum. After cooling to room temperature, the blocked prepolymer was kept in a closed container.
• Example 8 Example 8
• Example 16 300 g of the epsilon-caprolactam-blocked prepolymer from Example 7 were heated to 50 ° C. in a 1 liter reactor. After the prepolymer had been degassed for 1/2 hour, 7 grams of 4,4'-diaminodicyclohexylmethane were added and the mixture was evacuated for a further 15 minutes. The product was then filled into cartridges for storage.
• Example 16
• Example 10 The adhesive from Example 10 was applied from a cartridge preheated to 60 ° C. in the form of an adhesive bead to the glass coated with primer. The caterpillar was then allowed to cool to room temperature. This again became firm and non-sticky.
• the adhesive bead of the adhesive from Example 10 applied to the glass was stored at room temperature and normal atmospheric humidity for 1 month. There was no noticeable change in the consistency of the bead of adhesive during this storage.
• Diethylenetriamine stirred at room temperature. Then 25 parts by weight of the powdered IPDI trimers T1890 are dispersed in for 1 hour. Then 18 parts by weight of Jeffamin T5000 and 4 parts by weight of DETDA are added. After further stirring for 30 minutes, 10 parts by weight of carbon black and 15 parts by weight of calcium carbonate as a filler and 0.05 parts by weight parts of DBTL weighed as a catalyst. The mixture is degassed for 30 minutes and filled into cartridges for storage.
• the adhesive bead applied to the glass and stored at room temperature was heated in a convection oven preheated to 150 ° C. for 10 minutes. After this time the temperature in the adhesive bead was 140 ° C. The bead of adhesive was then allowed to cool again. After 6 hours the adhesive was cross-linked.
• Example 10 In a laboratory planetary mixer, 325 grams of the blocked prepolymer from Example 10 were mixed with 25 grams of carbon black and 150 grams of fillers for 1 hour at 50 ° C. under vacuum. The product was filled into an aluminum cartridge. From this product, a 13 cm long triangular bead was applied to a glass plate. The adhesive bead was irradiated with microwaves in a microwave oven for 40 s at 1000 W power. The bead temperature was measured with a fiber optic temperature measuring device and recorded with a flatbed recorder. After this microwave treatment, 130 ° C. were measured in the adhesive bead.
• Example 10 In a laboratory planetary mixer, 325 grams of the blocked prepolymer from Example 10 were mixed with 25 grams of carbon black and 150 grams of fillers for 1 hour at 50 ° C. under vacuum. The product was filled into an aluminum cartridge. The adhesive was applied to a glass substrate (25x100x4 mm). The sample was treated in an HF system (27 MHz) for 30 s with a power of 100 W / gram of adhesive. The temperature in the adhesive was measured with a fiber optic temperature measuring device and recorded with a flatbed recorder. After 30 seconds, a temperature of 140 ° C. was measured in the adhesive.
• Example 10 In a laboratory planetary mixer, 323 grams of the blocked prepolymer from Example 10 were mixed with 25 grams of filler and 150 grams of ferrite powder (ferrite cores N27 ground) under vacuum at 50 ° C. for 1 hour. The product was filled into an aluminum cartridge. From this product a 5 cm long triangular bead was applied to a glass plate. The glass plate with the triangular bead was brought into the center of an induction coil with a 60 mm diameter, which was connected to an induction generator of 3 kW power. The frequency of this device was approximately 200 kHz. The performance of the system was controlled by a microprocessor. The temperature profile was measured with a thermocouple and recorded with a flatbed recorder.
• ferrite powder ferrite cores N27 ground
• the adhesive-glass module was joined using a perforated panel (hole size 50x20 mm) and a suitable device with a painted trigger body (steel, 40x10x56 mm) in such a way that a glass-metal bond of 40x10x4 mm originated.
• the swollen material was removed with a 2 mm wide angled spatula.
• the sample was then exposed to a magnetic induction field from the glass side by means of an induction coil for 10 seconds.
• the adhesive was cured after the power source was turned off. After conditioning for 24 hours at 23 ° C. and 50% relative humidity on a tensile testing machine with a pretension of 10 N, it was pulled to a rate of 400 mm / minute. A maximum force of 4.5 MPa was measured and a cohesive fracture pattern was found within the adhesive bead.
• a triangular bead of the product of Example 19 was placed on a glass plate.
• the glass plate with the triangular bead was irradiated from below with a short-wave infrared source. After 20 seconds, a temperature of 100 ° C. was measured at the base of the adhesive bead. After this time, the base of the adhesive bead was hardened to a depth of approximately 1.5 mm, while the upper part of the adhesive bead was soft and not cross-linked. About 10 seconds after the infrared heating source was switched off, the adhesive was overlapped with a steel so that a tensile shear test specimen with an overlap width of 10 mm and a layer thickness of 3 mm was produced.
• the swelling material was removed with a 2 mm wide angled spatula. This was the sample exposed to a magnetic induction field from the glass side by means of an induction coil for 7 seconds. After the power source was turned off, all of the adhesive was cured. After storage for 24 hours at 23 ° C. and 50% relative air humidity, the determination of the tensile shear strength gave a value of 3.5 MPa with a cohesive fracture pattern within the bead of adhesive.
• a triangular bead of the product of Example 23 was placed on a glass plate.
• the glass plate with the triangular bead was irradiated from below with a short-wave infrared source. After 30 seconds, a temperature of 130 ° C. was measured at the base of the adhesive bead. After this time the adhesive bead was hardened to a depth of about 1 mm at the base, while the upper part of the adhesive bead was soft and not cross-linked. About 10 seconds after the infrared heating source was switched off, the adhesive was joined with a steel substrate in such a way that a tensile shear test specimen with an overlap width of 10 mm and a layer thickness of 3 mm was produced. The swollen material was removed with a 2 mm wide angled spatula. The sample was then exposed to a magnetic induction field for 7 seconds from the glass side using an induction coil. To the adhesive was cured when the power source was turned off.
• Example 29 The experiment from Example 29 was repeated, but without irradiation with the infrared source. After heating for 15 seconds by means of magnetic induction from the glass side, a temperature of 170 ° C. was measured on the steel side. After switching off the power source, the adhesive on the steel side was hardened. There was a layer of uncured material on the glass side.
• Example 33 The experiment from Example 29 was repeated with the difference that the induction heating was carried out using a power control which limited the temperature at the adhesive surface to the steel to 120 ° C. After 15 seconds the adhesive was completely hardened.
• Example 33
• Example 32 The experiment of Example 32 was repeated, but without previous exposure to infrared radiation. It took 3 minutes for the adhesive to harden completely.

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• 1994
  • 1994-02-10 BR BR9404200A patent/BR9404200A/pt not_active Application Discontinuation
  • 1994-02-10 US US08/318,702 patent/US6926949B1/en not_active Expired - Fee Related
  • 1994-02-10 EP EP94905641A patent/EP0638099A1/de not_active Ceased
  • 1994-02-10 CA CA002117915A patent/CA2117915A1/en not_active Abandoned
  • 1994-02-10 AU AU59682/94A patent/AU678209B2/en not_active Ceased
  • 1994-02-10 WO PCT/CH1994/000027 patent/WO1994018255A1/de not_active Application Discontinuation
  • 1994-02-10 KR KR1019940703605A patent/KR100311969B1/ko not_active IP Right Cessation
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