EP1480813A1 - Method for producing and treating epoxide resin moulding materials - Google Patents

Method for producing and treating epoxide resin moulding materials

Info

Publication number
EP1480813A1
EP1480813A1 EP03708109A EP03708109A EP1480813A1 EP 1480813 A1 EP1480813 A1 EP 1480813A1 EP 03708109 A EP03708109 A EP 03708109A EP 03708109 A EP03708109 A EP 03708109A EP 1480813 A1 EP1480813 A1 EP 1480813A1
Authority
EP
European Patent Office
Prior art keywords
mixer
molding
molding compositions
production
components
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
EP03708109A
Other languages
German (de)
French (fr)
Inventor
Heinz-Gunter Reichwein
Michael Schwab
Jens Steinmann
Thomas Dressen
Gunda Panik
Frank Bayerl
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.)
Hexion GmbH
Original Assignee
Bakelite 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 Bakelite AG filed Critical Bakelite AG
Publication of EP1480813A1 publication Critical patent/EP1480813A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether

Definitions

  • the invention relates to a new process for the production and processing of molding compositions based on epoxy resins.
  • Epoxy resin molding compounds are granules made of epoxy resin, hardener as well as fillers and additives that can be processed into thermally curable molded parts without the addition of an additive.
  • the molded articles produced in this way are distinguished by good mechanical and electrical properties.
  • the other fillers and additives are mixed into a liquid mixture of epoxy resin and hardener. At a moderately elevated temperature, the epoxy resins are allowed to prereact until the mass is tack-free and free-flowing at room temperature. Despite good wetting of the fillers, this process has the disadvantage that the setting of the pre-reaction is not exactly reproducible, so that the corresponding molding compositions differ in their reactivity from batch to batch. In addition, these molding compositions are not stable in storage.
  • the object is achieved by a process for the production and processing of epoxy resin molding compositions according to claims 1 to 7.
  • the molding compositions produced by the process are particularly suitable for the production of molded parts in the reaction injection molding process, for the encapsulation of electronic or electrical components or component components and for the production of mechatronic components, as claimed in claims 8 to 10.
  • the solution is achieved by mixing all the constituents of the molding composition together in a high-speed mixer and processing them into loose, free-flowing granules.
  • the direct further use of this granulate as a molding composition for the production of molded parts in the known manner by pressing in a mold does not lead to high-quality moldings, since the homogenization is not sufficient.
  • the granules have the property of forming a flowable mass under pressure.
  • This is used according to the invention in that the granules are homogenized under pressure shortly before shaping and hardening.
  • the granules which are not yet sufficiently homogeneous, are pressed under pressure and, if appropriate, with heating by a continuous mixer upstream of the molding tool, shortly before it is fed to the molding tool, and homogenized in the process.
  • this also works with molding compositions whose filler content is up to 95% by weight, based on the total composition.
  • the granulate is produced very quickly and easily.
  • the granules are storable and do not clump together in normal storage, but remain free-flowing. Only when using pressures> 5 bar, such as those that occur when passing through transport devices such as extruder screws or piston pumps, are these mixtures plasticized and can be homogenized in continuous mixers.
  • the homogeneous molding compound obtained is then injected directly into the mold. It is a further advantage of the method according to the invention that both the mixing machines and the device components, such as the devices and continuous mixers required for pressure generation, are common machines in the plastics processing industry and can be connected upstream of a molding tool in a simple manner. The previously customary production of shaped bodies is not significantly changed by this.
  • the structure of the epoxy resin molding compositions produced in accordance with the invention essentially corresponds to the epoxy resin molding compositions which have been customary to date.
  • epoxy resins with at least two epoxy groups per molecule whose melting range is below 70 ° C.
  • Preferred are epoxy compounds which are liquid at room temperature, such as diglycidyl ether from Bisphenols or pre-extended resins based on bisphenol A diglycidyl ethers.
  • Low-viscosity resins such as epoxy resins based on cycloolefins or tetraglycidyldianiline, or else mixtures of solid epoxy resins, such as, for example, epoxidized novolaks with what are known as reactive diluents, are particularly preferred.
  • the epoxy resins can optionally be modified with other polymers such as polyesters, acrylates, silicone polymers or polyvinyl derivatives.
  • latent hardeners are used as hardeners, such as, for example, alkyl-substituted aromatic amines, polycarboxylic acids and anhydrides, BC1 3 or BF 3 complexes, latent hetero compounds based on nitrogen or phosphorus or metal complex compounds.
  • latent hardeners are also microencapsulated hardeners. Hardeners which, in free form, lead to curing of the epoxy resins at room temperature, such as aliphatic or aromatic amines or polyamines, novolaks or imidazole derivatives, are encapsulated with an inert material.
  • the capsule walls are destroyed either by the thermal energy introduced or by the shear forces occurring during the homogenization, and the hardener is released and homogenized with the rest of the molding compound mixture.
  • the amount of hardener used is chosen in a manner known per se so that it is sufficient for the epoxy compounds to be fully cured.
  • All inorganic and / or organic fillers customary for such molding compositions with the grain sizes usually used can be used as fillers.
  • Examples are hydrophobized or untreated chalk, dolomite, precipitated or ground silica, wollastonite, mica, talc, silicates, clays, titanium dioxide, lithopone, aluminum oxide hydrate, antimony trioxide but also cellulose or polyamide powder.
  • fibers in particular short fibers with an average length of 0.5 to 4 mm, can also be used as particularly reinforcing fillers.
  • fibers are glass, ceramic, aramid, cellulose, polyester, polyamide or C fibers.
  • the amount of fillers used is up to 95% by weight, preferably up to 85% by weight, based on the total molding composition.
  • additives such as lubricants or release agents such as waxes, metal soaps or substituted fatty acid amides, pigments, flexibilizers, coupling reagents, accelerators or flame retardants can also be mixed into the epoxy resin molding materials prepared according to the invention in amounts which are customary per se.
  • the mixing process takes place in a mixer with rapidly rotating mixing tools, e.g. a multi-shaft dissolver, a fluidized bed, turbo internal or high performance centrifugal mixer. Preference is given to high-speed mixers in which there is the possibility of also tempering the mix so that the temperature rise resulting from the energy input is limited so that the temperature of the mixture can be kept below the starting point of the curing reaction of the epoxy resin. If necessary, a cooling mixer can be installed downstream of the mixer. Within a short mixing time, if vortex or high-performance centrifugal mixers are used within a mixing time of less than one minute, the not yet homogeneous molding compound is obtained as loose, pressure-stable granules and can be stored as such at room temperature for several months. The mixing process must be ended when the granules have formed, because the mixture clumps together if the mixing time is extended.
  • mixing tools e.g. a multi-shaft dissolver, a fluidized bed, turbo internal or high performance centrifug
  • this granulate can be used as a molding compound for the production of molded parts.
  • the fillers have not been wetted intensively by the mixing process and the mixture is not sufficiently homogeneous, the mechanical properties of the moldings produced therefrom are unsatisfactory.
  • the granules are therefore homogenized shortly before shaping and curing under pressure. This is done in that the granules, optionally with heating to a temperature which is below the light-off temperature of the curing of the epoxy resin or below the melting temperature of the capsule wall material, possibly used encapsulated hardener, by means of a pressure-building conveyor device, about a piston pump or a screw is pressed through a continuous mixer upstream of the molding tool.
  • Continuous mixers with built-in screw are continuously running single-shaft or multi-shaft mixers or cocneters. A simpler but equally effective homogenization can be achieved if the continuous mixer upstream of the molding tool is a static mixer which is preceded by a pressure-building conveyor device which plasticizes the granules and presses them through the static mixer.
  • the molding compositions produced according to the invention are suitable for all applications in which epoxy resin molding compositions are used. In particular, however, they are suitable for the production of molded parts in the reaction injection molding process, for the encapsulation of electronic or electrical components or component components and for the production of mechatronic components.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)

Abstract

The invention relates to a method for producing and treating epoxide resin moulding materials, said moulding materials containing epoxide resins, hardening agents, fillers and additives. According to the inventive method, the epoxide resins are mixed and granulated with the other constituents of the moulding material in a mixer comprising high-speed mixing tools, and the pourable granulated material obtained is homogenised under pressure shortly before being shaped and hardened.

Description

Verfahren zur Herstellung und Verarbeitung von Epoxidharz-FormmassenProcess for the production and processing of epoxy resin molding compounds
Die Erfindung betrifft ein neues Verfahren zur Herstellung und Verarbeitung von Formmassen auf Basis von Epoxidharzen.The invention relates to a new process for the production and processing of molding compositions based on epoxy resins.
Epoxidharz-Formmassen sind Granulate aus Epoxidharz, Härter sowie Füll- und Zusatzstoffen, die man ohne Beimischung eines Zusatzstoffes zu thermisch härtbaren Formteilen verarbeiten kann. Die so hergestellten Formkörper zeichnen sich durch gute mechanische und elektrische Eigenschaften aus.Epoxy resin molding compounds are granules made of epoxy resin, hardener as well as fillers and additives that can be processed into thermally curable molded parts without the addition of an additive. The molded articles produced in this way are distinguished by good mechanical and electrical properties.
Zur Herstellung von Epoxidharz-Formmassen gibt es verschiedene Verfahren (vergl. Kunststoff Handbuch Band 10 "Duroplaste", 2. Auflage, Hanser Verlag 1988, Seiten 338 - 342 ):There are various processes for the production of epoxy resin molding compositions (see plastic handbook volume 10 "Duroplasts", 2nd edition, Hanser Verlag 1988, pages 338 - 342):
• In ein flüssiges Gemisch aus Epoxidharz und Härter werden die übrigen Füll- und Zusatzstoffe eingemischt. Bei mäßig gesteigerter Temperatur läßt man die Epoxidharze soweit vorreagieren, bis die Masse bei Raumtemperatur klebfrei und rieselfähig ist. Trotz guter Benetzung der Füllstoffe hat dieses Verfahren den Nachteil, daß die Einstellung der Vorreaktion nicht exakt reproduzierbar ist, so daß die entsprechenden Formmassen sich in ihrer Reaktivität von Charge zu Charge unterscheiden. Außerdem sind diese Formmassen nicht lagerstabil.• The other fillers and additives are mixed into a liquid mixture of epoxy resin and hardener. At a moderately elevated temperature, the epoxy resins are allowed to prereact until the mass is tack-free and free-flowing at room temperature. Despite good wetting of the fillers, this process has the disadvantage that the setting of the pre-reaction is not exactly reproducible, so that the corresponding molding compositions differ in their reactivity from batch to batch. In addition, these molding compositions are not stable in storage.
• Beim sogenannten Trockenmischverfahren werden bei Raumtemperatur feste Epoxidharze und Härter mit den übrigen Bestandteilen der Formmasse gemahlen und innig vermischt. Danach muß das Pulver mechanisch verdichtet und granuliert werden. Harz und Härter liegen in dieser Masse als kleine Partikel nebeneinander vor. Dies ergibt eine gute Lagerstabilität der Massen. Allerdings ist bei diesem Verfahren die Benetzung der Füllstoffe nicht zufriedenstellend, so daß nur Formmassen mit relativ niedrigem Füllstoffanteil herstellen lassen, die zudem nur Formkörper mit wenig zufriedenstellenden mechanischen Eigenschaften ergeben.• In the so-called dry mixing process, solid epoxy resins and hardeners are ground with the other components of the molding compound at room temperature and intimately mixed. The powder must then be mechanically compacted and granulated. Resin and hardener are present in this mass as small particles side by side. This gives the masses good storage stability. However, the wetting of the fillers is unsatisfactory in this process, so that only molding compositions with a relatively low filler content can be produced, which moreover only give molded articles with unsatisfactory mechanical properties.
• Zur besseren Benetzung der Füllstoffe wird daher im Schmelzverfahren ein Vorgemisch aus festem Epoxidharz, Härter, Füll- und Zusatzstoffen als Schmelze homogenisiert und anschließend abgekühlt und granuliert. Allerdings treten bei diesem technologisch aufwendigen Verfahren mittels Schmelzhomogenisierung bereits wieder Härtungsreaktionen auf, die die Lagerstabilität der Formmasse reduzieren und sehr schnell zu einer überlagerten Masse fuhren. Dies kann vermieden werden, wenn Harz und Härter jeweils mit Füll- und Zusatzstoffen separat in Schmelzen homogenisiert und anschließend als Pulver vermischt werden. Dann sinken allerdings wieder die mechanischen Eigenschaften der damit hergestellten Formkörper.• For better wetting of the fillers, a premix of solid epoxy resin, hardener, fillers and additives is therefore homogenized as a melt in the melting process and then cooled and granulated. However, hardening reactions occur again in this technologically complex process by means of melt homogenization, which reduce the storage stability of the molding composition and very quickly lead to a superimposed composition. This can be avoided if the resin and hardener with fillers and additives are separately homogenized in melts and then mixed as a powder. Then, however, the mechanical properties of the moldings produced with it decrease again.
Es ist daher Aufgabe der vorliegenden Erfindung, ein einfaches, schnell durchzuführendes Verfahren zur Herstellung von Epoxidharz-Formmassen bereitzustellen, mit dem sich lagerstabile Formmassen mit hohem Füllstoffanteil herstellen lassen, die nach der Formgebung und Aushärtung Formkörper mit sehr guten mechanischen und elektrischen Eigenschaften ergeben.It is therefore an object of the present invention to provide a simple, quick-to-carry-out process for the production of epoxy resin molding compositions, with which storage-stable molding compositions with a high filler content can be produced, which after molding and curing result in moldings with very good mechanical and electrical properties.
Die Lösung der Aufgabe erfolgt durch ein Verfahren zur Herstellung und Verarbeitung von Epoxidharz-Formmassen gemäß der Ansprüche 1 bis 7. Die gemäß dem Verfahren hergestellten Formmassen eignen sich insbesondere zur Herstellung von Formteilen im Reaction-Injection-Molding- Verfahren, zur Umhüllung von elektronischen oder elektrischen Bauteilen oder Bauteilkomponenten sowie zur Herstellung von Mechatronik- Bauteilen, wie dies in den Ansprüchen 8 bis 10 beansprucht ist. Erfindungsgemäß erfolgt die Lösung dadurch, daß alle Bestandteile der Formmasse zusammen in einem schnellaufenden Mischer vermischt und zu einem lockeren, rieselfähigen Granulat verarbeitet werden. Die direkte Weiterverwendung dieses Granulats als Formmasse zur Herstellung von Formteilen in der bekannten Weise durch Verpressen in einer Form führt nicht zu hochwertigen Formkörpern, da die Homogenisierung nicht ausreichend ist. Es wurde aber gefunden, daß das Granulat die Eigenschaft hat, unter Druck eine fließfähige Masse zu bilden. Dies wird erfindungsgemäß dadurch genutzt, daß das Granulat kurz vor der Formgebung und Härtung unter Druck homogenisiert wird. In der praktischen Durchführung wird das noch nicht ausreichend homogene Granulat, kurz bevor es dem Formwerkzeug zugeführt wird, unter Druck und gegebenenfalls unter Erwärmung durch einen dem Formwerkzeug vorgeschalteten Durchlaufmischer gepreßt und dabei homogenisiert. Überraschenderweise funktioniert dies auch bei Formmassen, deren Füllstoffgehalt bis zu 95 Gew.%, bezogen auf die Gesamtmasse, beträgt.The object is achieved by a process for the production and processing of epoxy resin molding compositions according to claims 1 to 7. The molding compositions produced by the process are particularly suitable for the production of molded parts in the reaction injection molding process, for the encapsulation of electronic or electrical components or component components and for the production of mechatronic components, as claimed in claims 8 to 10. According to the invention, the solution is achieved by mixing all the constituents of the molding composition together in a high-speed mixer and processing them into loose, free-flowing granules. The direct further use of this granulate as a molding composition for the production of molded parts in the known manner by pressing in a mold does not lead to high-quality moldings, since the homogenization is not sufficient. However, it was found that the granules have the property of forming a flowable mass under pressure. This is used according to the invention in that the granules are homogenized under pressure shortly before shaping and hardening. In practice, the granules, which are not yet sufficiently homogeneous, are pressed under pressure and, if appropriate, with heating by a continuous mixer upstream of the molding tool, shortly before it is fed to the molding tool, and homogenized in the process. Surprisingly, this also works with molding compositions whose filler content is up to 95% by weight, based on the total composition.
Die Herstellung des Granulats erfolgt sehr schnell und einfach. Das Granulat ist lagerfähig und klumpt bei normaler Lagerung im Gebinde nicht zusammen, sondern bleibt rieselfähig. Erst bei Anwendung von Drucken > 5 bar, wie sie sich bei Durchgang durch Transportvorrichtungen wie Extruderschnecken oder Kolbenpumpen ergeben, werden diese Mischungen plastifiziert und lassen sich in Durchlaufmischern homogenisieren. Danach wird die erhaltene homogene Formmasse direkt in das Formwerkzeug eingespritzt. Es ist dabei ein weiterer Vorteil des erfindungsgemäßen Verfahrens, daß sowohl die Mischmaschinen, wie auch die Vorrichtungsbausteine wie die zur Druckerzeugung notwendigen Geräte und Durchlaufmischer in der kunststoffVerarbeitenden Industrie gebräuchliche Maschinen sind, die in einfacher Weise einem Formwerkzeug vorgeschaltet werden können. Die bislang übliche Fertigung von Formkörpern wird dadurch nicht wesentlich verändert.The granulate is produced very quickly and easily. The granules are storable and do not clump together in normal storage, but remain free-flowing. Only when using pressures> 5 bar, such as those that occur when passing through transport devices such as extruder screws or piston pumps, are these mixtures plasticized and can be homogenized in continuous mixers. The homogeneous molding compound obtained is then injected directly into the mold. It is a further advantage of the method according to the invention that both the mixing machines and the device components, such as the devices and continuous mixers required for pressure generation, are common machines in the plastics processing industry and can be connected upstream of a molding tool in a simple manner. The previously customary production of shaped bodies is not significantly changed by this.
Der Aufbau der erfindungsgemäß hergestellten Epoxidharz-Formmassen entspricht im wesentlichen dem bislang üblicher Epoxidharz-Formmassen.The structure of the epoxy resin molding compositions produced in accordance with the invention essentially corresponds to the epoxy resin molding compositions which have been customary to date.
Als Epoxidharze können alle Epoxidverbindungen mit mindestens zwei Epoxidgruppen pro Molekül eingesetzt werden, deren Schmelzbereich unter 70°C liegt.. Bevorzugt sind Epoxidverbindungen, die bei Raumtemperatur flüssig sind, wie Diglycidylether von Bisphenolen oder vorverlängerte Harze auf Basis von Bisphenol-A-Diglycidylethern. Insbesondere bevorzugt sind niedrigviskose Harze wie Epoxidharze auf Basis von Cycloolefinen oder Tetraglycidyldianilin oder aber auch Mischungen fester Epoxidharze wie z.B. epoxidierter Novolake mit sog. Reaktiwerdünnem. Die Epoxidharze können gegebenenfalls mit anderen Polymeren wie z.B. Polyestern, Acrylaten, Siliconpolymeren oder Polyvinylderivaten modifiziert sein.All epoxy compounds with at least two epoxy groups per molecule whose melting range is below 70 ° C. can be used as epoxy resins. Preferred are epoxy compounds which are liquid at room temperature, such as diglycidyl ether from Bisphenols or pre-extended resins based on bisphenol A diglycidyl ethers. Low-viscosity resins, such as epoxy resins based on cycloolefins or tetraglycidyldianiline, or else mixtures of solid epoxy resins, such as, for example, epoxidized novolaks with what are known as reactive diluents, are particularly preferred. The epoxy resins can optionally be modified with other polymers such as polyesters, acrylates, silicone polymers or polyvinyl derivatives.
Als Härter werden an sich bekannte latente Härter eingesetzt, wie z.B. alkylsubstituierte aromatische Amine, Polycarbonsäuren und -anhydride, BC13- oder BF3-Komplexe, latente HeteroVerbindungen auf Basis Stickstoff oder Phosphor oder Metallkomplexverbindungen. Latente Härter sind aber auch mikroverkapselte Härter. Dabei sind Härter, die in freier Form bereits bei Raumtemperatur zu einer Härtung der Epoxidharze führen, wie z.B. aliphatische oder aromatische Amine oder Polyamine, Novolake oder Imidazolderivate, mit einem inerten Material verkapselt. Unter den Verarbeitungsbedingungen des Granulats werden die Kapselwände entweder durch die eingebrachte thermische Energie oder durch die bei der Homogenisierung auftretenden Scherkräfte, zerstört und der Härter freigesetzt und mit dem Rest der Formmassenmischung homogenisiert. Die Menge der eingesetzten Härter wird in an sich bekannter Weise so gewählt, daß sie zur vollständigen Aushärtung der Epoxidverbindungen ausreicht.Known latent hardeners are used as hardeners, such as, for example, alkyl-substituted aromatic amines, polycarboxylic acids and anhydrides, BC1 3 or BF 3 complexes, latent hetero compounds based on nitrogen or phosphorus or metal complex compounds. However, latent hardeners are also microencapsulated hardeners. Hardeners which, in free form, lead to curing of the epoxy resins at room temperature, such as aliphatic or aromatic amines or polyamines, novolaks or imidazole derivatives, are encapsulated with an inert material. Under the processing conditions of the granulate, the capsule walls are destroyed either by the thermal energy introduced or by the shear forces occurring during the homogenization, and the hardener is released and homogenized with the rest of the molding compound mixture. The amount of hardener used is chosen in a manner known per se so that it is sufficient for the epoxy compounds to be fully cured.
Als Füllstoffe können alle für derartige Formmassen üblichen anorganischen und/oder organischen Füllstoffe mit den üblicherweise gebrauchten Korngrößen eingesetzt werden. Beispiele sind hydrophobierte oder unbehandelte Kreiden, Dolomit, gefällte oder gemahlene Kieselsäure, Wollastonit, Glimmer, Talkum, Silikate, Clays, Titandioxid, Lithopone, Aluminiumoxidhydrat, Antimontrioxid aber auch Cellulose- oder Polyamidpulver. Als besonders verstärkende Füllstoffe können aber auch Fasern, insbesondere Kurzfasern mit einer durchschnittlichen Länge von 0,5 bis 4 mm eingesetzt werden. Beispiele für derartige Fasern sind Glas-, Keramik-, Aramid-, Cellulose-, Polyester-, Polyamid- oder C-Fasern. Die Menge der eingesetzten Füllstoffe beträgt bis zu 95 Gew.%, bevorzugt bis zu 85 Gew.%, bezogen auf die gesamte Formmasse. Auch übliche Zusatzstoffe wie Gleit- oder Trennmittel wie z.B. Wachse, Metallseifen oder substituierte Fettsäureamide, Pigmente, Flexibilatoren, Kupplungsreagentien, Beschleuniger oder Flammschutzmittel können in die erfindungsgemäß hergestellten Epoxidharz-Formmassen in an sich gebräuchlichen Mengen eingemischt werden.All inorganic and / or organic fillers customary for such molding compositions with the grain sizes usually used can be used as fillers. Examples are hydrophobized or untreated chalk, dolomite, precipitated or ground silica, wollastonite, mica, talc, silicates, clays, titanium dioxide, lithopone, aluminum oxide hydrate, antimony trioxide but also cellulose or polyamide powder. However, fibers, in particular short fibers with an average length of 0.5 to 4 mm, can also be used as particularly reinforcing fillers. Examples of such fibers are glass, ceramic, aramid, cellulose, polyester, polyamide or C fibers. The amount of fillers used is up to 95% by weight, preferably up to 85% by weight, based on the total molding composition. Conventional additives such as lubricants or release agents such as waxes, metal soaps or substituted fatty acid amides, pigments, flexibilizers, coupling reagents, accelerators or flame retardants can also be mixed into the epoxy resin molding materials prepared according to the invention in amounts which are customary per se.
Alle Bestandteile der Epoxidharz-Formmassen werden möglichst gleichzeitig miteinander vermischt. Aus praktischen Gründen werden dabei bevorzugt die flüssigen Bestandteile der Massen vorgelegt und die festen Ingredientien in beliebiger Reihenfolge zugegeben.All components of the epoxy resin molding compounds are mixed together at the same time if possible. For practical reasons, the liquid constituents of the masses are preferably introduced and the solid ingredients are added in any order.
Der Mischvorgang erfolgt in einem Mischer mit schnell rotierenden Mischwerkzeugen, wie z.B. einem Mehrfachwellendissolver, einem Wirbelbett-, Turboinnen- oder Hochleistungsschleudermischer. Bevorzugt sind solche schnellaufenden Mischer, bei denen die Möglichkeit besteht, das Mischgut auch zu temperieren, damit der durch den Energieeintrag erfolgende Temperaturanstieg so begrenzt wird, daß die Temperatur der Mischung unter dem Anspringpunkt der Härtungsreaktion des Epoxidharzes gehalten werden kann. Gegebenenfalls kann dem Mischer ein Kühlmischer nachgeschaltet werden. Innerhalb einer kurzen Mischzeit, bei Einsatz von Wirbel- oder Hochleistungsschleudermischern innerhalb einer Mischzeit von weniger als einer Minute, wird die noch nicht homogene Formmasse als lockeres, für die Handhabung ausreichend druckstabiles Granulat erhalten und kann als solches bei Raumtemperatur mehrere Monate lang gelagert werden. Der Mischvorgang ist zu beenden, wenn sich das Granulat gebildet hat, denn bei verlängerter Mischzeit verklumpt die Mischung.The mixing process takes place in a mixer with rapidly rotating mixing tools, e.g. a multi-shaft dissolver, a fluidized bed, turbo internal or high performance centrifugal mixer. Preference is given to high-speed mixers in which there is the possibility of also tempering the mix so that the temperature rise resulting from the energy input is limited so that the temperature of the mixture can be kept below the starting point of the curing reaction of the epoxy resin. If necessary, a cooling mixer can be installed downstream of the mixer. Within a short mixing time, if vortex or high-performance centrifugal mixers are used within a mixing time of less than one minute, the not yet homogeneous molding compound is obtained as loose, pressure-stable granules and can be stored as such at room temperature for several months. The mixing process must be ended when the granules have formed, because the mixture clumps together if the mixing time is extended.
Theoretisch kann dieses Granulat als Formmasse zur Herstellung von Formteilen eingesetzt werden. Da aber durch den Mischvorgang die Füllstoffe nicht intensiv benetzt wurden und die Mischung nicht ausreichend homogen ist, sind die mechanischen Eigenschaften der daraus hergestellten Formkörper nicht zufriedenstellend. Erfindungsgemäß wird daher das Granulat kurz vor der Formgebung und Härtung unter Druck homogenisiert. Dies erfolgt dadurch, daß das Granulat, gegebenenfalls unter Erwärmung auf eine Temperatur, die unterhalb der Anspringtemperatur der Härtung des Epoxidharzes, bzw. unter der Schmelztemperatur des Kapselwandmaterials eventuell eingesetzter verkapselter Härter liegt, mittels einer Druck aufbauenden Fördervorrichtung, etwa einer Kolbenpumpe oder einer Schnecke durch einen dem Formwerkzeug vorgeschalteten Durchlaufmischer gepreßt wird. Durchlaufmischer mit eingebauter Schnecke sind kontinuierlich laufende Einwellen- oder Mehrwellenmischer oder Cokneter. Eine einfachere aber ebenso effektive Homogenisierung kann erzielt werden, wenn der dem Formwerkzeug vorgeschaltete Durchlaufmischer ein statischer Mischer ist, dem eine Druck aufbauende Fördervorrichtung vorgeschaltet ist, die das Granulat plastifiziert und durch den statischen Mischer preßt.In theory, this granulate can be used as a molding compound for the production of molded parts. However, since the fillers have not been wetted intensively by the mixing process and the mixture is not sufficiently homogeneous, the mechanical properties of the moldings produced therefrom are unsatisfactory. According to the invention, the granules are therefore homogenized shortly before shaping and curing under pressure. This is done in that the granules, optionally with heating to a temperature which is below the light-off temperature of the curing of the epoxy resin or below the melting temperature of the capsule wall material, possibly used encapsulated hardener, by means of a pressure-building conveyor device, about a piston pump or a screw is pressed through a continuous mixer upstream of the molding tool. Continuous mixers with built-in screw are continuously running single-shaft or multi-shaft mixers or cocneters. A simpler but equally effective homogenization can be achieved if the continuous mixer upstream of the molding tool is a static mixer which is preceded by a pressure-building conveyor device which plasticizes the granules and presses them through the static mixer.
Die erfindungsgemäß hergestellten Formmassen eignen sich für alle Anwendungen, bei denen Epoxidharz-Formmassen werden. Insbesondere aber eignen sie sich zur Herstellung von Formteilen im Reaction-Injection-Molding-Verfahren, zur Umhüllung von elektronischen oder elektrischen Bauteilen oder Bauteilkomponenten sowie zur Herstellung von Mechatronik-Bauteilen. The molding compositions produced according to the invention are suitable for all applications in which epoxy resin molding compositions are used. In particular, however, they are suitable for the production of molded parts in the reaction injection molding process, for the encapsulation of electronic or electrical components or component components and for the production of mechatronic components.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung und Verarbeitung von Epoxidharz-Formmassen aus Epoxidharzen , Härtern, Füll- und Zusatzstoffen, dadurch gekennzeichnet, daß Epoxidharze mit den übrigen Bestandteilen der Masse in einem Mischer mit schnellaufenden Mischwerkzeugen vermischt und granuliert werden und das erhaltene rieselfahige Granulat kurz vor der Formgebung und Härtung unter Druck homogenisiert wird.1. Process for the production and processing of epoxy resin molding compositions from epoxy resins, hardeners, fillers and additives, characterized in that epoxy resins are mixed and granulated with the other constituents of the composition in a mixer with high-speed mixing tools and the free-flowing granules obtained shortly before Shaping and curing is homogenized under pressure.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die eingesetzten Epoxidharze bei Raumtemperatur flüssig sind.2. The method according to claim 1, characterized in that the epoxy resins used are liquid at room temperature.
3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß die eingesetzten Härter latente Epoxidharz-Härter sind.3. The method according to claim 1 and 2, characterized in that the hardeners used are latent epoxy resin hardeners.
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Mischung der Bestandteile in einem Wirbelbett-, Turboinnen- oder Hochleistungsschleudermischer erfolgt.4. The method according to one or more of claims 1 to 3, characterized in that the mixing of the components takes place in a fluidized bed, turbo-internal or high-performance centrifugal mixer.
5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Homogenisierung der Masse in einem dem Formwerkzeug vorgeschalteten Durchlaufmischer erfolgt.5. The method according to one or more of claims 1 to 4, characterized in that the homogenization of the mass takes place in a continuous mixer upstream of the molding tool.
6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Homogenisierung der Masse in einem dem Formwerkzeug vorgeschalteten statischen Mischer erfolgt. 6. The method according to one or more of claims 1 to 4, characterized in that the homogenization of the mass takes place in a static mixer upstream of the molding tool.
7. Verfahren nach Anspruch 5 oder 6, dadurch gekennzeichnet, daß dem Durchlaufmischer eine Schnecke oder Kolbenpumpe vorgeschaltet ist, mit deren Hilfe das Granulat verdichtet und durch den Durchlaufmischer gepreßt wird.7. The method according to claim 5 or 6, characterized in that the continuous mixer is preceded by a screw or piston pump, with the aid of which the granulate is compressed and pressed through the continuous mixer.
8. Verwendung der gemäß der Ansprüche 1 bis 7 hergestellten Formmassen zur Herstellung von Formteilen im Reaction-Injection-Molding- Verfahren.8. Use of the molding compositions prepared according to claims 1 to 7 for the production of moldings in the reaction injection molding process.
9. Verwendung der gemäß der Ansprüche 1 bis 7 hergestellten Formmassen zur Umhüllung von elektrischen oder elektronischen Bauteilen oder Bauteilkomponenten.9. Use of the molding compositions prepared according to claims 1 to 7 for the encapsulation of electrical or electronic components or component components.
10. Verwendung der gemäß der Ansprüche 1 bis 7 hergestellten Formmassen zur Herstellung von Mechatronik-Bauteilen. 10. Use of the molding compositions prepared according to claims 1 to 7 for the production of mechatronic components.
EP03708109A 2002-02-28 2003-02-19 Method for producing and treating epoxide resin moulding materials Ceased EP1480813A1 (en)

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DE2002108644 DE10208644A1 (en) 2002-02-28 2002-02-28 Process for the production and processing of epoxy resin molding compounds
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