EP0486651A1 - Prepreg, process for manufacturing it, and use of the prepreg - Google Patents

Prepreg, process for manufacturing it, and use of the prepreg

Info

Publication number
EP0486651A1
EP0486651A1 EP91910945A EP91910945A EP0486651A1 EP 0486651 A1 EP0486651 A1 EP 0486651A1 EP 91910945 A EP91910945 A EP 91910945A EP 91910945 A EP91910945 A EP 91910945A EP 0486651 A1 EP0486651 A1 EP 0486651A1
Authority
EP
European Patent Office
Prior art keywords
prepreg
phenolic resin
mixture
phenol
fibers
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Withdrawn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
EP91910945A
Other languages
German (de)
French (fr)
Inventor
Walter Eichberger
Peter Walter
Wolfgang Wimmer
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.)
Isovolta AG
Original Assignee
Isovolta Osterreichische Isolierstoffwerke AG
Isovolta 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 Isovolta Osterreichische Isolierstoffwerke AG, Isovolta AG filed Critical Isovolta Osterreichische Isolierstoffwerke AG
Publication of EP0486651A1 publication Critical patent/EP0486651A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention relates to a prepreg based on unidirectionally arranged reinforcements impregnated with durable plastics.
  • Kung fibers such as glass fibers, carbon fibers, aramid fibers and the like.
  • prepregs are produced by impregnating reinforcing fibers with 10 thermosetting plastics. These prepregs are preferably used to manufacture composite parts for aircraft and mechanical engineering and for the manufacture of sports articles. These composite parts are now subject to a number of requirements, such as high dynamic mechanical properties and high temperature and chemical resistance . It is known to use prepregs for such composite parts, the reinforcing fibers of which are impregnated with highly functional epoxy resins, whereby the desired temperature and chemical resistance may not be achieved, but the required dynamic mechanical properties such as sufficient toughness can be achieved in the finished composite parts.
  • the invention is based on the object, a prepreg based on unidirectionally arranged, with thermoset plastic
  • the prepreg according to the invention which is characterized in that its reinforcing fibers with a plastic mixture, an epoxy resin, a phenolic resin, optionally an accelerator and optionally additives such as fillers, flame retardants, elasticizers, wetting agents and the like ., are impregnated, the proportions of reinforcing fibers in the prepreg advantageously being 30-80% by weight, 70-20% by weight of epoxy-phenolic resin mixture and 0-30% by weight of additives.
  • the prepreg according to the invention contains a phenol-formaldehyde condensation product in the molar ratio of phenol to formaldehyde in the resin mixture as phenolic resin from 1: 0.5 to 1: 0.9, but advantageously from 1: 0.6 to 1: 0 , 85.
  • the invention is also based on the object of specifying a method for producing the prepreg according to the invention.
  • a solvent in the range of 0-20% by weight is added to the epoxy-phenolic resin mixture before the impregnation process, this mixture being applied by means of a doctor blade to a continuously moving film in the form of a layer, into which then the tapered, endless reinforcing fibers are pressed in and thereby impregnated.
  • a solvent-free epoxy resin-phenolic resin mixture is used for the impregnation, which is brought to an elevated temperature before the impregnation process in order to reduce the viscosity.
  • This scrim advantageously runs through impregnated Reinforcing fibers additionally a heating device in which the epoxy resin-phenolic resin mixture is converted into the B state and the solvent which may be present is evaporated, and then, if appropriate, a calender. Furthermore, a phenol-formaldehyde condensation product with a molar ratio of phenol to formaldehyde of 1: 0.5 to 1: 0.9, advantageously from 1: 0.6 to 1: 0.85, is preferably used.
  • the prepregs according to the invention are advantageously used for the production of hot-cured composite materials, the curing taking place, for example, in a closed form, but also in a state wound on a mandrel.
  • the bending strength losses of the laminate A produced from the prepreg according to the invention are compared before and after a so-called high-pressure cooker test in comparison to the corresponding measured values on comparative products B, C and D.
  • These are laminates which have been produced from prepregs which have been cured with nitrogen-containing compounds.
  • the phenol-formaldehyde condensation product required for the preparation of the prepreg is produced in two stages, the first stage being phenol and formaldehyde in an aqueous solution in a molar ratio of phenol: formaldehyde in the range from about 1: 0.3 to 1: 0 , 7 are added, an acidic medium is established by adding a volatile acid and the whole is kept at an elevated temperature until the condensation reaction has ended, so that in a second stage the reaction product of the first stage is added a small part consists of phenol and otherwise predominantly dihydroxydiphenylmethane, formaldehyde is added in an amount so that the molar ratio in the first stage Phenol used
  • the total amount of formaldehyde reacted in both stages is advantageously in the range from 1: 0.5 to 1: 0.9, advantageously 1: 0.6 to 1: 0.85, and the condensation reaction is continued at elevated temperature and ended, and that the condensation product is separated from the water and allowed to solidify outside the reaction kettle and com
  • the resulting composite is passed through a heating zone, in which a temperature of 110 ° to 160 ° C prevails, whereby the desired B state of the impregnating resin is achieved.
  • the prepreg is then passed through a calender and then cooled to room temperature in a cooling zone.
  • test specimens for the High-pressure cooker test 15 layers of the prepregs produced as described are pressed into laminates and cured under a pressure of 7 bar at 170 ° C.
  • the test specimens for the High-pressure cooker test For this purpose, the test specimens A, B, C and D are heated in an autoclave for one hour at 120 ° C./1.5 bar and then for two hours at 140 ° C./2.7 bar under steam.
  • the flexural strength (MPa) of the test specimens was determined before and after the test.
  • Hot-hardened composite materials with high permanent temperature and chemical resistance as well as composite parts for aircraft and mechanical engineering as well as for the manufacture of sporting goods are manufactured.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Data Exchanges In Wide-Area Networks (AREA)
  • Telephonic Communication Services (AREA)

Abstract

Préimprégné à base de fibres de renforcement, comme des fibres de verre, des fibres de carbone, des fibres d'aramide et similaires, disposées dans une seule direction et imprégnées par un mélange de matières plastiques duromères, dans lequel le mélange de matières plastiques contient une résine époxyde, une résine phénolique, le cas échéant un accélérateur et le cas échéant des additifs comme des charges, des retardateurs de flamme, des élastifiants, des agents mouillants et similaires. Ce préimprégné sert de matériau de départ pour des matériaux composites pressés à chaud ainsi que pour des éléments composites à constance thermique élevée et résistance élevée aux produits chimiques.Prepreg based on reinforcing fibers, such as glass fibers, carbon fibers, aramid fibers and the like, arranged in a single direction and impregnated with a mixture of duromeric plastics, in which the mixture of plastics contains an epoxy resin, a phenolic resin, optionally an accelerator and optionally additives such as fillers, flame retardants, elasticizers, wetting agents and the like. This prepreg serves as a starting material for hot-pressed composite materials as well as for composite elements with high thermal consistency and high chemical resistance.

Description

Prepreg, Verfahren zu dessen Herstellung und dessen Verwendung Prepreg, process for its production and its use
Technisches GebietTechnical field
* Die Erfindung betrifft ein Prepreg auf Basis von unidirektional angeordneten mit duro eren Kunststoffen imprägnierten Verstär-* The invention relates to a prepreg based on unidirectionally arranged reinforcements impregnated with durable plastics.
* 5 kungsfasern wie Glasfasern, Kohlenstoffasern, Aramidfasern und dgl., ein Verfahren zu dessen Herstellung sowie eine vorteilhafte Verwendung.* 5 Kung fibers such as glass fibers, carbon fibers, aramid fibers and the like., A method for its production and an advantageous use.
Stand der TechnikState of the art
Solche Prepregs werden durch Tränken von Verstärkungsfasern mit 10 duromeren Kunststoffen hergestellt. Aus diesen Prepregs werden vorzugsweise Composite-Teile für den Flugzeug- und Maschinenbau sowie für die Sportartikelhersteflung gefertigt.An diese Compo¬ site-Teile werden nun eine Reihe von Anforderungen wie hohe dyna¬ mische mechanische Eigenschaften sowie hohe Temperatur- und Che- 15 ikalienbeständigkeit gestellt. Es ist bekannt, für derartige Composite-Teile Prepregs zu verwenden, deren Verstärkungsfasern mit hochfunktionellen Epoxydharzen imprägniert sind, wodurch wohl die gewünschte Temperatur- und Chemikalienbeständigkeit nicht aber die geforderten dynamisch mechanischen Eigenschaften wie 20 ausreichende Zähigkeit die gefertigen Composite-Teile erreicht werden.Such prepregs are produced by impregnating reinforcing fibers with 10 thermosetting plastics. These prepregs are preferably used to manufacture composite parts for aircraft and mechanical engineering and for the manufacture of sports articles. These composite parts are now subject to a number of requirements, such as high dynamic mechanical properties and high temperature and chemical resistance . It is known to use prepregs for such composite parts, the reinforcing fibers of which are impregnated with highly functional epoxy resins, whereby the desired temperature and chemical resistance may not be achieved, but the required dynamic mechanical properties such as sufficient toughness can be achieved in the finished composite parts.
Ferner ist es bekannt, für die Imprägnierung Epoxydharzmischun¬ gen, denen ein stickstoffh ltiger Härter zugesetzt wird, einzu¬ setzen, was zwar die geforderte Zähigkeit, nicht aber die ausrei- 25 chende Chemikalien- und Temperaturbeständigkeit der gefertigten Composite-Teile mit sich bringt.Furthermore, it is known to use epoxy resin mixtures, to which a nitrogen-containing hardener is added, for impregnation, which brings with it the required toughness but not the sufficient chemical and temperature resistance of the composite parts produced.
Darstellung der ErfindungPresentation of the invention
Der Erfindung liegt zunächst die Aufgabe zugrunde, ein Prepreg auf Basis von unidirektional angeordneten, mit duromeren Kunst-The invention is based on the object, a prepreg based on unidirectionally arranged, with thermoset plastic
30 Stoffen imprägnierten Verstärkungsfasern anzugeben, wobei die aus diesen Prepregs hergestellten Laminate eine hohe Chemikalien- und Temperaturbeständigkeit ohne Verminderung ihrer dynamisch mecha¬ nischen Eigenschaften wie der Zähigkeit aufweisen sollen.30 substances impregnated reinforcing fibers, the laminates made from these prepregs a high chemical and Should have temperature resistance without reducing their dynamic mechanical properties such as toughness.
Diese Aufgabe wird in dem erfindungsgemäßen Prepreg gelöst, das dadurch gekennzeichnet ist, daß seine Verstärkungsfasern mit ei¬ nem Kunststoffgemisch, das ein Epoxydharz, ein Phenolharz, gege¬ benenfalls einen Beschleuniger sowie gegebenenfalls Zusatzstoffe wie Füllstoffe, Flammschutzmittel, Elastifizierungsmittel , Netz¬ mittel und dgl. enthält, imprägniert sind, wobei im Prepreg die Anteile an Verstärkungsfasern vorteilhafterweise 30 - 80 Gew.%, an Epoxydharz-Phenolharz-Gemisch 70 - 20 Gew.% sowie an Zusatz¬ stoffen 0 - 30 Gew.% betragen.This object is achieved in the prepreg according to the invention, which is characterized in that its reinforcing fibers with a plastic mixture, an epoxy resin, a phenolic resin, optionally an accelerator and optionally additives such as fillers, flame retardants, elasticizers, wetting agents and the like ., are impregnated, the proportions of reinforcing fibers in the prepreg advantageously being 30-80% by weight, 70-20% by weight of epoxy-phenolic resin mixture and 0-30% by weight of additives.
Bei einer vorteilhaften Ausgestaltung der Erfindung enthält das erfindungsgemäße Prepreg im Harzgemisch als Phenolharz ein Phenol-Formaldehyd-Kondensationsprodukt im MolVerhältnis Phenol zu Formaldehyd von 1:0,5 bis 1:0,9, vorteilhaft aber von 1:0,6 bis 1:0,85.In an advantageous embodiment of the invention, the prepreg according to the invention contains a phenol-formaldehyde condensation product in the molar ratio of phenol to formaldehyde in the resin mixture as phenolic resin from 1: 0.5 to 1: 0.9, but advantageously from 1: 0.6 to 1: 0 , 85.
Der Erfindung liegt ferner die Aufgabe zugrunde, ein Verfahren zum Herstellen des erfindungsgemäßen Prepregs anzugeben.The invention is also based on the object of specifying a method for producing the prepreg according to the invention.
In diesem Verfahren wird dem Epoxydharz-Phenolharz-Gemisch vor dem Imprägniervorgang ein Lösungsmittel im Bereich von 0 - 20 Gew.% zugesetzt, wobei dieses Gemisch mittels einer Rakel auf ei¬ ne kontinuierlich bewegte Treπnfolie in Form einer Schicht auf¬ gebracht wird, in welche dann die zulaufenden, endlosen Verstär¬ kungsfasern hineingedrückt und dadurch imprägniert werden.In this process, a solvent in the range of 0-20% by weight is added to the epoxy-phenolic resin mixture before the impregnation process, this mixture being applied by means of a doctor blade to a continuously moving film in the form of a layer, into which then the tapered, endless reinforcing fibers are pressed in and thereby impregnated.
Bei einer vorteilhaften Ausgestaltung dieses Verfahrens wird ein lösungsmittelfreies Epoxydharz-Phenolharz-Gemisch zum Impräg¬ nieren eingesetzt, das vor dem Imprägniervorgang zwecks Verrin¬ gerung der Viskosität auf erhöhte Temperatur gebracht wird.In an advantageous embodiment of this method, a solvent-free epoxy resin-phenolic resin mixture is used for the impregnation, which is brought to an elevated temperature before the impregnation process in order to reduce the viscosity.
Vorteilhafterweise durchläuft dieses Gelege aus imprägnierten Verstärkungsfasern zusätzlich eine Heizeinrichtung, in der das Epoxydharz-Phenolharz-Gemisch in den B-Zustand übergeführt und das gegebenenfalls vorhandene Lösungsmittel abgedampft wird, und danach gegebenenfalls einen Kalander. Ferner wird vorzugsweise ein Phenol-Formaldehyd-Kondensationsprodukt mit einem Molver¬ hältnis Phenol zu Formaldehyd von 1:0,5 bis 1:0.9, vorteilhaft von 1:0.6 bis 1:0,85, eingesetzt.This scrim advantageously runs through impregnated Reinforcing fibers additionally a heating device in which the epoxy resin-phenolic resin mixture is converted into the B state and the solvent which may be present is evaporated, and then, if appropriate, a calender. Furthermore, a phenol-formaldehyde condensation product with a molar ratio of phenol to formaldehyde of 1: 0.5 to 1: 0.9, advantageously from 1: 0.6 to 1: 0.85, is preferably used.
Die erfindungsgemäßen Prepregs werden vorteilhaft zur Herstellung von heiß ausgehärteten Verbundwerkstoffen verwendet, wobei die Aushärtung zum Beispiel in einer geschlossenen Form, aber auch in einem auf einem Dorn aufgewickelten Zustand erfolgt.The prepregs according to the invention are advantageously used for the production of hot-cured composite materials, the curing taking place, for example, in a closed form, but also in a state wound on a mandrel.
Kurze Beschreibung eines für die Erfindung relevanten Diagramms im Zusammenhang mit einem Weg zur Ausführung der Erfindung.Brief description of a diagram relevant to the invention in connection with a way of carrying out the invention.
In dem Diagramm gemäß Fig. 1 sind die Biegefestigkeitsverluste des aus dem erfindungsgemäßen Prepreg hergestellten Laminates A vor und nach einem sogenannten High-Pressure-Cooker-Test im Ver¬ gleich zu den entsprechenden Meßwerten an Vergleichsprodukten B, C und D gegenübergestellt. Diese sind Laminate, die aus Prepregs hergestellt wurden, die mit stickstoffhaltigen Verbindungen aus¬ gehärtet wurden.In the diagram according to FIG. 1, the bending strength losses of the laminate A produced from the prepreg according to the invention are compared before and after a so-called high-pressure cooker test in comparison to the corresponding measured values on comparative products B, C and D. These are laminates which have been produced from prepregs which have been cured with nitrogen-containing compounds.
Das für die Prepregherstel lung benötigte Phenol-Formaldehyd-Kon¬ densationsprodukt wird in zwei Stufen hergestellt, wobei man in der ersten Stufe Phenol und Formaldehyd in einer wässrigen Lösung im MolVerhältnis Phenol: Formaldehyd im Bereich von etwa 1:0,3 bis 1:0,7 versetzt, durch Zugabe einer flüchtigen Säure ein sau- res Milieu einstellt und das Ganze- bis zum Abschluß der Konden¬ sationsreaktion auf einer erhöhten Temperatur hält, daß man da¬ nach - in einer zweiten Stufe dem Reaktionsprodukt der ersten Stufe, das zu einem geringen Teil aus Phenol und sonst überwie¬ gend aus Dihydroxydiphenylmethan besteht, Formaldehyd in einer Menge zusetzt, so daß das MolVerhältnis aus in der ersten Stufe eingesetzte Phenol Gesamtmenge des in beiden Stufen umgesetzten Formaldehyds vorteilhaft im Bereich von 1:0,5 bis 1:0,9, vorteil¬ haft 1:0,6 bis 1:0,85, liegt, und man die Kondensationsreaktion bei erhöhter Temperatur fortsetzt und beendet, und daß man das Kondensationsprodukt vom Wasser abtrennt und außerhalb des Reak¬ tionskessels erstarren läßt und zerkleinert. Dabei kann nach Be¬ endigung der Kondensationsreaktion und der Entfernung des Wassers das noch verbliebene Phenol (Monohydroxybenzol ) durch Wasser¬ dampfdestillation zumindest zum größten Teil entfernt werden.The phenol-formaldehyde condensation product required for the preparation of the prepreg is produced in two stages, the first stage being phenol and formaldehyde in an aqueous solution in a molar ratio of phenol: formaldehyde in the range from about 1: 0.3 to 1: 0 , 7 are added, an acidic medium is established by adding a volatile acid and the whole is kept at an elevated temperature until the condensation reaction has ended, so that in a second stage the reaction product of the first stage is added a small part consists of phenol and otherwise predominantly dihydroxydiphenylmethane, formaldehyde is added in an amount so that the molar ratio in the first stage Phenol used The total amount of formaldehyde reacted in both stages is advantageously in the range from 1: 0.5 to 1: 0.9, advantageously 1: 0.6 to 1: 0.85, and the condensation reaction is continued at elevated temperature and ended, and that the condensation product is separated from the water and allowed to solidify outside the reaction kettle and comminuted. After the condensation reaction has ended and the water has been removed, the remaining phenol (monohydroxybenzene) can be at least largely removed by steam distillation.
Für die Prepregherstellung werdenFor prepreg production
Zu 100g Epoxydharz vom Typ eines Bisphenol-A-Diglycidylethers und 80g Phenol-Formaldehyd-Kondensationsprodukt im Molverhältis Phenol zu Formaldehyd von 1: 0,75 0,2g BDMA (= Benzyldimethylamin) als Beschleuniger zugegeben, und dieses Gemisch auf 40°C erwärmt, so daß sich eine Viskosität von 15.000 mPa.s einstellt. Dieses vorerwärmte Harzgemisch wird mit einer Rakel in einer Stärke von 0,15 mm auf eine Trennfolie auf¬ getragen. In diesen Harzfilm werden auf einer konvex gekrümmten Fläche vorgespannte, parallelisierte Glasrovings eingedrückt, wo¬ bei die Durchtränkung der Glasrovings mit dem Harzgemisch er¬ folgt. Der so entstandene Verbund wird durch eine Heizzone ge¬ führt, in der eine Temperatur von 110° bis 160°C herrscht, wo¬ durch der gewünschte B-Zustand des Imprägnierharzes erreicht wird. Anschließend wird das Prepreg durch einen Kalander geführt und sodann in einer Kühlzone auf Raumtemperatur abgekühlt.To 100 g of bisphenol A diglycidyl ether-type epoxy resin and 80 g of phenol-formaldehyde condensation product in a molar ratio of phenol to formaldehyde of 1: 0.75 0.2 g of BDMA (= benzyldimethylamine) as an accelerator, and this mixture was heated to 40 ° C. so that a viscosity of 15,000 mPa.s is established. This preheated resin mixture is applied to a release film with a doctor blade in a thickness of 0.15 mm. Prestressed, parallelized glass rovings are pressed into this resin film on a convexly curved surface, the glass rovings being impregnated with the resin mixture. The resulting composite is passed through a heating zone, in which a temperature of 110 ° to 160 ° C prevails, whereby the desired B state of the impregnating resin is achieved. The prepreg is then passed through a calender and then cooled to room temperature in a cooling zone.
3) Laminatherstellung und Biegefestigkeitsprüfung dieser Laminate3) Laminate production and bending strength test of these laminates
15 Lagen der wie beschrieben hergestellten Prepregs werden unter einem Druck von 7 bar bei 170°C zu Laminaten verpreßt und ausge¬ härtet. Aus diesen Laminaten werden dann die Probekörper für den High-Pressure-Cooker-Test hergestellt. Dazu werden die Probekör¬ per A, B, C und D in einem Autoklaven eine Stunde bei 120°C/1,5 bar und danach zwei Stunden bei 140°C/2,7 bar unter Wasserdampf erhitzt. Es wurde die Biegefestigkeit (MPa) der Probekörper vor und nach dem Test ermittelt.15 layers of the prepregs produced as described are pressed into laminates and cured under a pressure of 7 bar at 170 ° C. The test specimens for the High-pressure cooker test. For this purpose, the test specimens A, B, C and D are heated in an autoclave for one hour at 120 ° C./1.5 bar and then for two hours at 140 ° C./2.7 bar under steam. The flexural strength (MPa) of the test specimens was determined before and after the test.
In nachstehender Tabelle werden die Biegefestigkeitsverluste dieser Probekörper einander gegenübergestellt.The bending strength losses of these test specimens are compared in the table below.
Biegefestigkeitsverlust (%)Flexural strength loss (%)
Laminat aus erfindungsgem. Prepreg A 14.5 Vergleichskörper B 17.4Laminate from the invention. Prepreg A 14.5 reference block B 17.4
C 17,7C 17.7
D 39,5D 39.5
Diese Meßwerte sind im Diagramm gemäß Fig. 1 graphisch dargelegt, wobei ersichtlich ist, daß das Absinken der Biegefestigkeit bei den Vergleichsproben B, C, D nach erfolgtem High-Pressure- Cooker-Test wesentlich höher ist als bei dem aus den erfindungs¬ gemäßen Prepreg hergestellten Laminat.These measured values are shown graphically in the diagram according to FIG. 1, whereby it can be seen that the decrease in the bending strength in the comparison samples B, C, D after the high-pressure cooker test has been carried out is considerably higher than in the prepreg according to the invention manufactured laminate.
Gewerbliche AnwendbarkeitIndustrial applicability
Mit Hilfe des erfindungsgemäßen Prepregs können auf einfacheWith the help of the prepreg according to the invention, simple
Weise heiß ausgehärtete Verbundwerkstoffe mit hoher Dauertem¬ peratur- und Chemikalienbeständigkeit sowie Composite-Teile für den Flugzeug- und Maschinenbau sowie für die Sportartikelher¬ stellung gefertigt werden. Hot-hardened composite materials with high permanent temperature and chemical resistance as well as composite parts for aircraft and mechanical engineering as well as for the manufacture of sporting goods are manufactured.

Claims

Patentansprüche Claims
1. Prepreg auf Basis von unidirektional angeordneten, mit einem duromeren Kunststoffgemisch imprägnierten Verstärkungsfasern wie Glasfasern, Kohlenstoffasern, Aramidfasern und dgl., da¬ durch gekennzeichnet, daß das Kunststoffgemisch ein Epoxyd¬ harz, ein Phenolharz, gegebenenfalls einen Beschleuniger sowie gegebenenfalls Zusatzstoffe wie Füllstoffe, Flamm¬ schutzmittel, Elastifizierungsmittel , Netzmittel und dgl. enthält.1. Prepreg based on unidirectionally arranged reinforcing fibers impregnated with a thermosetting plastic mixture such as glass fibers, carbon fibers, aramid fibers and the like, characterized in that the plastic mixture is an epoxy resin, a phenolic resin, optionally an accelerator and optionally additives such as fillers, Contains flame retardants, elasticizers, wetting agents and the like.
2. Prepreg nach Anspruch 1, dadurch gekennzeichnet, daß im Prepreg die Anteile an Epoxydharz-Phenolharz-Gemisch 70 - 20 Gew.%, an Verstärkungsfasern 30 - 80 Gew.% sowie an Zusatzstoffen 0 - 30 Gew.% betragen.2. Prepreg according to claim 1, characterized in that the proportions of epoxy resin-phenolic resin mixture in the prepreg are 70-20% by weight, in reinforcing fibers 30-80% by weight and in additives 0-30% by weight.
3. Prepreg nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, daß es im Harzgemisch als Phenolharz ein Phenol-Formaldehyd- Kondensationsprodukt im Molverhältnis Phenol zu Formaldehyd von 1:0,5 bis 1,09, vorteilhaft aber von 1:0,6 bis 1:0,85, aufweist.3. Prepreg according to claims 1 or 2, characterized in that it is a phenol-formaldehyde condensation product in the molar ratio of phenol to formaldehyde in the resin mixture as a phenolic resin from 1: 0.5 to 1.09, but advantageously from 1: 0.6 to 1: 0.85.
4. Verfahren zur Herstellung eines Prepregs nach einem der Ansprüche 1 - 3, dadurch gekennzeichnet, daß gegebenenfalls dem Epoxydharz-Phenolharz-Gemisch vor dem Imprägniervorgang ein Lösungsmittel im Bereich von 0 - 20 Gew.% zugesetzt wird und daß dieses Gemisch mittels einer Rakel auf eine kontinu¬ ierlich bewegte Trennfolie in Form einer Schicht aufgebracht wird, in welche dann die zulaufenden, endlosen Verstärkungs¬ fasern hineingedrückt und dadurch imprägniert werden.4. A method for producing a prepreg according to any one of claims 1-3, characterized in that a solvent in the range of 0-20% by weight is optionally added to the epoxy-phenolic resin mixture before the impregnation process and that this mixture is applied by means of a doctor blade a continuously moving separating film is applied in the form of a layer, into which the tapering, endless reinforcing fibers are then pressed and thereby impregnated.
5. Verfahren zur Herstellung eines Prepregs nach Anspruch 4, dadurch gekennzeichnet, daß ein lösungsmittelfreies Epoxyd- harz-Phenolharz-Ge isch eingesetzt wird und daß dieses lö¬ sungsmittelfreie Epoxydharz-Phenolharz-Gemisch vor dem Im¬ prägniervorgang zwecks Verringerung der Viskosität auf er¬ höhte Temperatur gebracht wird.5. A method for producing a prepreg according to claim 4, characterized in that a solvent-free epoxy Resin-phenolic resin mixture is used and that this solvent-free epoxy resin-phenolic resin mixture is brought to an elevated temperature before the impregnation process in order to reduce the viscosity.
6. Verfahren zur Herstellung eines Prepregs nach den Ansprüchen 4 oder 5, dadurch gekennzeichnet, daß man das Gelege aus imprägnierten Verstärkungsfasern zusätzlich durch eine Heiz¬ einrichtung führt, in der das Epoxyd-Phenolharz-Gemisch in den B-Zustand übergeführt und das gegebenenfalls vorhandene Lösungsmittel abgedampft wird, wonach das Prepreg gegebenen¬ falls einen Kalander durchläuft.6. A process for the production of a prepreg according to claims 4 or 5, characterized in that the scrim made of impregnated reinforcing fibers is additionally passed through a heating device in which the epoxy-phenolic resin mixture is converted into the B state and any that is present Solvent is evaporated, after which the prepreg optionally passes through a calender.
7. Verfahren nach einem der Ansprüche 4 - 6, dadurch gekenn¬ zeichnet, daß als Phenolharz ein Phenolformaldehyd-Konden¬ sationsprodukt mit einem Molverhältnis Phenol zu Formaldehyd von 1:0,5 bis 1:0,9, vorteilhaft von 1:0,6 bis 1:0,85, einge¬ setzt wird.7. The method according to any one of claims 4-6, characterized gekenn¬ characterized in that the phenolic resin is a phenol formaldehyde condensation product with a molar ratio of phenol to formaldehyde from 1: 0.5 to 1: 0.9, advantageously from 1: 0, 6 to 1: 0.85, is used.
8. Verwendung eines Prepregs nach einem der Ansprüche 1 bis 3 als Ausgangsmaterial zur Herstellung von heiß ausgehärteten Verbundwerkstoffen. 8. Use of a prepreg according to one of claims 1 to 3 as a starting material for the production of hot-cured composite materials.
EP91910945A 1990-06-13 1991-06-13 Prepreg, process for manufacturing it, and use of the prepreg Withdrawn EP0486651A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT1284/90 1990-06-13
AT0128490A AT396240B (en) 1990-06-13 1990-06-13 PREPREG PROCESS FOR ITS PRODUCTION AND USE

Publications (1)

Publication Number Publication Date
EP0486651A1 true EP0486651A1 (en) 1992-05-27

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EP (1) EP0486651A1 (en)
JP (1) JPH05501283A (en)
KR (1) KR920702385A (en)
AT (1) AT396240B (en)
WO (1) WO1991019755A1 (en)

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Publication number Priority date Publication date Assignee Title
ATE131556T1 (en) * 1991-11-08 1995-12-15 Ruetgerswerke Ag BINDER SYSTEMS BASED ON EPOXY RESIN-PHENOLIC RESIN COMBINATIONS
AT404240B (en) * 1996-04-25 1998-09-25 Isovolta LAMINATE CONSISTING OF A BASE AND COVER LAYER AND METHOD FOR PRODUCING A DECORATIVE SURFACE ON THIS LAMINATE
GB2352249B (en) * 1999-07-21 2004-04-14 Rover Group A method of manufacture of a glass fibre pre-preg for use in a polymer glazing application
US8153244B2 (en) * 2008-10-15 2012-04-10 3M Innovative Properties Company Reinforcement patches with unidirectionally-aligned fibers
WO2015149063A1 (en) 2014-03-28 2015-10-01 E. I. Du Pont De Nemours And Company Fiber-reinforced composite laminate and articles made therefrom

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US3784659A (en) * 1972-01-13 1974-01-08 R Lupert Method of producing continuous plastic shapes
US3898113A (en) * 1972-09-07 1975-08-05 Gen Tire & Rubber Co Method of making a continuous strand sheet molding compound
JPS6037810B2 (en) * 1978-12-08 1985-08-28 東邦レーヨン株式会社 Strand prepreg composition
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Also Published As

Publication number Publication date
JPH05501283A (en) 1993-03-11
KR920702385A (en) 1992-09-03
ATA128490A (en) 1992-11-15
AT396240B (en) 1993-07-26
WO1991019755A1 (en) 1991-12-26

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